Home

Weiteres zum Thema:

Chemische Kinetik

Physikalische Chemie

Thermodynamik

Buecher zum Thema

Themenbezogene Artikel

- Chemie, allgemein

- Physikalische Chemie

Weitere Themenbereiche

English Version

Verwandte Themen:

Aktuelles

Chemie Nachrichten

Stellenmarkt Chemie

Chemie Konferenzen

Chemie A bis Z

Index Chemie

Chemikalien

Internetchemie Lexikon

Produkte und Firmen

About Internetchemie

Internetchemie

Impressum

Service

Chemische Kinetik, Reaktionskinetik - Aktuelle Forschungsartikel

 
Aktuelle Fachartikel Kinetik chemischer Reaktionen (Reaktionskinetik), sortiert nach Erscheinungsdatum.

Die Urheberrechte und Veroeffentlichungsrechte der in der nachfolgenden Liste aufgefuehrten Fachartikel liegen bei den jeweiligen Verlagen, die am Ende des jeweiligen Artikels als Quelle genannt werden. Diese sind auch fuer die Inhalte verantwortlich.

Hinweise zur Veroeffentlichung Ihrer Pressmitteilung unter Internetchemie.Info entnehmen Sie bitte der entsprechenden Info-Seite.

Diese Seite koennen Sie mit folgender Tastenkombination nach Stichwoertern durchsuchen: <STRG> und <F>.

Auf dieser Seite beruecksichtige naturwissenschaftliche Journale:

Aktuelle wissenschaftliche Fachartikel der genannten Journale:

High-temperature rate constants for H/D + C2H6 and C3H8 Abstract The reactions of H/D with C2H6 and C3H8 have been studied with both shock-tube experiments and ab initio transition-state theory calculations. Rate constants for the reactions of D with C2H6 and C3H8 have been measured in reflected shock wave experiments over the temperature range, 1128–1299 K, at pressures 0.3–1 atm. D atoms are detected using atomic resonance absorption spectrometry. The measured D-atom profiles are sensitive to only the thermal dissociation of the D-atom source molecule, C2D5I, and to the title reactions. Since the dissociation has been previously studied in this laboratory, modeling the temporal evolution of the D-atom profiles allows determinations of the rate constants for the title reactions. Over the T range, 1128–1228 K, rate constants from the present experiments for D + C2H6 can be represented by the Arrhenius expression The experimental total rate constants for D + C3H8 over the T range, 1128–1299 K, can be represented by the Arrhenius expression The title reactions have been studied at the CCSD(T)/aug-cc-pv∞z level of theory using saddle point geometries at B3LYP/6-311++G(d,p) and MP2/6-311++G(d,p) levels of theory. The reaction endothermicities are in good agreement with current Active Thermochemical Tables values. Theoretical rate constants were estimated using transition state theory. The theoretical rate constants are in good agreement with the present experiments and lower temperature literature data. Over the T range of the present experiments, the theoretically predicted isotope effects are close to unity. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 194–205, 2012 Quelle: International Journal of Chemical Kinetics | 1 Mar 2012 | 6:00 am CET

Detailed chemical kinetic modeling of JP-10 (exo-tetrahydrodicyclopentadiene) high-temperature oxidation: Exploring the role of biradical species in initial decomposition steps Abstract The initial pathways of JP-10 (exo-tetrahydrodicyclopentadiene) decomposition are expected to have a significant effect on combustion and pyrolysis behavior of the fuel, affecting, for example, product distribution and ignition delay. Modeling of JP-10 decomposition should capture these initial decomposition processes as accurately as possible. Two classes of computational approaches have been applied to study intramolecular disproportionation—an important class of reactions in the initial stages of JP-10 decomposition: (1) the second-order, multiconfigurational, quasidegenerate perturbation theory employing the complete active space self-consistent field (CASSCF) reference; and (2) the size-extensive, left-eigenstate, completely renormalized (CR) coupled-cluster (CC) method with singles, doubles, and noniterative triples, termed CR-CC(2,3), capable of describing reaction pathways involving biradicals. Applying higher levels of theory to points along the CASSCF reaction paths, the barriers to intramolecular disproportionation are much smaller and some barriers appear to vanish. The conventional ring-opening + disproportionation pathway is compared with an alternative concerted reaction pathway. Overall, this investigation has yielded insights into alkyl disproportionation and ring-opening reactions that may be of more general use in chemical kinetic modeling. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 179–193, 2012 Quelle: International Journal of Chemical Kinetics | 1 Mar 2012 | 6:00 am CET

Gas-phase oxidation of cresol isomers initiated by OH or NO3 radicals in the presence of NO2 Abstract We have studied the reaction mechanism for both the NO3- and OH-initiated atmospheric oxidation of three cresol isomers, p-cresol, m-cresol, and o-cresol, in the presence of high NO2 concentration. We have focused on the reaction mechanism leading to ring-retaining products. Geometries of the reactants, intermediates, transition states, and products have been optimized at DFT-BB1K level of theory with the 6-311+G(d,p) basis set. The single point energy calculations have been carried out at the CCSD(T) level of theory with the cc-pVDZ basis set. Several energetically favorable reaction pathways were revealed for the first time. In the NO3-initiated reaction, the NO3 radical is added to the carbon atom with the OH group, then the NO2 radical is added to one of the neighboring carbon atoms, and finally HNO3 is eliminated, leading to a methylnitrophenol isomer. In the OH-initiated reaction, the OH radical is added to the carbon atom adjacent to the carbon atom with the OH group; second, the NO2 radical is added to the carbon atom with the original OH group, and, finally, HNO2 is eliminated, leading to a dihydroxymethylbenzene isomer. The calculated results were compared with available experimental observations. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 165–178, 2012 Quelle: International Journal of Chemical Kinetics | 1 Mar 2012 | 6:00 am CET

Computational study on the recombination reaction between benzyl and propargyl radicals Abstract The kinetics and mechanisms of the recombination reaction between benzyl and propargyl radicals have been computationally investigated by using the B3LYP, CBS-QB3, and CASPT2 quantum chemical methods, and the steady-state unimolecular master equation analysis based on the Rice–Ramsperger–Kassel–Marcus theory. Six distinct recombination channels arising from the radicals' nonequivalent resonance structures (three for benzyl and two for propargyl) were investigated at the CASPT2/cc-pVTZ//B3LYP/6-311G(d,p) level, and the respective rate constants were calculated with the variational transition state theory. It was found that the reaction dominantly proceeds by the addition of the propargyl radical to the alpha(CH2) site of the benzyl radical and the additions to the ortho- and the para-sites are unfavorable due to the loss of the aromaticity. The isomerization reaction pathways of the initially formed adducts to methylenecyclopenta-fused compounds through diradical intermediates were identified. Methylene–indanyl radicals were also identified as products, which are produced by direct H-atom elimination reactions from the diradical and methylenated indanes. The results of the master equation analyses indicated that the 1-methylene-2-indanyl radical is dominantly produced at high temperature (>1500 K), but the overall rate constant is significantly smaller than the high-pressure limit within the pressure range studied (0.001–100 atm). The reactions of the triplet biradicals via the intersystem crossing were also suggested to be important and are discussed qualitatively. Investigations on the subsequent reactions of 1-methylene-2-indanyl radicals revealed that the radicals rapidly decompose to 1-methyleneindene or naphthalene + H. The temperature- and pressure-dependent rate expressions are proposed for kinetic modeling. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 206–218, 2012 Quelle: International Journal of Chemical Kinetics | 1 Mar 2012 | 6:00 am CET

Rate constants for hydrogen abstraction by HȮ2 from n-butanol Abstract Rate constants of hydrogen-atom abstraction from n-butanol by the HȮ2 radical have been calculated. Conventional transition state theory employing rigid-rotor harmonic-oscillator approximations for all but the torsional degrees of freedom is used with tight transition states. The Pitzer–Gwinn-like approximation using Fourier fits to internal rotations was applied to determine the one-dimensional hindered potentials. Asymmetric Eckart barriers were used to model tunneling in one-dimensional through saddle points. Activation entropies for all of the reaction channels have been determined. Hydrogen bonds formed in the transition states lead to ring structures, which lower the energy barrier and thus an increase in the rate constant for abstraction. Conversely, entropy is lost when the ring structure is formed and this decreases the frequency factor for abstraction; therefore, both of these effect influence the rate constants in opposite ways. Abstraction of an α hydrogen atom is dominant throughout the whole temperature range, and the branching ratio decreases from 96.1% at 500 K to 46.6% at 2000 K. As the carbon chain lengthens, the influence from the OH group lessens and hence δ hydrogens behave in a similar fashion to primary H-atoms in n-butane. The estimated uncertainty for the individual rate constants is a factor of 2.5. Computed total, kt, and individual rate constants, based on the CCSD(T)/cc-pVTZ//MP2/6-311G(d,p) potential energy surface, in the temperature range of 500–2000 K for n-butanol + HȮ2 are reported as follows (cm3 mol−1 s−1): © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 155–164, 2012 Quelle: International Journal of Chemical Kinetics | 1 Mar 2012 | 6:00 am CET

Effects of nonionic micellar aggregates on the electron transfer reaction between l-glutamic acid and gold(III) complexes Abstract The effect of nonionic micelles of Triton X-100 on the oxidative decarboxylation of l-glutamic acid by chloroaurate(III) complexes has been investigated in acetate buffer medium. The reaction is first order with respect to Au(III), but a complex order with respect to glutamate. H+ ion has both accelerating and retarding effects in the pH range 3.72–4.80, whereas a Cl− ion has an inhibiting effect in the range 0.02–0.56 mol dm−3. Under the experimental conditions, AuCl−4 and AuCl3(OH)− are the predominant and effective oxidizing species, whereas the zwitterion (H2A) and mononegative anion (HA−) are the predominant reducing species of the amino acid. The reaction involves a one-step two-electron transfer process and passes through the intermediate formation of iminic cation. In the presence of surfactant, the reaction passes through a maximum and it appears to follow Berezin's model, where both the oxidant and the substrate are partitioned between the aqueous and the micellar phase and then react. The binding constants between the reactants and the surfactant have been evaluated at different temperatures. Compensation between substrate–water interaction and substrate–micelle interaction plays an important role in such redox reactions in the presence of a surfactant. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–12, 2012 Quelle: International Journal of Chemical Kinetics | 2 Feb 2012 | 11:06 pm CET

Multispecies laser measurements of n-butanol pyrolysis behind reflected shock waves Abstract Time histories of OH, H2O, and 306.8 nm absorbance were measured behind reflected shock waves in mixtures of 1% n-butanol in Ar. Reflected shock conditions covered temperatures (T5) from 1274 to 1439 K and pressures (P5) near 1.5 atm. OH was measured using laser absorption of the R1(5) line of the A–X (0, 0) transition at 306.7 nm. Each experiment was repeated with the laser tuned off the narrow OH absorption feature to subtract broadband interference from CH2O and CH3CHO. Knowledge of the absorption coefficients of CH2O and CH3CHO at this nonresonant wavelength was then used to compare ultraviolet (UV) absorbance to model predictions. H2O was measured using DFB diode laser absorption of a well-characterized absorption feature near 2.5 μm. These measured time histories, which should prove highly useful in reaction mechanism development, were then compared to simulations based on the comprehensive n-butanol oxidation mechanism by Curran et al. (Combust Flame, 2010, 157, 363–373). Using that mechanism, it was determined that the n-butanol decomposition pathways through C4H8OH(γ) should be strongly favored over C4H8OH(α) and that the C4H8OH(δ) pathway should also be increased by 25%. The specific rate adjustments inferred in this work were found to be highly mechanism dependent, though the overall reaction path analyses were very similar for all the mechanisms studied. In addition to Curran et al. (2010), two other mechanisms were examined, revealing the importance of four specific sets of reactions in n-butanol pyrolysis. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–11, 2012 Quelle: International Journal of Chemical Kinetics | 30 Jan 2012 | 10:26 pm CET

The enthalpy and entropy of activation for ethyl acetate saponification Abstract The saponification of ethyl acetate was measured by conductimetry at different temperatures within a batch reactor. A new mathematical model for obtaining concentration profiles from conductivity was presented and used for reaction-kinetics' determination. The Arrhenius parameters (A, Ea) showed good agreement with the previously published values. Basic transition-state theory was used for obtaining the Gibbs energy (ΔG‡), the enthalpy (ΔH‡), and the entropy (ΔS‡) of activation. The low enthalpy of activation and negative entropy of activation were consistent with a reaction pathway when forming a transition-state complex. The suggested mechanism involves OH−, acting as a general base for removing proton from one of the hydroxide hydrating water, placed directly between it and the ester. The nucleophile from the water then attacks at the electrophilic C of the ester, breaking the π bond, and creating a tetrahedral intermediate. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–7, 2012 Quelle: International Journal of Chemical Kinetics | 24 Jan 2012 | 11:05 pm CET

High-temperature dissociation of ethyl radicals and ethyl iodide Abstract The decomposition of ethyl iodide and subsequent dissociation of ethyl radicals have been investigated behind incident shock waves in a diaphragmless shock tube by laser-schlieren (LS) densitometry (1150–1870 K, 55 ± 2 Torr and 123 ± 3 Torr). The LS density-gradient profiles were simulated assuming that the initial dissociation of C2H5I proceeded by 87% C–I fission and 13% HI elimination. Excellent agreement was found between the simulations and experimental profiles. Rate coefficients for the C–I scission reaction were obtained and show strong falloff. Gorin model RRKM (Rice, Ramsperger, Kassel, and Marcus) calculations are in excellent agreement with the experimental data with E0 = 55.0 kcal/mol, which is in very good agreement with recent thermochemical measurements and evaluations. However, E0 is approximately 2.7 kcal/mol higher than previous estimates. First-order rate coefficients for dissociation of C2H5I were determined to be k55Torr = 8.65 × 1068T−16.65 exp(−37,890/T) s−1, k123Torr = 3.01 × 1069T−16.68 exp(−38,430/T) s−1, k∞ = 2.52 × 1019T−1.01 exp(−28,775/T) s−1. Rates of dissociation for ethyl radicals were also obtained, and these are in very good agreement with theoretical predictions (Miller J. A. and Klippenstein S. J. Phys Chem Chem Phys 2004, 6, 1192–1202). The simulations show that at low temperatures ethyl radicals are consumed through recombination reactions as well as dissociation, whereas at high temperatures, dissociation dominates. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–11, 2012 Quelle: International Journal of Chemical Kinetics | 24 Jan 2012 | 11:05 pm CET

Substituent effects on enol nitrosation of 1,3-diketones Abstract The keto–enol tautomerism of 3-chloro-pentane-2,4-dione (ClPD) was studied in aqueous micellar solutions of cationic, anionic, and nonionic surfactants. The enol of ClPD tautomerizes rapidly in water to the equilibrium proportions of the keto form, KE=0.55; whereas the keto–enol conversion of 3-ethyl-pentane-2,4-dione (EPD) is a much slower reaction than the enol nitrosation. Kinetics of enol –nitrosation of both ClPD and EPD in aqueous acid medium using nitrous acid shows first-order dependence upon [ketone] and linear or curve relationships of the observed rate constant, ko, as a function of [nitrite] or [H+]; the observed behavior depends on the molecular structure of diketone and varies with the experimental conditions. The reaction is strongly catalyzed by Cl−, Br−, or SCN−, and the observed rate constant shows a curve dependence on [Br−] or [SCN−], which is more pronounced at high acidity. The results are consistent with a reaction mechanism in which the nitrosation occurs initially on the enol–oxygen and releasing a proton to form a chelate–nitrosyl complex intermediate in steady state. Fine differences on the mechanistic spectrum of enols nitrosation are considered on the basis of the molecular structure of the diketone. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–12, 2012 Quelle: International Journal of Chemical Kinetics | 23 Jan 2012 | 2:18 pm CET

Radical formation during phenol oxidation in aqueous media Abstract Kinetics of oxygen consumption, reaction product formation, and chemiluminescence during polyphenol oxidation by molecular oxygen in alkaline aqueous media with additions of l-ascorbic acid (AscH2) and homocysteine (HCys) has been investigated. In these processes, AscH2 and HCys have been shown to act as typical radical-reaction inhibitors that can be used for determinations of the radical formation rates. The rates of radical formation during oxidation of hydroquinone (p-QH2), chlorohydroquinone (Cl-QH2), 2,5-dichlorohydroquinone (2,5Cl-QH2), catechol (PK), 4-methylcatechol (4CH3-PK), pyrogallol (PG), gallic acid (GK) have been estimated. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–9, 2012 Quelle: International Journal of Chemical Kinetics | 19 Jan 2012 | 6:10 pm CET

Solvent effects on the activation parameters of the reaction between an α-tocopherol analogue and dpph•: The role of H-bonded complexes Abstract The analysis of the activation parameters for the formal H-atom transfer reaction between 2,2,5,7,8-pentamethyl-6-chromanol (ChrOH) and 2,2-diphenyl-1-picrylhydrazyl (dpph•) reveals that these parameters are effective probes of the actual reaction mechanism. Indeed, the A factors measured in various polar and apolar solvents are localized in three distinct domains according to whether the reaction occurs via outer-sphere electron transfer (ET) from the anion ChrO− or hydrogen atom transfer (HAT). For instance, A = 5.9 × 105 M−1 s−1 and Ea = 2.5 kcal mol−1 in cyclohexane where the reaction proceeds by HAT, whereas in methanol, ethanol, and their mixtures with water where there is a substantial ET contribution A > 109 M−1s−1 and Ea > 7 kcal mol−1. Interestingly, in nonhydroxylic polar solvents, A∼ 107 M−1s−1 and the Ea values reflect the H-bond accepting ability of the solvent in agreement with the “standard” kinetic solvent effects on HAT reactions. Addition of small quantities of pyridine accelerates the reaction rates in these solvents. This suggests that the H-bonded complex (ChrOH···Py) is able to react via intermolecular ET with dpph•. It is known, in fact, that pyridine lowers the oxidation potential of phenols by ∼0.5 V and the ΔGET of ChrOH + dpph• consequently decreases by about 10 kcal mol−1. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–8, 2012 Quelle: International Journal of Chemical Kinetics | 17 Jan 2012 | 4:12 pm CET

Mechanistic aspects of ligand substitution on [(H2O)(tap)2RuORu(tap)2(H2O)]2+ ion {tap = 2-(m-tolylazo)pyridine} by some amino acids in aqueous medium at physiological pH Abstract The interaction of the title complex with selected amino acids such as glycine (L1H), l-valine (L2H), and l-leucine (L3H) has been studied spectrophotometrically in aqueous medium as a function of [substrate complex], [ligand], and temperature. The reaction has been monitored at 600 nm, where the spectral difference between the reactant and product is maximum. At pH 7.4, the reaction has been found to proceed via two distinct consecutive steps, i.e., it shows a nonlinear dependence on the concentration of ligands: The first process is [ligand] dependent, but the second step is [ligand] independent. The rate constants for the processes are k1∼10−3 s−1 and k2∼10−4 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 Δ Go 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 characterized with the help of conductance measurement, IR, NMR, and ESI-mass spectroscopic analysis. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–12, 2012 Quelle: International Journal of Chemical Kinetics | 14 Jan 2012 | 12:14 am CET

IR laser absorption diagnostic for C2H4 in shock tube kinetics studies Abstract An IR laser absorption diagnostic has been further developed for accurate and sensitive time-resolved measurements of ethylene in shock tube kinetic experiments. The diagnostic utilizes the P14 line of a tunable CO2 gas laser at 10.532 μm (the (0 0 1) → (1 0 0) vibrational band) and achieves improved signal-to-noise ratio by using IR photovoltaic detectors and accurate identification of the P14 line via an MIR wavemeter. Ethylene absorption cross sections were measured over 643–1959 K and 0.3–18.6 atm behind both incident and reflected shock waves, showing evident exponential decay with temperature. Very weak pressure dependence was observed over the pressure range of 1.2–18.6 atm. By measuring ethylene decomposition time histories at high-temperature conditions (1519–1895 K, 2.0–2.8 atm) behind reflected shocks, the rate coefficient of the dominant elementary reaction C2H4 + M → C2H2 + H2 + M was determined to be k1 = (2.6 ± 0.5) × 1016exp(−34,130/T, K) cm3 mol−1 s−1 with low data scatter. Ethylene concentration time histories were also measured during the oxidation of 0.5% C2H4/O2/Ar mixtures varying in equivalence ratio from 0.25 to 2. Initial reflected shock conditions ranged from 1267 to 1440 K and 2.95 to 3.45 atm. The measured time histories were compared to the modeled predictions of four ethylene oxidation mechanisms, showing excellent agreement with the Ranzi et al. mechanism (updated in 2011). This diagnostic scheme provides a promising tool for the study and validation of detailed hydrocarbon pyrolysis and oxidation mechanisms of fuel surrogates and realistic fuels. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–10, 2012 Quelle: International Journal of Chemical Kinetics | 10 Jan 2012 | 9:01 pm CET

Donor property of cobalt(II) Schiff base complexes toward triphenyltin(IV)- chloride: A kinetic study Abstract In this study, some cobalt(II)tetraaza Schiff base complexes were used as donors in coordinating to triphenyltin(IV)chloride as acceptors; the kinetics and mechanism of the adduct formation were studied spectrophotometrically. Co(II)tetraaza Schiff base complexes used were [Co(amaen)][N,N′-ethylene-bis-(o-amino-α-methylbenzylideneiminato)cobalt(II)] (1), [Co(appn)] [N,N′-1,2-propylene-bis-(o-amino-α-phenylbenzylideneiminato)cobalt(II)] (2), [Co(ampen)] [N,N′-ethylene-bis-(o-amino-α-phenylbenzylideneiminato)cobalt-(II)] (3), [Co(cappn)][N,N′-1,2-proylene-bis-(5-chloro-o-amino-α-phenylbenzylideneiminato)cobalt(II)] (4), and [Co(campen)] [N,N′-ethylene-bis-(5-chloro-o-amino-α-phenylbenzylid-eneiminato)cobalt(II)] (5). The reactivity trend of the complexes in interaction with triphenyltin(IV)chloride was Co(amaen) > Co(appn) > Co(ampen) > Co(cappn) > Co(campen). The linear plots of kobs versus the molar concentration of the triphenyltin(IV)chloride, a high span of the second-order rate constant k2 values, and large negative values of ΔS≠ and low ΔH≠ values suggest an associative (A) mechanism for the acceptor–donor adduct formation. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–6, 2012 Quelle: International Journal of Chemical Kinetics | 6 Jan 2012 | 6:31 pm CET

Kinetic studies of reactions of 4-nitrobenzofuroxan with carbanions derived from benzyltriflones in methanol Abstract This paper reports the rate measurements for the reactions of carbanions derived from benzyltriflones, 2, with 4-nitrobenzofuroxan, 4, in methanol, to give anionic σ-adducts. 1H NMR studies in DMSO-d6 indicate that the products formed by the reaction of 2 and 4 in the presence of triethylamine are consistent with the products formed by the elimination of trifluoromethylsulfinic acid from σ-adducts, initially formed by a carbanion attack at the 5 position of 4. The low value of β, which is the slope of the linear plot of log k5 versus pKa, provides evidence for the high steric requirements of the benzyltriflone anions. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–9, 2012 Quelle: International Journal of Chemical Kinetics | 5 Jan 2012 | 5:32 pm CET

Kinetic modeling and optimization of operating parameters for transvinylation of lauric acid Abstract The transition metal complex catalyzed transvinylation of carboxylic acid with vinyl acetate monomer is of significant interest to industry. The palladium complex catalyzed transvinylation of lauric acid using vinyl acetate monomer is a reversible reaction. In present article, design of experiments (DOE) statistics is used to study effects of various operating parameters on transvinylation of lauric acid. The kinetic parameters forward and backward rate constants and the thermodynamic parameters such as equilibrium constant and energy of activation of the transvinylation of lauric acid were estimated using the Dynochem model. The optimum operating parameters for the transvinylation of lauric acid were then predicted using the Dynochem model and verified by performing the actual experiments to validate the model. It was found that the experimental results match with the predicted one. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–11, 2012 Quelle: International Journal of Chemical Kinetics | 4 Jan 2012 | 10:27 pm CET

Concerted aminolysis of diaryl carbonates: Kinetic sensitivity on the basicity of the nucleophile, nonleaving group, and nucleofuge Abstract The kinetics of the reactions of 4-methylphenyl, phenyl, and 4-chlorophenyl 2,4,6-trinitrophenyl carbonates (1, 2, and 3, respectively) with a series of anilines and secondary alicyclic (SA) amines has been carried out spectrophotometrically in 44 wt% ethanol–water, at 25.0°C, ionic strength 0.2 M. The Brønsted plots (statistically corrected) for the reactions of carbonates 1–3 with anilines and SA amines were linear with slopes (βN) in the range of 0.69–0.78 and 0.45–0.48, respectively, attributed to a concerted mechanism. The negative values found for the sensitivity of log kN to the basicity of the nonleaving (βnlg) and leaving (βlg) groups are discussed. Anilines are more reactive than isobasic SA amines, probably because of the greater steric hindrance offered by the latter. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–8, 2011 Quelle: International Journal of Chemical Kinetics | 4 Jan 2012 | 10:10 pm CET

Comprehensive H2/O2 kinetic model for high-pressure combustion Abstract An updated H2/O2 kinetic model based on that of Li et al. (Int J Chem Kinet 36, 2004, 566–575) is presented and tested against a wide range of combustion targets. The primary motivations of the model revision are to incorporate recent improvements in rate constant treatment and resolve discrepancies between experimental data and predictions using recently published kinetic models in dilute, high-pressure flames. Attempts are made to identify major remaining sources of uncertainties, in both the reaction rate parameters and the assumptions of the kinetic model, affecting predictions of relevant combustion behavior. With regard to model parameters, present uncertainties in the temperature and pressure dependence of rate constants for HO2 formation and consumption reactions are demonstrated to substantially affect predictive capabilities at high-pressure, low-temperature conditions. With regard to model assumptions, calculations are performed to investigate several reactions/processes that have not received much attention previously. Results from ab initio calculations and modeling studies imply that inclusion of H + HO2 = H2O + O in the kinetic model might be warranted, though further studies are necessary to ascertain its role in combustion modeling. In addition, it appears that characterization of nonlinear bath-gas mixture rule behavior for H + O2(+ M) = HO2(+ M) in multicomponent bath gases might be necessary to predict high-pressure flame speeds within ∼15%. The updated model is tested against all of the previous validation targets considered by Li et al. as well as new targets from a number of recent studies. Special attention is devoted to establishing a context for evaluating model performance against experimental data by careful consideration of uncertainties in measurements, initial conditions, and physical model assumptions. For example, ignition delay times in shock tubes are shown to be sensitive to potential impurity effects, which have been suggested to accelerate early radical pool growth in shock tube speciation studies. In addition, speciation predictions in burner-stabilized flames are found to be more sensitive to uncertainties in experimental boundary conditions than to uncertainties in kinetics and transport. Predictions using the present model adequately reproduce previous validation targets and show substantially improved agreement against recent high-pressure flame speed and shock tube speciation measurements. Comparisons of predictions of several other kinetic models with the experimental data for nearly the entire validation set used here are also provided in the Supporting Information. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 1–31, 2011 Quelle: International Journal of Chemical Kinetics | 7 Dec 2011 | 12:23 am CET

Time-of-flight mass spectrometry for time-resolved measurements: Some developments and applications Abstract In this paper, the time resolution for kinetic studies of reactions with mass spectrometric detection is characterized in detail, and it is shown how this allows faster kinetic processes to be determined. The time-resolved technique used pulsed laser photolysis to initiate reaction and a time-of-flight mass spectrometer (TOFMS) to monitor progress, where the reactant gas was sampled by a sampling orifice and photoionized using pulsed, laser vacuum ultraviolet light before being analyzed by the TOFMS. Characterization of this setup has been carried out to identify the parameters that affect the time for “sampling,” which limits the fastest reactions that can be measured. A simple mathematical equation has been developed to correct for “sampling” delays (ksampling∼25, 000 s−1), which extends the range of rate coefficients to be measured in a kinetic mass spectrometry reactor to k′ < 7000 s−1. This method could be applied to any other kinetic mass spectrometry system where ksampling can be measured; an important advantage since it allows the study of reactions over a wider range of conditions (e.g., larger concentrations of reagents/products can be used to minimize the contribution from wall losses). The system can produce reliable kinetic data whether monitoring reactant decay or product growth even when the reaction and sampling processes are occurring on a similar timescale (k′ < 7000 s−1). Reproducible and reliable kinetic data have been obtained for the following reactions: SO + NO2 → products (R1), ClSO + NO2 → products (R2), where SO and ClSO were monitored under pseudo-first-order conditions, and HCO + O2 → CO + HO2 (R3), where CO was monitored by a [1+1] resonance enhanced ionization multiphoton ionization (REMPI) scheme with HCO reacting under pseudo–first-order conditions. The limitations and potential developments of this setup are described. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 1–14, 2011 Quelle: International Journal of Chemical Kinetics | 23 Nov 2011 | 4:49 pm CET

Ab initio calculations and RRKM/Master Equation modeling of chloroalkanes → alkenes + HCl reactions for use in comparative rate studies Abstract This paper reports computations that were done in conjunction with an experimental study, reported in an accompanying paper, involving single pulse shock tube measurements of the thermal decomposition of 2-chloropropane, chlorocyclopentane, and chorocyclohexane. The overall aim of the combined work is to provide a well-defined, self-consistent, and reliable set of rate constants for those species over an extended temperature range for use as reference reactions in comparative rate studies. To provide additional validation of the results for the compounds of direct interest, the dehydrochlorination reactions of the related compounds chloroethane, 1-chloropropane, and 2-chlorobutane are also considered. The present work reviews and summarizes the literature information regarding the molecular properties, thermochemistry, and chemical kinetic data for the above six alkyl chlorides. Quantum chemical methods are used to compute the structure and energies of reactants, products, and transition states and the fundamental nature of these types of reaction (four-centered “semi-ion pair” transition states) is discussed. The experimental and theoretical results are compared in detail, and uncertainties are assessed. The computations are used, in conjunction with experimentally determined rate constants, to develop Rice–Ramsperger–Kassel–Marcus (RRKM)/Master Equation models and thereby allow extrapolation of the experimental data over an extended range of temperatures. © 2011 Wiley Periodicals, Inc.† Int J Chem Kinet 1–17, 2011 Quelle: International Journal of Chemical Kinetics | 23 Nov 2011 | 4:14 pm CET

Standard reactions for comparative rate studies: Experiments on the dehydrochlorination reactions of 2-chloropropane, chlorocyclopentane, and chlorocyclohexane Abstract Single pulse shock tube studies of the thermal dehydrochlorination reactions (chlorocyclopentane → cyclopentene + HCl) and (chlorocyclohexane → cyclohexene + HCl) at temperatures of 843–1021 K and pressures of 1.4–2.4 bar have been carried out using the comparative rate technique. Rate constants have been measured relative to (2-chloropropane → propene + HCl) and the decyclization reactions of cyclohexene, 4-methylcyclohexene, and 4-vinylcyclohexene. Absolute rate constants have been derived using k(cyclohexene → ethene + butadiene) = 1.4 × 1015 exp(−33,500/T) s−1. These data provide a self-consistent temperature scale of use in the comparison of chemical systems studied with different temperature standards. A combined analysis of the present results with the literature data from lower temperature static studies leads to k(2-chloropropane) = 10(13.98±0.08) exp(−26, 225 ± 130) K/T) s−1; 590–1020 K; 1–3 bar k(chlorocylopentane) = 10(13.65 ± 0.10) exp(−24,570 ± 160) K/T) s−1; 590–1020 K; 1–3 bar k(chlorocylohexane) = 10(14.33 ± 0.10) exp(−25,950 ± 180) K/T) s−1; 590–1020 K; 1–3 bar Including systematic uncertainties, expanded standard uncertainties are estimated to be about 15% near 600 K rising to about 25% at 1000 K. At 2 bar and 1000 K, the reactions are only slightly under their high-pressure limits, but falloff effects rapidly become significant at higher temperatures. On the basis of computational studies and Rice–Ramsperger–Kassel–Marcus (RRKM)/Master Equation modeling of these and reference dehydrochlorination reactions, reported in more detail in an accompanying article, the following high-pressure limits have been derived: k∞ (2-chloropropane) = 5.74 × 109T1.37 exp(−25,680/T) s−1; 600–1600 K k∞ (chlorocylopentane) = 7.65 × 107T1.75 exp(−23,320/T) s−1; 600–1600 K k∞ (chlorocylohexane) = 8.25 × 109T1.34 exp(−25,010/T) s−1; 600–1600 K © 2011 Wiley Periodicals, Inc.† Int J Chem Kinet 1–18, 2011 Quelle: International Journal of Chemical Kinetics | 23 Nov 2011 | 4:14 pm CET

Synthesis of propylene glycol methyl ether over amine modified porous silica Abstract  Amine functionalized silica catalysts (3-aminopropyltrimethoxysilane (APTMS)) NH2/SiO2, (Diazabicycloundecene/SiO2) DBU/SiO2 and (1,5,7-triazabicyclo[4,4,0]dec-5-ene/SiO2) TBD/SiO2, which were characterized by 29Si NMR, element analysis and indicator dye adsorption, were prepared by ultrasonic technique under mild conditions. Such hybrid solid bases showed high catalytic activity and good reusability towards for the synthesis of propylene glycol methyl ether. Content Type Journal Article Pages 349-353 DOI 10.1007/s11144-009-0086-1 Authors Xuehong Zhang, Shijiazhuang University Chemistry Department 050031 Shijiazhuang China Wenguang Cui, Shijiazhuang University Chemistry Department 050031 Shijiazhuang China Weirong Han, Shijiazhuang University Chemistry Department 050031 Shijiazhuang China Yunxiao Zhang, Shijiazhuang University Chemistry Department 050031 Shijiazhuang China Shubin Liu, Shijiazhuang University Chemistry Department 050031 Shijiazhuang China Wei Mu, Shijiazhuang University Chemistry Department 050031 Shijiazhuang China Yongfang Chang, Shijiazhuang University Chemistry Department 050031 Shijiazhuang China Ruisheng Hu, Shijiazhuang University Chemistry Department 050031 Shijiazhuang China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 6 Nov 2009 | 8:34 pm CET

Hydrogen storage and delivery: immobilization of a highly active homogeneous catalyst for the decomposition of formic acid to hydrogen and carbon dioxide Abstract  The homogeneous catalytic system, based on water-soluble ruthenium(II)–TPPTS catalyst (TPPTS = meta-trisulfonated triphenylphosphine), selectively decomposes HCOOH into H2 and CO2 in aqueous solution. Although this reaction results in only two gas products, heterogeneous catalysts could be advantageous for recycling, especially for dilute formic acid solutions, or for mobile, portable applications. Several approaches have been used to immobilize/solidify the homogeneous ruthenium–TPPTS catalyst based on ion exchange, coordination and physical absorption. The activity of the various heterogeneous catalysts for the decomposition of formic acid has been determined. These heterogenized catalysts offer the advantage of easy catalyst separation/recycling in dilute formic acid, or for mobile, portable applications. Content Type Journal Article Pages 205-213 DOI 10.1007/s11144-009-0096-z Authors Weijia Gan, École Polytechnique Fédérale de Lausanne (EPFL) Institut des Sciences et Ingénierie Chimiques 1015 Lausanne Switzerland Paul J. Dyson, École Polytechnique Fédérale de Lausanne (EPFL) Institut des Sciences et Ingénierie Chimiques 1015 Lausanne Switzerland Gábor Laurenczy, École Polytechnique Fédérale de Lausanne (EPFL) Institut des Sciences et Ingénierie Chimiques 1015 Lausanne Switzerland Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 6 Nov 2009 | 8:34 pm CET

Inactivity of iridium–triphenylphosphine complexes for catalytic imine hydrogenation: formation of neutral, dihydrido-ortho-metallated species Abstract  Reactions of cis,trans,cis-[Ir(H)2(PPh3)2(MeOH)2]PF6 in MeOH with the imines Ph(R′)C=NR under 1 atm H2 precipitate the neutral, Ir(III)-dihydrido complexes [Ir(H)2{RN=C(R′)(o-C 6H4)}(PPh3)2], where R = alkyl or benzyl, and R′ = Ph, H, or Me; the dihydrides are well characterized through elemental analysis, NMR and IR data and, in one case, with the imine Ph2C=NCH2Ph, an X-ray structure. These products are formed via intermediate ortho-metallated species, exemplified by [Ir(H){PhCH2N=CPh(o-C 6H4)}(PPh3)2(MeOH)]PF6 in the case of the Ph2C=NCH2Ph reaction; the intermediate then reacts with H2 (via net heterolytic cleavage: H2 → H− + H+) to give the neutral dihydride and HPF6 as co-product. The ‘unique’ imine PhCH=NPh, under the same conditions, does not form a dihydride and instead is readily catalytically hydrogenated to PhCH2N(H)Ph; remarkably, we have shown previously that this imine is ‘unique’ within the corresponding Rh system in that no catalytic hydrogenation occurs because the amine product ‘poisons’ the Rh centre by coordination through the N-phenyl ring. Content Type Journal Article Pages 193-204 DOI 10.1007/s11144-009-0095-0 Authors Paolo Marcazzan, University of British Columbia Department of Chemistry Vancouver BC V6T 1Z1 Canada Brian R. James, University of British Columbia Department of Chemistry Vancouver BC V6T 1Z1 Canada Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 6 Nov 2009 | 8:34 pm CET

Photocatalytic efficiency of nanocrystalline zeolite TS-1 for the degradation of methyl orange Abstract  The photocatalytic properties of nanocrystalline TS-1 were confirmed via the degradation of an aqueous solution of the model compound methyl orange (MO). The light intensity and quantum yield were measured by ferrioxalate actinometry and the values are 1.7 × 10−5 einstein l−1 s−1 and 0.71, respectively. The experimental parameters such as catalyst loading, pH and initial concentration of MO were optimized at 1.5 g/L, 10 and 300 μM, in order. The results showed that the dye molecules are completely degraded to CO2, H2O and simple inorganic ions. Content Type Journal Article Pages 265-272 DOI 10.1007/s11144-009-0087-0 Authors Hsiu-Ling Hsu, Lunghwa University of Science and Technology Department of Chemical and Materials Engineering 300, Wan-shou Rd., Sec. 1 Kueishan Taoyuan Taiwan Rosilda Selvin, Lunghwa University of Science and Technology Department of Chemical and Materials Engineering 300, Wan-shou Rd., Sec. 1 Kueishan Taoyuan Taiwan L. Selva Roselin, National Central University Department of Chemical and Materials Engineering Jhong-Li 320 Taiwan Prajitha Kumari, Lunghwa University of Science and Technology Department of Chemical and Materials Engineering 300, Wan-shou Rd., Sec. 1 Kueishan Taoyuan Taiwan Jia-Wei Cao, Lunghwa University of Science and Technology Department of Chemical and Materials Engineering 300, Wan-shou Rd., Sec. 1 Kueishan Taoyuan Taiwan Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 5 Nov 2009 | 7:41 pm CET

Photocatalytic activity of TiO2 prepared by microwave/sol–gel method Abstract  This study addresses the photodegradation efficiency of bisphenol A (4,4′-isopropylidenephenol, BPA) and the generation of hydroxyl radicals using the UV/TiO2 system. Photocatalysts were formed by the microwave/sol–gel method and TiO2 was prepared with anatase and rutile phases with a high surface area. The hydroxyl radicals generated by the preparation of TiO2 by a microwave/sol–gel process, and its photoactivity, exceeded those of TiO2 prepared using a sol–gel process. Content Type Journal Article Pages 241-247 DOI 10.1007/s11144-009-0083-4 Authors Han-Yu Lin, National Yunlin University of Science and Technology Graduate School of Engineering Science and Technology Douliou Yunlin Taiwan Chao-Yin Kuo, National Yunlin University of Science and Technology Department of Safety Health and Environmental Engineering 123 University Rd., Sec. 3 Douliou 640 Yunlin Taiwan Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 5 Nov 2009 | 7:41 pm CET

Photocatalytic action of ZnO thin films prepared by the sol–gel method Abstract  Nanostructured ZnO thin films were deposited on glass by the dip-coating sol–gel method. The films exhibited pronounced activity to destroy malachite green in water both under UV-light illumination and in the dark. Content Type Journal Article Pages 259-263 DOI 10.1007/s11144-009-0081-6 Authors Nina V. Kaneva, University of Sofia Laboratory of Nanoparticle Science and Technology, Department of General and Inorganic Chemistry, Faculty of Chemistry 1164 Sofia Bulgaria Georgi G. Yordanov, University of Sofia Laboratory of Nanoparticle Science and Technology, Department of General and Inorganic Chemistry, Faculty of Chemistry 1164 Sofia Bulgaria Ceco D. Dushkin, University of Sofia Laboratory of Nanoparticle Science and Technology, Department of General and Inorganic Chemistry, Faculty of Chemistry 1164 Sofia Bulgaria Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 5 Nov 2009 | 7:41 pm CET

Effects of the preparation method and calcination temperature on Cu–Cr–Mg–Al catalysts for the dehydrogenation of cyclohexanol Abstract  The activities of the Cu–Cr–Mg–Al catalysts in the dehydrogenation of cyclohexanol to cyclohexanone were correlated with particle sizes and the reducibility of the copper species based on XRD and TPR characterizations. Cu0 was proven to be the active center of the catalysts calcined at low temperatures and some solid solution (MgCu2O3) and spinel (CuAl2O4 or MgAl2O4) were produced when the calcination temperature reached 1,000 °C. The Cu–Cr–Mg–Al catalyst prepared by the co-precipitation method and calcined at 400 °C showed the best activity, with a conversion of 79.7% and a selectivity of 98.6% at 300 °C. Content Type Journal Article Pages 341-348 DOI 10.1007/s11144-009-0082-5 Authors Guoyi Bai, Hebei University College of Chemistry and Environmental Science 071002 Baoding Hebei People’s Republic of China Xinxin Fan, Hebei University College of Chemistry and Environmental Science 071002 Baoding Hebei People’s Republic of China Hailong Wang, Hebei University College of Chemistry and Environmental Science 071002 Baoding Hebei People’s Republic of China Fei He, Tianjin University School of Chemical Engineering and Technology 300072 Tianjin People’s Republic of China Huisen Ning, Hebei University College of Chemistry and Environmental Science 071002 Baoding Hebei People’s Republic of China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 3 Nov 2009 | 12:02 pm CET

Kinetics of the thermal isomerization of cis-methylcyclopropane carboxylic acid Abstract  The gas-phase thermal decomposition of cis-2-methylcyclopropane carboxylic acid was investigated in the temperature range 692–753 K and pressure between 10 and 70 Torr. Arrhenius parameters were determined for homogeneous, unimolecular formation of the isomeric products and for the overall loss-rate of the reactant. The determined values are in accordance with the Arrhenius parameters that were reported previously for the thermal unimolecular reactions of cyclopropane and other substituted cyclopropanes. The formation of isomeric products and the observed Arrhenius parameters are consistent with a biradical mechanism. The effect of surface on the reaction was studied at 732 K using the packed reaction vessel. It was observed that the rate of production of all isomeric products and the total loss of cis-2-methylcyclopropane carboxylic acid were not affected by increasing surface to volume ratio. Content Type Journal Article Pages 375-381 DOI 10.1007/s11144-009-0091-4 Authors Jan Nisar, University of Peshawar Gas-Phase Kinetics Research Laboratory, National Center of Excellence in Physical Chemistry Peshawar 25120 Pakistan Mukhtiar Ali, University of Peshawar Gas-Phase Kinetics Research Laboratory, National Center of Excellence in Physical Chemistry Peshawar 25120 Pakistan Iftikhar Ahmad Awan, University of Peshawar Gas-Phase Kinetics Research Laboratory, National Center of Excellence in Physical Chemistry Peshawar 25120 Pakistan Amir Badshah, Quaid-i-Azam University Department of Chemistry Islamabad Pakistan Sadullah Mir, Quaid-i-Azam University Department of Chemistry Islamabad Pakistan Rafaqat Ali Khan, Quaid-i-Azam University Department of Chemistry Islamabad Pakistan Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 3 Nov 2009 | 12:02 pm CET

Microwave assisted heterogeneous catalysis: effects of varying oxygen concentrations on the oxidative coupling of methane Abstract  The oxidative coupling of methane was investigated over alumina supported La2O3/CeO2 catalysts under microwave dielectric heating conditions at different oxygen concentrations. It was observed that, at a given temperature using microwave heating, selectivities for both ethane and ethylene were notably higher when oxygen was absent than that in oxygen/methane mixtures. The differences were attributed to the localised heating of microwave radiation resulting in temperature inhomogeneity in the catalyst bed. A simplified model was used to estimate the temperature inhomogeneity; the temperature at the centre of the catalyst bed was 85 °C greater than that at the periphery when the catalyst was heated by microwaves in a gas mixture with an oxygen concentration of 12.5% (v/v), and the temperature difference was estimated to be 168 °C in the absence of oxygen. Content Type Journal Article Pages 287-302 DOI 10.1007/s11144-009-0089-y Authors Binghua Ni, Xi’an Shiyou University College of Chemistry and Chemical Engineering Xi’an 710065 China Colleen Lee, Imperial College of Science, Technology and Medicine Department of Chemistry South Kensington London SW7 2AY UK Run-Cang Sun, Beijing Forestry University College of Material Science and Engineering Beijing 100083 China Xunli Zhang, Imperial College of Science, Technology and Medicine Department of Chemistry South Kensington London SW7 2AY UK Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 3 Nov 2009 | 12:02 pm CET

Preparation of 3,6-dibenzoylacenapthene in the presence of Lewis acidic ionic liquids Abstract  The reactivity of Lewis acidic ionic liquids for the acylation of acenaphthene to 3,6-dibenzoylacenaphthene was investigated. Ionic liquids of different alkyl chain length and metal chloride were synthesized and tested for the reaction to discuss the effects of Lewis acidity of the ionic liquid on the alkylation. Pure 3,6-dibenzoylacenaphthene was obtained and the structure of 3,6-dibenzoylacenaphthene was identified by GC/MS, FT-IR and 1H NMR spectra. [Emim]C1/A1C13 ionic liquid was found to be the most active catalyst in the acylation. The yield of 3,6-dibenzoylacenaphthene was up to 89.6% and the selectivity towards 3,6-dibenzoylacenaphthene was up to 92.2%. The experiment shows that [Emim]Cl/AlCl3 can be used as both catalyst and solvent, it is reusable and environmentally friendly for the preparation of 3,6-dibenzoylacenaphthene. Content Type Journal Article Pages 355-363 DOI 10.1007/s11144-009-0088-z Authors Min Chen, Jiangsu University School of Chemistry and Chemical Engineering 301 Xuefu Road Zhenjiang 212013 Jiangsu People’s Republic of China Lijing Huang, Jiangsu University School of Chemistry and Chemical Engineering 301 Xuefu Road Zhenjiang 212013 Jiangsu People’s Republic of China Ying Luo, Jiangsu University School of Chemistry and Chemical Engineering 301 Xuefu Road Zhenjiang 212013 Jiangsu People’s Republic of China Minqiang He, Jiangsu University School of Chemistry and Chemical Engineering 301 Xuefu Road Zhenjiang 212013 Jiangsu People’s Republic of China Jimin Xie, Jiangsu University School of Chemistry and Chemical Engineering 301 Xuefu Road Zhenjiang 212013 Jiangsu People’s Republic of China Xinhua Yuan, Jiangsu University School of Material Science and Engineering 301 Xuefu Road Zhenjiang 212013 Jiangsu People’s Republic of China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 3 Nov 2009 | 12:02 pm CET

The inhibitory effect of dissolved carbaryl in dioxane on physically adsorbed acetylcholinesterase Abstract  Acetylcholinesterase was immobilized by means of physical adsorption. The aim of this work is to describe the kinetic characterization of the immobilized acetylcholinesterase. Here we report the effects of immobilization, carbaryl and its solvent dioxane on the kinetic properties of acetylcholinesterase. The immobilized product has significant storage stability. Dioxane could decrease the acetylcholinesterase activity and increase the inhibitory effect of carbaryl. Immobilization could change acetylcholinesterase activity cooperatively. The inhibitory mechanism is hyperbolic noncompetitive. Carbaryl and dioxane could eliminate the substrate inhibition by a competitive mechanism and by changing the native conformation of acetylcholinesterase. Content Type Journal Article Pages 391-401 DOI 10.1007/s11144-009-0094-1 Authors Amir Norouzy, Babol University of Medical Sciences Department of Biochemistry and Biophysics Babol Iran Durdi Qujeq, Babol University of Medical Sciences Department of Biochemistry and Biophysics Babol Iran Mehran Habibi-Rezaei, University of Tehran School of Biology, University College of Science Tehran Iran Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 3 Nov 2009 | 12:02 pm CET

Heterogeneous Heck reaction catalysed by silica gel-supported 1,2-diaminocyclohexane–Pd complex Abstract  A 1,2-diaminocyclohexane–Pd complex was immobilized onto the surface of silica gel and investigated as a catalyst for Heck coupling reactions. The immobilized catalyst exhibited high catalytic activity in the coupling of activated and nonactivated aryl substrates with various acrylates. Moreover, the catalyst was air-stable that could be recycled and reused without significant loss of catalytic activity. Content Type Journal Article Pages 383-389 DOI 10.1007/s11144-009-0085-2 Authors Md. Nazmul Alam, Shahjalal University of Science and Technology Department of Chemistry, School of Physical Sciences Sylhet 3114 Bangladesh Shaheen M. Sarkar, Inha University Department of Chemical Engineering Incheon 402-751 South Korea Md. Rezwan Miah, Shahjalal University of Science and Technology Department of Chemistry, School of Physical Sciences Sylhet 3114 Bangladesh Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 3 Nov 2009 | 12:02 pm CET

Syngas production from methane reforming with O2 and CO2 over Ni–La2O3/SiO2 catalysts using EDTA salt precursors Abstract  Ni–La2O3/SiO2 catalysts (NLS) were prepared by the incipient-wetness impregnation method using EDTA salt precursors. XRD measurements revealed that the promoter of La2O3 is highly dispersed on the NLS. The TPR profiles indicated a strong interaction between NiO and La2O3 to form a La–Ni complex oxide like species over the NLS, which may be the origin of its high catalytic performance. Content Type Journal Article Pages 303-309 DOI 10.1007/s11144-009-0090-5 Authors Wanjin Yu, Zhejiang University Institute of Catalysis, Key Lab of Applied Chemistry of Zhejiang Province Hangzhou 310028 China Yuzhan Xu, Zhejiang Education Institute Department of Chemistry Hangzhou 310012 China Liuye Mo, Zhejiang University Institute of Catalysis, Key Lab of Applied Chemistry of Zhejiang Province Hangzhou 310028 China Hui Lou, Zhejiang University Institute of Catalysis, Key Lab of Applied Chemistry of Zhejiang Province Hangzhou 310028 China Xiaoming Zheng, Zhejiang University Institute of Catalysis, Key Lab of Applied Chemistry of Zhejiang Province Hangzhou 310028 China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 3 Nov 2009 | 12:01 pm CET

Synthesis and characterization of CeO2 by the hydrothermal method assisted by carboxymethylcellulose sodium Abstract  Nano-CeO2 with different crystallite sizes, surface areas and morphologies were synthesized with a hydrothermal method assisted by carboxymethylcellulose sodium (CMC) at 110 °C. It was found that the reducible properties of CeO2 samples showed a significant influence on the active carbon (AC) combustion. Content Type Journal Article Pages 311-318 DOI 10.1007/s11144-009-0093-2 Authors Jing Liu, Zhejiang University, Key Lab of Applied Chemistry of Zhejiang Province Institute of Catalysis 310028 Hangzhou People’s Republic of China Lina Wang, Zhejiang Sci-Tech University Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education 310018 Hangzhou People’s Republic of China Hongmiao Wu, Zhejiang University, Key Lab of Applied Chemistry of Zhejiang Province Institute of Catalysis 310028 Hangzhou People’s Republic of China Liuye Mo, Zhejiang University, Key Lab of Applied Chemistry of Zhejiang Province Institute of Catalysis 310028 Hangzhou People’s Republic of China Hui Lou, Zhejiang University, Key Lab of Applied Chemistry of Zhejiang Province Institute of Catalysis 310028 Hangzhou People’s Republic of China Xiaoming Zheng, Zhejiang University, Key Lab of Applied Chemistry of Zhejiang Province Institute of Catalysis 310028 Hangzhou People’s Republic of China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 3 Nov 2009 | 12:01 pm CET

Kinetic investigation of propane oxidation on diluted Mo1–V0.3–Te0.23–Nb0.125–Ox mixed-oxide catalysts Abstract  Reaction kinetics and proposed mechanism for the oxidation of propane over diluted Mo1–V0.3–Te0.23–Nb0.125–O x are described. The kinetic study allowed determination of the orders of propane disappearance, propene formation, CO x formation, and acids formation. The results show that selective oxidation of propane to propylene over this catalyst follows the Langmuir-Hinshelwood mechanism. Deep oxidation of propane to carbon dioxide is first order with respect to hydrocarbon, and partial order (0.21) with respect to oxygen. The selective oxidation of propane to acrylic acid is half order with respect to hydrocarbon and partial order (0.11) with respect to oxygen, while water does not participate directly in propane transformation. The result also shows that the overall reaction consists of three parallel process channels. One main sequence of consecutive reactions leads to the desired product. Content Type Journal Article Pages 273-286 DOI 10.1007/s11144-009-0092-3 Authors Restu Kartiko Widi, University of Surabaya Department of Chemical Engineering TG Building 6th floor, Raya Kalirungkut Tenggilis Surabaya 60293 Indonesia Sharifah Bee Abd Hamid, Institute of Postgraduate Studies, University of Malaya Combinatorial Technology and Catalysis Research Centre, COMBICAT 3rd floor, Block A 50603 Kuala Lumpur Malaysia Robert Schlogl, Fritz-Haber-Institut Anorganische Chemie Faradayweg 4-6 14195 Berlin Germany Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 3 Nov 2009 | 12:01 pm CET

Hydrogen production on iron–magnesium oxide in the high-temperature water-gas shift reaction Abstract  Fe–Cr–O and Fe–Mg–O catalysts were used for hydrogen production via the water-gas shift reaction. Fe–Cr–O catalysts were synthesized by different methods such as co-precipitation, impregnation and substitution technique. Catalysts were characterized by XRD, TG, BET and TPR. Addition of Mg improved the catalytic activity of Fe–O by favouring the development of small and well dispersed Fe particles (MgFe2O4). As a consequence, MgO prevented iron phase sintering in the presence of a large amount of water in the WGS reaction. Content Type Journal Article Pages 319-325 DOI 10.1007/s11144-009-0084-3 Authors Amel Boudjemaa, Laboratoires C. G. N. et L. S. V. E. R., Faculté de Chimie, USTHB, BP32, El-Alia, Bab-Ezzouar, Algiers, Algeria Aline Auroux, Institut de Recherches sur la Catalyse et l’environnement de Lyon, UMR 5256, CNRS-UCB Lyon1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex, France Souhila Boumaza, Laboratoires C. G. N. et L. S. V. E. R., Faculté de Chimie, USTHB, BP32, El-Alia, Bab-Ezzouar, Algiers, Algeria Mohamed Trari, Laboratoires C. G. N. et L. S. V. E. R., Faculté de Chimie, USTHB, BP32, El-Alia, Bab-Ezzouar, Algiers, Algeria Ouiza Cherifi, Laboratoires C. G. N. et L. S. V. E. R., Faculté de Chimie, USTHB, BP32, El-Alia, Bab-Ezzouar, Algiers, Algeria Rabah Bouarab, Laboratoires C. G. N. et L. S. V. E. R., Faculté de Chimie, USTHB, BP32, El-Alia, Bab-Ezzouar, Algiers, Algeria Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 3 Nov 2009 | 12:01 pm CET

Leaving group effect in the sulfonyl transfer reactions of aryl benzenesulfonates with Grignard reagents Abstract  The C–S coupling reactions of aryl benzenesulfonates with phenylmagnesium bromide in THF:toluene (7:10) at 90 °C have been studied. A Hammett-type kinetic study of the leaving group effect of aryloxy groups provides a conclusive support for a two step addition-elimination mechanism in which C–S bond formation is rate determining step. Content Type Journal Article Pages 365-373 DOI 10.1007/s11144-009-0053-x Authors Fatma Eroğlu, Science Faculty, Ankara University, 06100 Besevler, Ankara, Turkey Didem Kâhya, Science Faculty, Ankara University, 06100 Besevler, Ankara, Turkey Ender Erdik, Science Faculty, Ankara University, 06100 Besevler, Ankara, Turkey Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 24 Sep 2009 | 6:48 pm CEST

Partial oxidation of methane into syngas on Pt-supported mixed oxides: effect of surface/lattice oxygen mobility in complex oxides on the kinetic features of the reaction and performance stability Abstract  Partial oxidation of methane (POM) into syngas at short contact times on two catalysts containing Pt/PrCeZrO and Pt/LaCeZrO deposited on single channels of a corundum monolithic substrate was investigated. The effects of the catalyst composition, pretreatment and process parameters on activity and selectivity of the syngas formation were studied. The oxygen mobility in complex oxides was shown to determine both their stability to coking and realization of a direct selective oxidation route of the syngas generation. Content Type Journal Article Pages 27-33 DOI 10.1007/s11144-009-0063-8 Authors Natalya N. Sazonova, Boreskov Institute of Catalysis SB RAS 630090 Novosibirsk Russia Vladislav A. Sadykov, Boreskov Institute of Catalysis SB RAS 630090 Novosibirsk Russia Aleksey S. Bobin, Boreskov Institute of Catalysis SB RAS 630090 Novosibirsk Russia Svetlana A. Pokrovskaya, Boreskov Institute of Catalysis SB RAS 630090 Novosibirsk Russia Elena L. Gubanova, Boreskov Institute of Catalysis SB RAS 630090 Novosibirsk Russia Claude Mirodatos, CNRS Institut de Recherches sur la Catalyse 2 Avenue Albert Einstein Villeurbanne Cédex France Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 18 Sep 2009 | 1:09 am CEST

Catalytic oxidation of ethylene to acetic acid on Pd–HPA/SiO2 catalysts with different heteropoly acids Abstract  The effect of different heteropoly acids (HPA) on the catalytic properties of Pd–HPA/SiO2 in the selective oxidation of ethylene to acetic acid was investigated in this work. The results demonstrated that a good balance of Brönsted acid sites and Pd2+ ions stabilized by Brönsted acid sites was an indispensable factor in producing acetic acid. Content Type Journal Article Pages 107-115 DOI 10.1007/s11144-009-0074-5 Authors Shuliang Xu, Chinese Academy of Sciences State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics P.O. Box 110 116023 Dalian China Lixia Wang, Chinese Academy of Sciences State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics P.O. Box 110 116023 Dalian China Wenling Chu, Chinese Academy of Sciences State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics P.O. Box 110 116023 Dalian China Weishen Yang, Chinese Academy of Sciences State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics P.O. Box 110 116023 Dalian China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 18 Sep 2009 | 1:09 am CEST

Cobalt Schiff base complexes with symmetric or asymmetric ligands: syntheses and application for the redox carbonylation of aniline to diphenyl urea Abstract  Two asymmetric salophen ligands (salophen(OH)(H) and salophen(NO2)(H)) were successfully synthesized via a step-wise approach. The catalytic results using redox carbonylation of aniline as model reaction showed that cobalt(II)–salophen(OH)(H) complexes is the most reactive catalyst. Content Type Journal Article Pages 99-105 DOI 10.1007/s11144-009-0073-6 Authors Li-Juan Chen, Huazhong University of Science and Technology Department of Chemistry 430074 Wuhan Peoples Republic of China Fu-Ming Mei, Huazhong University of Science and Technology Department of Chemistry 430074 Wuhan Peoples Republic of China Guang-Xing Li, Huazhong University of Science and Technology Department of Chemistry 430074 Wuhan Peoples Republic of China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 18 Sep 2009 | 1:09 am CEST

In situ FTIR study of transformation of 3-cyanopyridine on V–Ti–O catalyst Abstract  Surface complexes of cyanopyridine on a V–Ti–O catalyst were studied by in situ FTIR spectroscopy. In the temperature range of 130–290 °C, two types of adsorbed cyanopyridine bound to different sites (Lewis acid sites or Brönsted acid sites) were found to transform into surface nicotinamide. At 220–290 °C, surface heterocyclic complexes decompose to form carboxylates and ammonium ions. Content Type Journal Article Pages 43-50 DOI 10.1007/s11144-009-0065-6 Authors Yuriy A. Chesalov, Boreskov Institute of Catalysis 630090 Novosibirsk Russia Galina Ya. Popova, Boreskov Institute of Catalysis 630090 Novosibirsk Russia Galina B. Chernobay, Boreskov Institute of Catalysis 630090 Novosibirsk Russia Tamara V. Andrushkevich, Boreskov Institute of Catalysis 630090 Novosibirsk Russia Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 18 Sep 2009 | 1:09 am CEST

Dry reforming of methane over fluorite-like mixed oxides promoted by Pt Abstract  Dry reforming of methane into syngas was studied over complex Pt-promoted fluorite-like oxides (PrCeZrO, GdCeZrO and LaCeZrO) supported on a corundum substrate. Activity and syngas selectivity of these catalysts were found to depend strongly on their composition, pretreatment and reaction conditions. At low temperatures and short contact times, the H2/CO ratio in the syngas is below 1 due to a fast reverse water–gas shift reaction. The catalyst performance was found to correlate with the bulk oxygen mobility in complex fluorite-like oxides, which prevents the surface coking. Content Type Journal Article Pages 35-41 DOI 10.1007/s11144-009-0064-7 Authors Natalya N. Sazonova, Boreskov Institute of Catalysis SB RAS 630090 Novosibirsk Russia Vladislav A. Sadykov, Boreskov Institute of Catalysis SB RAS 630090 Novosibirsk Russia Aleksey S. Bobin, Boreskov Institute of Catalysis SB RAS 630090 Novosibirsk Russia Svetlana A. Pokrovskaya, Boreskov Institute of Catalysis SB RAS 630090 Novosibirsk Russia Elena L. Gubanova, Boreskov Institute of Catalysis SB RAS 630090 Novosibirsk Russia Claude Mirodatos, CNRS Institut de Recherches sur la Catalyse 2 Avenue Albert Einstein Villeurbanne Cédex France Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 18 Sep 2009 | 1:09 am CEST

Partial oxidation of methane into synthesis gas over a Pt-supported complex fluorite-like oxide: one-channel studies in realistic feeds Abstract  Partial oxidation of methane (POM) into synthesis gas over a single channel of monolithic catalyst 1.4 wt% Pt/Gd0.3Ce0.35Zr0.35Ox/α-Al2O3 was investigated. The effect of the catalyst pretreatment and of the process parameters (temperature, contact time, feed composition) on the catalytic activity and synthesis gas (syngas) selectivity was studied at conditions close to realistic ones with a minimum impact of the mass and heat transfer phenomena. Experimental data are in favor of the direct route of the syngas formation via the methane pyrolysis—selective oxidation sequence. Content Type Journal Article Pages 19-26 DOI 10.1007/s11144-009-0062-9 Authors Natalya N. Sazonova, Boreskov Institute of Catalysis SB RAS Novosibirsk 630090 Russia Vladislav A. Sadykov, Boreskov Institute of Catalysis SB RAS Novosibirsk 630090 Russia Aleksey S. Bobin, Boreskov Institute of Catalysis SB RAS Novosibirsk 630090 Russia Svetlana A. Pokrovskaya, Boreskov Institute of Catalysis SB RAS Novosibirsk 630090 Russia Elena L. Gubanova, Boreskov Institute of Catalysis SB RAS Novosibirsk 630090 Russia Claude Mirodatos, CNRS Institut de Recherches sur la Catalyse 2 Avenue Albert Einstein Villeurbanne Cedex France Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 18 Sep 2009 | 1:09 am CEST

Stability of [(N-pyrrolidine)metylene]daunorubicin in aqueous solutions Abstract  The stability of [(N-pyrrolidine)metylene]daunorubicin (PMD) in aqueous solutions was studied in the pH range 0.42–12.03 at four temperatures. Its degradation was evaluated by using an HPLC method with UV detection (254 nm). The hydrolysis of PMD involved: (a) hydrolysis of protonated molecules of PMD depending on hydrogen ions and (b) spontaneous hydrolysis under the influence of water depending on the substrate charge. Content Type Journal Article Pages 69-75 DOI 10.1007/s11144-009-0068-3 Authors Anna Jelińska, Poznan University of Medical Sciences Department of Pharmaceutical Chemistry, Faculty of Pharmacy Grunwaldzka 6 60-780 Poznań Poland Justyna Uszak, Biofarm Sp. Z o.o. Wałbrzyska 13 60-198 Poznań Poland Judyta Cielecka-Piontek, Poznan University of Medical Sciences Department of Pharmaceutical Chemistry, Faculty of Pharmacy Grunwaldzka 6 60-780 Poznań Poland Marianna Zając, Poznan University of Medical Sciences Department of Pharmaceutical Chemistry, Faculty of Pharmacy Grunwaldzka 6 60-780 Poznań Poland Anna Lamberti, Poznan University of Medical Sciences Department of Pharmaceutical Chemistry, Faculty of Pharmacy Grunwaldzka 6 60-780 Poznań Poland Irena Oszczapowicz, Institute of Biotechnology and Antibiotics Department of Modified Antibiotics Starościńska 5 02-515 Warsaw Poland Małgorzata Łukawska, Institute of Biotechnology and Antibiotics Department of Modified Antibiotics Starościńska 5 02-515 Warsaw Poland Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 16 Sep 2009 | 3:14 pm CEST

Comparison of the substrate dependent performance of Pt-, Au- and Ag-doped TiO2 photocatalysts in H2-production and in decomposition of various organics Abstract  Pt-, Au- and Ag-deposited Degussa P25 photocatalysts [at 1% (m/m) noble metal loading] were prepared in which the noble metals are most likely to be very finely dispersed on the surface of the TiO2 nanocrystals. Deposition of noble metals increased the photocatalytic efficiency (relative to the bare photocatalyst) in the decomposition of oxalic- and formic acid, while decreased it in phenol containing systems. In H2-production, a very high quantum yield has been found for the Pt–TiO2 photocatalyst in the presence of oxalic and formic acids as sacrificial reagents, which opens the possibility for the economic use of industrial side products (e.g., oxalic- and formic acid) for photocatalytic H2-production. Content Type Journal Article Pages 215-225 DOI 10.1007/s11144-009-0052-y Authors Károly Mogyorósi, University of Szeged Department of Inorganic and Analytical Chemistry, Research Group for Environmental Chemistry, ReGECh PO Box 440 6701 Szeged Hungary Ákos Kmetykó, University of Szeged Department of Inorganic and Analytical Chemistry, Research Group for Environmental Chemistry, ReGECh PO Box 440 6701 Szeged Hungary Nóra Czirbus, University of Szeged Department of Inorganic and Analytical Chemistry, Research Group for Environmental Chemistry, ReGECh PO Box 440 6701 Szeged Hungary Gábor Veréb, University of Szeged Department of Inorganic and Analytical Chemistry, Research Group for Environmental Chemistry, ReGECh PO Box 440 6701 Szeged Hungary Pál Sipos, University of Szeged Department of Inorganic and Analytical Chemistry, Research Group for Environmental Chemistry, ReGECh PO Box 440 6701 Szeged Hungary András Dombi, University of Szeged Department of Inorganic and Analytical Chemistry, Research Group for Environmental Chemistry, ReGECh PO Box 440 6701 Szeged Hungary Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 16 Sep 2009 | 3:14 pm CEST

Catalytic oxidation of fatty acids. II. Epoxidation and oxidative cleavage of unsaturated fatty acid esters containing additional functional groups Abstract  Methyl esters of monounsaturated fatty acids were oxidized with aqueous hydrogen peroxide in biphasic organic-aqueous systems in the presence of catalyst [Me(n-C8H17)3N]3{PO4[WO(O2)2]4}. Epoxidation and oxidative cleavage of the C=C bond were found to proceed with high conversion and selectivity in the absence of organic solvents and under rather mild conditions (T < 100 °C, 1 atm). Content Type Journal Article Pages 9-17 DOI 10.1007/s11144-009-0054-9 Authors Tatiana B. Khlebnikova, Boreskov Institute of Catalysis Novosibirsk 630090 Russia Zinaida P. Pai, Boreskov Institute of Catalysis Novosibirsk 630090 Russia Larisa A. Fedoseeva, Institute of Cytology and Genetics Novosibirsk 630090 Russia Yulia V. Mattsat, Boreskov Institute of Catalysis Novosibirsk 630090 Russia Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 16 Sep 2009 | 3:14 pm CEST

Catalytic oxidation of fatty acids. I. Epoxidation of unsaturated fatty acids Abstract  Unsaturated fatty acids and their derivatives were oxidized with aqueous hydrogen peroxide in two-phase systems in the presence of homogeneous catalysts Q3{PO4[WO(O2)2]4}, where Q is [Bu4n]3 +, [C5H5N(n-C16H33)]3 + or [Me(n-C8H17)3N]3 +. The reactions occurred under mild conditions (T < 100 °C, atmospheric pressure), without organic solvents, and exhibited high conversion and selectivity. Content Type Journal Article Pages 1-8 DOI 10.1007/s11144-009-0069-2 Authors Zinaida P. Pai, Boreskov Institute of Catalysis Novosibirsk 630090 Russia Tatiana B. Khlebnikova, Boreskov Institute of Catalysis Novosibirsk 630090 Russia Yulia V. Mattsat, Boreskov Institute of Catalysis Novosibirsk 630090 Russia Valentin N. Parmon, Boreskov Institute of Catalysis Novosibirsk 630090 Russia Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 16 Sep 2009 | 3:14 pm CEST

Promoted aromatization and isomerization performance over ZSM-5 zeolite modified by the combined alkali-steam treatment Abstract  The combined alkali-steam treatment was employed to prepare the ZSM-5 zeolite possessing the micro-mesopore hierarchical structure and proper acidity simultaneously. The tailored zeolite displayed superior catalytic performance in the aromatization and isomerization of 1-hexene. Content Type Journal Article Pages 117-124 DOI 10.1007/s11144-009-0075-4 Authors Yuning Li, Chinese Academy of Sciences State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics 116023 Dalian People’s Republic of China Shenglin Liu, Chinese Academy of Sciences State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics 116023 Dalian People’s Republic of China Sujuan Xie, Chinese Academy of Sciences State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics 116023 Dalian People’s Republic of China Longya Xu, Chinese Academy of Sciences State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics 116023 Dalian People’s Republic of China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Phosphomolybdic acid dispersed in Al-pillared clay (PMA/Al-PILC) as heterogeneous catalyst for the benign synthesis of benzoxanthenes under solvent free conditions Abstract  Phosphomolybdic acid dispersed in the micropores of Al-pillared clay (PMA/Al-PILC) was prepared by the impregnation method and characterized by XRD and sorptomeric studies. The interlayer structure of the Al-pillared clay was found to be retained in the PMA/Al-PILC catalyst which displays high surface area and micropore volume. The PMA/Al-PILC material was used as a heterogeneous and recyclable catalyst for efficient condensation of β-naphthol with arylaldehydes to afford a variety of structurally diverse aryl-14H-dibenzo[a,j]xanthenes in excellent yield and purity in short reaction time under microwave irradiation. Content Type Journal Article Pages 125-131 DOI 10.1007/s11144-009-0076-3 Authors Mallari A. Naik, Birla Institute of Technology and Science Chemistry Group Pilani 333031 India S. Samantaray, National Institute of Technology Chemistry Department Rourkela 769008 India Braja Gopal Mishra, National Institute of Technology Chemistry Department Rourkela 769008 India Amit Dubey, Birla Institute of Technology and Science Chemistry Group Pilani 333031 India Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Corrosivity of catalysts based on aqueous solutions of Mo–V–P heteropoly acids Abstract  Corrosion resistance of metallic titanium, alloys KhN65MV and 06KhN28MDT, and stainless steels 10Kh17N13M2T and 12Kh18N10T towards the action of homogenous oxidation catalysts based on aqueous solutions of Mo–V–P heteropoly acids was studied by an example of the 0.25 M aqueous solution of H12P3Mo18V7O85. It was established that the corrosivity of this solution towards these materials grows in the series: Ti < 06KhN28MDT < 10Kh17N13M2T < 12Kh18N10T << KhN65MV. The highest corrosion resistance of the steels 06KhN28MDT and 10Kh17N13M2T was attributed to the fact that their Ni:Cr atomic ratio is in the range from 0.6 to 1.1. Content Type Journal Article Pages 51-58 DOI 10.1007/s11144-009-0066-5 Authors Elena G. Zhizhina, Boreskov Institute of Catalysis, Novosibirsk, 630090 Russia Viktor F. Odyakov, Boreskov Institute of Catalysis, Novosibirsk, 630090 Russia Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Comparative study of nucleophilic efficacy of pralidoxime towards phosphorus, sulfur and thiophosphorus based esters Abstract  The nucleophilic substitution reaction of p-nitrophenyl diphenyl phosphate, p-nitrophenyl p-toluene sulfonate and insecticide fenitrothion with pralidoxime have been studied at 27 °C in the presence of different cationic surfactants. Micellar rate enhancements increase as the cationic head group is made less polar. The order of cleavage of different electrophilic centres by pralidoxime is P = O > S = O > P = S. Content Type Journal Article Pages 91-97 DOI 10.1007/s11144-009-0072-7 Authors Shuchi Tiwari, Pt. Ravishankar Shukla University School of Studies in Chemistry Raipur CG 492010 India Kallol K. Ghosh, Pt. Ravishankar Shukla University School of Studies in Chemistry Raipur CG 492010 India Jan Marek, Faculty of Military Health Sciences Center of Advanced Studies and Department of Toxicology Trebesska1575 500 01 Hradec Kralove Czech Republic Kamil Kuca, Faculty of Military Health Sciences Center of Advanced Studies and Department of Toxicology Trebesska1575 500 01 Hradec Kralove Czech Republic Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Photocatalytic activity of sol–gel derived TiO2 co-doped with iron and niobium Abstract  Titanium dioxide (TiO2) photocatalysts co-doped with iron (Fe) and niobium (Nb) were synthesized using a temperature-controlled sol–gel method. The photocatalysis products were characterized and the photocatalytic activities were evaluated by the degradation of aqueous methyl orange solution. Enhanced photocatalytic activity compared to undoped TiO2 was attributed to the cooperative effects of metal dopants, Fe and Nb. Content Type Journal Article Pages 187-192 DOI 10.1007/s11144-009-0061-x Authors Carl Renan Estrellan, Tokyo Institute of Technology Department of International Development Engineering 2-12-1 Ookayama, Meguro-ku Tokyo 152-8552 Japan Chris Salim, Tokyo Institute of Technology Department of International Development Engineering 2-12-1 Ookayama, Meguro-ku Tokyo 152-8552 Japan Hirofumi Hinode, Tokyo Institute of Technology Department of International Development Engineering 2-12-1 Ookayama, Meguro-ku Tokyo 152-8552 Japan Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

The effect of mixed surfactants of sodium dodecyl sulfate and Triton X-100 on the base hydrolysis of Malachite green Abstract  The base hydrolysis of Malachite green (MG+) was studied in aqueous solution of mixed surfactants of sodium dodecyl sulfate (SDS) and Triton X-100 (TX-100) at 25 °C. The results show that the SDS/TX-100 system compositions has relatively significant influence on the rate constant of the base hydrolysis of MG+ when compared with the reaction in the respective single surfactant systems. Content Type Journal Article Pages 77-82 DOI 10.1007/s11144-009-0070-9 Authors O. Oladega Soriyan, Obafemi Awolowo University Department of Chemistry Ile-Ife Nigeria Olanrewaju Owoyomi, Obafemi Awolowo University Department of Chemistry Ile-Ife Nigeria J. T. Bamgbose, Federal University of Agriculture Department of Chemistry Abeokuta Nigeria Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Peculiarities of dehydroaromatization of CH4–C2H6 and CH4 over Mo/ZSM-5 catalysts Abstract  The peculiarities of dehydroaromatization (DHA) of a CH4–C2H6 mixture over 1–10% Mo/ZSM-5 catalysts (Si/Al = 17, 30, 45) were studied in comparison with reactions of individual hydrocarbons. For a (90 vol.% CH4 + 10 vol.% Ar) mixture, the methane conversion passes through a maximum and decreases with the time-on-stream, being about 12% after 6 h. Experiments with a mixture (85 vol.% CH4 + 5 vol.% C2H6 + 10 vol.% Ar) demonstrated that the presence of ethane leads to the suppression of the methane conversion practically to zero and to an increase in the benzene formation rate in comparison with the (CH4 + Ar) mixture. Characterization of the spent Mo/ZSM-5 catalysts by DTA and TGA showed that both the condensation degree of the carbonaceous deposits (C/H ratio) and their content are higher in the presence of ethane. For both feed compositions, the maximal benzene formation rate was observed over the catalyst with 2 wt% Mo and Si/Al = 17. It is proposed that the formation of C2 intermediates from methane and their further transformations in DHA compete with the ethane aromatization, presumably on the same Mo active sites. Content Type Journal Article Pages 59-67 DOI 10.1007/s11144-009-0080-7 Authors Ekaterina V. Matus, Boreskov Institute of Catalysis 630090 Novosibirsk Russia Olga B. Sukhova, Boreskov Institute of Catalysis 630090 Novosibirsk Russia Ilyas Z. Ismagilov, Boreskov Institute of Catalysis 630090 Novosibirsk Russia Lidiya T. Tsikoza, Boreskov Institute of Catalysis 630090 Novosibirsk Russia Zinfer R. Ismagilov, Boreskov Institute of Catalysis 630090 Novosibirsk Russia Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Synthesis of MgAPO-5 molecular sieves and their kinetic behavior for n-hexane cracking Abstract  Five magnesium substituted aluminophosphate molecular sieves (denoted as MgAPO-5 (a–e), AFI topology) with different magnesium contents were synthesized hydrothermally and characterized by XRD, ICP-AES, IR, and NH3-TPD techniques. The characterization data show that the isomorphous substitution of magnesium for aluminum in the pure AFI framework results in MgAPO-5 (a–e) with weak and strong acid sites and that the number of strong acid sites linearly increases with increasing magnesium content (correlation coefficient: 0.9960). n-Hexane catalytic cracking over MgAPO-5 (a–e) was investigated at low conversions (≤5%) in a microflow fixed bed reactor. Under controlled conditions, the reaction was first order in both the n-hexane concentration and the magnesium content. The analysis of the kinetic parameters and the product selectivities suggests that the cracking transformation is effected by strong Mg(II)-related acid sites rather than weak ones and predominantly undergoes the monomolecular protolytic mechanism, which is consistently explained by a proposed kinetic model. Content Type Journal Article Pages 327-339 DOI 10.1007/s11144-009-0078-1 Authors Lili Feng, Beijing University of Aeronautics and Astronautics School of Chemistry and Environment 37 Xueyuan Road, HaiDian District Beijing 100191 People’s Republic of China Xingyi Qi, Beijing University of Aeronautics and Astronautics School of Chemistry and Environment 37 Xueyuan Road, HaiDian District Beijing 100191 People’s Republic of China Junying Li, Beijing University of Aeronautics and Astronautics School of Chemistry and Environment 37 Xueyuan Road, HaiDian District Beijing 100191 People’s Republic of China Yuelin Zhu, Beijing University of Aeronautics and Astronautics School of Chemistry and Environment 37 Xueyuan Road, HaiDian District Beijing 100191 People’s Republic of China Liqun Zhu, Beijing University of Aeronautics and Astronautics School of Chemistry and Environment 37 Xueyuan Road, HaiDian District Beijing 100191 People’s Republic of China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Conversion of n-heptane to LPG and aromatics over Mo2C and W2C catalysts supported on ZSM-5 Abstract  We have investigated the catalytic activity of W2C/HZSM-5 and Mo2C/HZSM-5 for conversion of n-heptane to LPG and aromatic products. The results show that the catalytic activity of the metallic carbides increases markedly in the presence of ZSM-5. For pure carbides, the main cracking products are methane and ethane as a result of the cleavage of the C–C bond at the end of the hydrocarbon chain. In contrast, the zeolitic catalysts produce LPG (propane, i-butane, and n-butane) through the cleavage of C–C bond in the medial bonds. It is observed that the metallic carbides play a key role in producing the aromatics, concerning the formation of olefin species and cyclization of them in the channels of zeolite. Content Type Journal Article Pages 133-138 DOI 10.1007/s11144-009-0077-2 Authors M. R. Toosi, Shahid Beheshti University Department of Chemistry, Faculty of Science Tehran 1983963113 Iran M. H. Peyrovi, Shahid Beheshti University Department of Chemistry, Faculty of Science Tehran 1983963113 Iran R. Mondgarian, Research Institute of Petroleum Industry (RIPI) Tehran 1485733111 Iran Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Aldol condensation of acetone over Mg–Al mixed oxides catalyst prepared by a citric acid route Abstract  Mg–Al mixed oxides with different Mg/Al molar ratios were prepared by using a citric acid route and tested as catalysts for the gas phase self-aldol condensation of acetone to isophorone. The sample with Mg/Al ratio of 1.0 exhibits relatively high activity and stability, and its catalytic performance could be further improved by adding alkali promoter. Content Type Journal Article Pages 149-156 DOI 10.1007/s11144-009-0055-8 Authors Chunxiang Ma, Jilin University Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry 130012 Changchun China Gang Liu, Jilin University Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry 130012 Changchun China Zhenlu Wang, Jilin University Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry 130012 Changchun China Yufei Li, Jilin University Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry 130012 Changchun China Jing Zheng, Jilin University Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry 130012 Changchun China Wenxiang Zhang, Jilin University Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry 130012 Changchun China Mingjun Jia, Jilin University Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry 130012 Changchun China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Single step conversion of benzene to phenol using hydrogen peroxide over modified V2O5–Al2O3 systems Abstract  Alumina supported vanadia catalysts were prepared by the wet impregnation method. The effect of vanadium content was investigated with 1.92–16.93 wt% V2O5 loading over the support. Physical characterization of the catalysts was done by techniques such as energy dispersive X-ray (EDX), X-ray diffraction (XRD), BET surface area measurement, FTIR spectroscopy and temperature programmed reduction (TPR) studies. Characterization techniques have revealed that vanadia is well dispersed over alumina up to 13.91 wt%, after which aggregation into vanadia crystallites was observed. Single step liquid-phase hydroxylation of benzene to phenol by hydrogen peroxide was studied over these catalysts. The phenol selectivity can be attributed to amorphous surface vanadyl units in the catalysts. The supported analogues were modified with oxides of iron and cerium. Ceria incorporation to alumina enhanced the activity towards hydroxylation of benzene. Content Type Journal Article Pages 139-147 DOI 10.1007/s11144-009-0079-0 Authors Ammanchery Velandy Shijina, University of Calicut Department of Chemistry Kerala India Neeroli Kizhakayil Renuka, University of Calicut Department of Chemistry Kerala India Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Studies on the photocatalytic degradation of 2,3-dichlorophenol using different oxidants in aqueous solutions Abstract  In the present study, the photocatalytic degradation of 2,3-dichlorophenol(2,3-DCP) has been investigated in a batch reactor under UV light in slurry mode using titania P-25 (surface area 50 m2/g) as a photocatalyst and H2O2/NaOCl as oxidants. The variables studied include catalyst dose, solution pH, oxidant concentration and initial substrate concentration. The rate of degradation was studied in terms of changes in the concentration of the pollutants and reduction in chemical oxygen demand. The degradation rate of (2,3-DCP) was favorable at acidic pH with both oxidants. The optimum value of catalyst dose and oxidant concentration was found to be 0.75 g/L and 10 mM. The disappearance of 2,3-DCP obeyed pseudo-first order kinetics and the rate constant values were found to be 1.06 × 10−3s−1 and 8.7 × 10−4s−1 for TiO2 + H2O2 and TiO2 + NaOCl respectively. Content Type Journal Article Pages 177-186 DOI 10.1007/s11144-009-0058-5 Authors S. K. Kansal, University Institute of Chemical Engineering & Technology, Panjab University Chandigarh India G. Kaur, University Institute of Chemical Engineering & Technology, Panjab University Chandigarh India S. Singh, University Institute of Chemical Engineering & Technology, Panjab University Chandigarh India Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Photocatalytic degradation of C.I. Acid Blue 80 in aqueous suspensions of titanium dioxide under sunlight Abstract  The dye C.I. Acid Blue 80 (AB80) was easily degraded by TiO2-P25 assisted photocatalysis in aqueous dispersion under irradiation of sunlight. The optimal reaction conditions were [TiO2] = 2.0 g/L, pH = 10, [H2O2] = 5 mmol/L. The photocatalytic reaction followed pseudo-first order kinetics. The adsorption of AB80 onto TiO2 was in accord with Langmuir equation. Content Type Journal Article Pages 227-240 DOI 10.1007/s11144-009-0059-4 Authors Yingying Su, Institute of Oceanology, Chinese Academy of Sciences 266071 Qingdao Shandong China Liping Deng, Institute of Oceanology, Chinese Academy of Sciences 266071 Qingdao Shandong China Ning Zhang, Institute of Oceanology, Chinese Academy of Sciences 266071 Qingdao Shandong China Xinting Wang, Institute of Oceanology, Chinese Academy of Sciences 266071 Qingdao Shandong China Xiaobin Zhu, Institute of Oceanology, Chinese Academy of Sciences 266071 Qingdao Shandong China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Hydrolyzed octadecyltrichlorosilane functionalized with amino acids as heterogeneous enantioselective catalysts Abstract  Heterogeneous asymmetric catalysts using amino acids as chiral promoter were synthesized by attachment of amino acids such as l-glutamic acid and l-phenylalanine onto the hydrophilic part of hydrolyzed octadecyltrichlorosilane (OTS). The catalysts exhibited 12–18% enantiomeric excess (ee) for the asymmetric hydration of epoxycyclohexene to yield (1R,2R)-trans-1,2-cyclohexanediol and (1S,2S)-trans-1,2-cyclohexanediol. Content Type Journal Article Pages 157-164 DOI 10.1007/s11144-009-0056-7 Authors Hadi Nur, Universiti Teknologi Malaysia (UTM) Ibnu Sina Institute for Fundamental Science Studies 81310 Skudai, Johor Malaysia Lim Kheng Wei, Universiti Teknologi Malaysia (UTM) Ibnu Sina Institute for Fundamental Science Studies 81310 Skudai, Johor Malaysia Salasiah Endud, Universiti Teknologi Malaysia (UTM) Ibnu Sina Institute for Fundamental Science Studies 81310 Skudai, Johor Malaysia Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Gas phase degradation of acetone using a TiO2 photocatalyst supported on a polyester fabric Abstract  The feasibility of using a titanium dioxide photocatalyst supported on polyester fabric for the removal of low concentrations of VOCs was evaluated. A series of experiments was conducted to evaluate photocatalytic efficiency in terms of the following: catalytic activity; reaction temperature; influence of mass transfer and type of VOC. Content Type Journal Article Pages 165-175 DOI 10.1007/s11144-009-0057-6 Authors Hana Žabová, Institute of Chemical Process Fundamentals of the AS CR, v.v.i Rozvojová 135 165 02 Prague Czech Republic Bohumír Dvořák, Institute of Chemical Technology in Prague Department of Organic Technology Technická 5 166 28 Prague Czech Republic Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Kinetic and mechanistic study of photocatalytic degradation of 4,4′-biphenol in TiO2 suspension Abstract  The photodegradation of 4,4′-biphenol (BIP) under a metal halide lamp followed the Langmuir–Hinshelwood kinetic model and the hydroxylation reaction was considered as the main initial step for BIP degradation on the basis of GC/MS analysis. Content Type Journal Article Pages 249-258 DOI 10.1007/s11144-009-0060-y Authors Yanhua Gong, School of Resources and Environmental Science, Wuhan University Wuhan 430079 People’s Republic of China Xu Zhang, School of Resources and Environmental Science, Wuhan University Wuhan 430079 People’s Republic of China Lijie Bai, School of Resources and Environmental Science, Wuhan University Wuhan 430079 People’s Republic of China Nansheng Deng, School of Resources and Environmental Science, Wuhan University Wuhan 430079 People’s Republic of China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Kinetic modeling of sucrose hydrogenation in the production of sorbitol and mannitol with ruthenium and nickel-Raney catalysts Abstract  Experimental and modeling studies in the catalytic hydrogenation of glucose and fructose were carried out for the production of sorbitol and mannitol on ruthenium and nickel catalysts. Ruthenium based catalyst showed better results when compared to the Ni-Raney catalyst, achieving close to 100% of reactant conversion after 3 h of reaction at 130 °C and 750 psia conditions. The application of hybrid autocatalytic kinetic models for the reaction network of the formation of sorbitol and mannitol led to simulation results that represented the data obtained experimentally well. The autocatalytic terms were observed in the concentration profiles of sorbitol and mannitol. From the correlation between the experimental data and the simulation results of the autocatalytic kinetic models, it was possible to determine the kinetic parameters of the hydrogenation using both the nickel and ruthenium catalysts (Ni/Raney and Ru/Al2O3, respectively). Content Type Journal Article Pages 83-89 DOI 10.1007/s11144-009-0071-8 Authors Márcia C. M. Castoldi, Escola de Química, Universidade Federal do Rio de Janeiro (EQ-UFRJ), Ilha do Fundão, Centro de Tecnologia GREENTEC—Laboratório de Tecnologia Verde bloco E-sala 211 CEP 21949-900 Rio de Janeiro RJ Brazil Leôncio Diógenes T. Câmara, Instituto Politécnico da Universidade do Estado do Rio de Janeiro (IPRJ-UERJ) Dep. Eng. Mecânica e Energia- DEMEC Nova Friburgo RJ Brazil Donato A. G. Aranda, Escola de Química, Universidade Federal do Rio de Janeiro (EQ-UFRJ), Ilha do Fundão, Centro de Tecnologia GREENTEC—Laboratório de Tecnologia Verde bloco E-sala 211 CEP 21949-900 Rio de Janeiro RJ Brazil Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 98 Journal Issue Volume 98, Number 1 Quelle: Reaction Kinetics and Catalysis Letters | 3 Sep 2009 | 8:41 am CEST

Glycerol hydrogenolysis to propylene glycol Abstract  A nickel catalyst showed a considerable selectivity to propylene glycol (up to 98%) at 30% glycerol conversion, under moderate hydrogenation conditions: 200 °C reaction temperature, 20–25 bar hydrogen pressure, 5 wt% catalyst and unprecedented low reaction time of 8 h. Content Type Journal Article Pages 315-320 DOI 10.1007/s11144-009-0032-2 Authors Adriana Marinoiu, Research Center OLTCHIM S.A 1 Uzinei St Ramnicu Valcea 240050 Romania Gheorghe Ionita, ANDRAD National Agency for Radioactive Waste Pitesti Romania Costinela-Laura Gáspár, Research Center OLTCHIM S.A 1 Uzinei St Ramnicu Valcea 240050 Romania Claudia Cobzaru, Technical University Iasi Faculty of Industrial Chemistry 71, D. Mangeron Ave Iasi 70050 Romania Spiridon Oprea, Technical University Iasi Faculty of Industrial Chemistry 71, D. Mangeron Ave Iasi 70050 Romania Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 97 Journal Issue Volume 97, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 21 Jul 2009 | 2:08 am CEST

Tap study of the impact of the oxidation state of Pt/PrCeZrO and Pt/GdCeZrO catalysts on their reactivity in the partial/deep oxidation of methane Abstract  The temporal analysis of products (TAP) technique coupled with the oxygen TPD was used to elucidate the effects of the Pt-supported fluorite-like doped ceria–zirconia oxide chemical composition and the type of pretreatment on their oxygen bonding strength, mobility, and reactivity as related to catalytic properties in the partial oxidation of methane into synthesis gas. A rapid evolution of hydrogen under CH4 pulse observed for oxidized catalysts agrees with the direct route of the methane selective oxidation into syngas. This route is favored by the Pt-support interaction and a moderate bonding strength of surface oxygen species along with a high lattice oxygen mobility. Content Type Journal Article Pages 349-354 DOI 10.1007/s11144-009-0040-2 Authors Elena L. Gubanova, Université de Lyon - Université Claude Bernard Lyon1 Institut de Recherches sur la catalyse et l’environnement de Lyon (IRCELYON), UMR 5256 (CNRS/Université Claude Bernard Lyon1) 2 Avenue Albert Einstein Villeurbanne Cedex 69626 France Vladislav A. Sadykov, Boreskov Institute of Catalysis SB RAS Pr. Lavrentieva 5 Novosibirsk 630090 Russia Andre C. van Veen, Université de Lyon - Université Claude Bernard Lyon1 Institut de Recherches sur la catalyse et l’environnement de Lyon (IRCELYON), UMR 5256 (CNRS/Université Claude Bernard Lyon1) 2 Avenue Albert Einstein Villeurbanne Cedex 69626 France Claude Mirodatos, Université de Lyon - Université Claude Bernard Lyon1 Institut de Recherches sur la catalyse et l’environnement de Lyon (IRCELYON), UMR 5256 (CNRS/Université Claude Bernard Lyon1) 2 Avenue Albert Einstein Villeurbanne Cedex 69626 France Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 97 Journal Issue Volume 97, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 14 Jul 2009 | 1:09 pm CEST

Facile preparation of visible-light-sensitive sulfur–nitrogen-codoped titanium dioxide Abstract  S–N-codoped TiO2 powders have been synthesized through a facile one-step sol–gel method by using tetrabutyltitanate and thiourea as precursors. The S–N-codoped TiO2 treated at 500 °C showed the highest photocatalytic activity for degrading methylene blue under visible light irradiation. XRD, XPS and UV–vis studies revealed that the high visible-light photocatalytic activity of the doped TiO2 may originate from the synergetic effect of sulfur and nitrogen codoping into TiO2. Content Type Journal Article Pages 199-205 DOI 10.1007/s11144-009-0051-z Authors Shujuan Zhang, College of Science, Tianjin University of Science & Technology, Tianjin, 300457 People’s Republic of China Limin Song, College of Materials Science and Chemical Engineering & Tianjin Key Laboratory of Fiber Modification and Functional Fiber, Tianjin Polytechnic University, Tianjin, 300160 People’s Republic of China Shuna Zhang, ZheJiang Industry Polytechnic College, Shaoxing, 312000 People’s Republic of China Donglan Sun, College of Science, Tianjin University of Science & Technology, Tianjin, 300457 People’s Republic of China Bin Chen, College of Materials Science and Chemical Engineering & Tianjin Key Laboratory of Fiber Modification and Functional Fiber, Tianjin Polytechnic University, Tianjin, 300160 People’s Republic of China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 97 Journal Issue Volume 97, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 14 Jul 2009 | 1:09 pm CEST

Effect of ionic liquid BMImBr on palladium-catalyzed oxidation of ethylene with LiNO3 Abstract  Oxidative bromination of ethylene was found to proceed effectively in the presence of a catalytic system Pd(OAc)2–LiNO3 in two-component BMImBr–HOAc and three-component BMImBr–HOAc–H2O solvents. At a large content of BMImBr, conversion of ethylene was found to yield 1,2-dibromoethane with a selectivity over 95%. The composition of the Pd(OAc)2–LiNO3 solutions was followed during the reaction of ethylene by means of UV–Vis spectroscopy. Content Type Journal Article Pages 191-197 DOI 10.1007/s11144-009-0043-z Authors Tatiana A. Balandina, Boreskov Institute of Catalysis, SB RAS Novosibirsk 630090 Russian Federation Tatiana V. Larina, Boreskov Institute of Catalysis, SB RAS Novosibirsk 630090 Russian Federation Dmitry V. Trebushat, Boreskov Institute of Catalysis, SB RAS Novosibirsk 630090 Russian Federation Nikolai Yu. Adonin, Boreskov Institute of Catalysis, SB RAS Novosibirsk 630090 Russian Federation Nina I. Kuznetsova, Boreskov Institute of Catalysis, SB RAS Novosibirsk 630090 Russian Federation Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 97 Journal Issue Volume 97, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 14 Jul 2009 | 1:09 pm CEST

Steady state energy distribution function of adatoms in reactive adsorption Abstract  The interplay between the energy distribution function of adatoms and the rate of diatom formation in catalytic reaction is studied by means of mean field rate equations. The recombination of adatoms is described as a multi-channel process where adatom desorption arises from several energy levels. It is shown that the distribution function can be computed, analytically, as a function of the ratio between recombination probability and rate constant for energy disposal to the solid. This parameter is the key quantity of the kinetics since it governs both reaction rate and the shape of the energy distribution function. It is found that, in order to obtain steady state conditions, the control parameter is constrained within a well defined interval of values which result lower than unity. It is shown that a kinetic transition takes place for the highest value of the parameter, which entails hyperthermal reaction rate. Content Type Journal Article Pages 179-189 DOI 10.1007/s11144-009-0039-8 Authors Massimo Tomellini, Università di Roma Tor Vergata Dipartimento di Scienze e Tecnologie Chimiche Via della Ricerca Scientifica Rome 00133 Italy Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 97 Journal Issue Volume 97, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 14 Jul 2009 | 1:09 pm CEST

Markedly enhancing the visible-light photocatalytic activity of LaFeO3 by post-treatment in molten salt Abstract  The visible-light photoactivity of LaFeO3 prepared by conventional co-precipitation method can be markedly enhanced by a simple and efficient post-treatment method. The catalyst treated with molten KNO3 exhibited the highest rate constant of 0.061 min−1 and after 60 min visible-light irradiation, 98% Acid Red 18 was decolorized, which was much higher than P25 TiO2. Content Type Journal Article Pages 269-274 DOI 10.1007/s11144-009-0025-1 Authors Jun Yang, Jinan University Department of Chemistry Guangzhou 510632 People’s Republic of China Huiqiong Zhong, Jinan University Department of Chemistry Guangzhou 510632 People’s Republic of China Ming Li, Jinan University Department of Chemistry Guangzhou 510632 People’s Republic of China Lizhen Zhang, Jinan University Department of Chemistry Guangzhou 510632 People’s Republic of China Yuanming Zhang, Jinan University Department of Chemistry Guangzhou 510632 People’s Republic of China Journal Reaction Kinetics and Catalysis Letters Online ISSN 1588-2837 Print ISSN 0133-1736 Journal Volume Volume 97 Journal Issue Volume 97, Number 2 Quelle: Reaction Kinetics and Catalysis Letters | 11 Jul 2009 | 8:57 am CEST