Showing papers on "Reaction rate published in 2006"

Enhancement of cellulose saccharification kinetics using an ionic liquid pretreatment step.

Abstract: Hydrolysis of cellulose to glucose in aqueous media catalyzed by the cellulase enzyme system suffers from slow reaction rates due in large part to the highly crystalline structure of cellulose and inaccessibility of enzyme adsorption sites. In this study, an attempt was made to disrupt the cellulose structure using the ionic liquid (IL), 1-n-butyl-3-methylimidazolium chloride, in a cellulose regeneration strategy which accelerated the subsequent hydrolysis reaction. ILs are a new class of non-volatilesolventsthatexhibituniquesolvatingproper- ties. They can be tuned to dissolve a wide variety of compounds including cellulose. Because of their extre- mely low volatility, ILs are expected to have minimal environmental impact on air quality compared to most other volatile solvent systems. The initial enzymatic hydrolysis rates were approximately 50-fold higher for regenerated cellulose as compared to untreated cellulose (Avicel PH-101) as measured by a soluble reducing sugar

Multiple Equilibria in Complex Chemical Reaction Networks: II. The Species-Reaction Graph

Abstract: For mass action kinetics, the capacity for multiple equilibria in an isothermal homogeneous continuous flow stirred tank reactor is determined by the structure of the underlying network of chemical reactions. We suggest a new graph-theoretical method for discriminating between complex reaction networks that can admit multiple equilibria and those that cannot. In particular, we associate with each network a species-reaction graph, which is similar to reaction network representations drawn by biochemists, and we show that, if the graph satisfies certain weak conditions, the differential equations corresponding to the network cannot admit multiple equilibria {\em no matter what values the rate constants take}. Because these conditions are very mild, they amount to powerful (and quite delicate) necessary conditions that a network must satisfy if it is to have the capacity to engender multiple equilibria. Broad qualitative results of this kind are especially apt, for individual reaction rate constants are rare...

Direct observation of reactive trapped holes in TiO2 undergoing photocatalytic oxidation of adsorbed alcohols: evaluation of the reaction rates and yields.

Abstract: To investigate the primary process of photocatalytic oxidation of TiO2, interfacial charge-transfer reaction of trapped holes formed in nanocrystalline TiO2 films by UV irradiation was directly measured by highly sensitive femtosecond and nanosecond transient absorption spectroscopy under low intensity excitation condition to avoid fast electron−hole recombination. Accordingly, the rates and yields of photocatalytic oxidation of several alcohols adsorbed on TiO2 were evaluated successfully.

Effect of water on sulfuric acid catalyzed esterification

Abstract: This paper reports on an investigation into the impact of water on liquid-phase sulfuric acid catalyzed esterification of acetic acid with methanol at 60 °C. In order to diminish the effect of water on the catalysis as a result of the reverse reaction, initial reaction kinetics were measured using a low concentration of sulfuric acid (1 × 10 −3 M) and different initial water concentrations. It was found that the catalytic activity of sulfuric acid was strongly inhibited by water. The catalysts lost up to 90% activity as the amount of water present increased. The order of water effect on reaction rate was determined to be −0.83. The deactivating effect of water also manifested itself by changes in the activation energy and the pre-exponential kinetic factor. The decreased activity of the catalytic protons is suggested to be caused by preferential solvation of them by water over methanol. A proposed model successfully predicts esterification rate as reaction progresses. The results indicate that, as esterification progresses and byproduct water is produced, deactivation of the sulfuric acid catalyst occurs. Autocatalysis, however, was found to be hardly impacted by the presence of water, probably due to compensation effects of water on the catalytic activity of acetic acid, a weak acid.

Effect of Pressure on the Behavior of Copper-, Iron-, and Nickel-Based Oxygen Carriers for Chemical-Looping Combustion

Abstract: The combustion process integrated by coal gasification and chemical-looping combustion (CLC) could be used in power plants with a low energy penalty for CO2 capture. This work analyzes the main characteristics related to the CLC process necessary to use the syngas obtained in an integrated gasification combined cycle (IGCC) power plant. The kinetics of reduction with H2 and CO and oxidation with O2 of three high-reactivity oxygen carriers used in the CLC system have been determined in a thermogravimetric analyzer at atmospheric pressure. The iron- and nickel-based oxygen carriers were prepared by freeze-granulation, and the copper-based oxygen carrier was prepared by impregnation. The changing grain size model (CGSM) was used for the kinetic determination, assuming spherical grains for the freeze-granulated particles containing iron and nickel and a platelike geometry for the reacting surface of the copper-based impregnated particles. The dependence of the reaction rates on temperature was low, with the a...

Catalytic hydrodeoxygenation of methyl-substituted phenols: correlations of kinetic parameters with molecular properties.

Abstract: The hydrodeoxygenation of methyl-substituted phenols was carried out in a flow microreactor at 300 degrees C and 2.85 MPa hydrogen pressure over a sulfided CoMo/Al(2)O(3) catalyst. The primary reaction products were methyl-substituted benzene, cyclohexene, cyclohexane, and H(2)O. Analysis of the results suggests that two independent reaction paths are operative, one leading to aromatics and the other to partially or completely hydrogenated cyclohexanes. The reaction data were analyzed using Langmuir-Hinshelwood kinetics to extract the values of the reactant-to-catalyst adsorption constant and of the rate constants characterizing the two reaction paths. The adsorption constant was found to be the same for both reactions, suggesting that a single catalytic site center is operative in both reactions. Ab initio electronic structure calculations were used to evaluate the electrostatic potentials and valence orbital ionization potentials for all of the substituted phenol reactants. Correlations were observed between (a) the adsorption constant and the two reaction rate constants measured for various methyl-substitutions and (b) certain moments of the electrostatic potentials and certain orbitals' ionization potentials of the isolated phenol molecules. On the basis of these correlations to intrinsic reactant-molecule properties, a reaction mechanism is proposed for each pathway, and it is suggested that the dependencies of adsorption and reaction rates upon methyl-group substitution are a result of the substituents' effects on the electrostatic potential and orbitals rather than geometric (steric) effects.

Degradation of pesticides in water using solar advanced oxidation processes

Abstract: Alachlor, atrazine and diuron dissolved in water at 50, 25 and 30 mg/L, respectively were photodegraded by Fe2+/H2O2, Fe3+/H2O2, TiO2 and TiO2/Na2S2O8 treatments driven by solar energy at pilot-plant scale using a compound parabolic collector (CPC) photoreactor. All the advanced oxidation processes (AOPs) employed mainly compared the TOC mineralisation rate to evaluate treatment effectiveness. Parent compound disappearance, anion release and oxidant consumption are discussed as a function of treatment time. The use of Fe2+ or Fe3+ showed no influence on the reaction rate under illumination and the reaction using 10 or 55 mg/L of iron was quite similar. TiO2/Na2S2O8 showed a quicker reaction rate than TiO2 and a similar rate compared to photo-Fenton. The main difference found was between TiO2/Na2S2O8 and photo-Fenton, detected during atrazine degradation, where pesticide transformation into cyanuric acid was confirmed only for TiO2/Na2S2O8

The effect of varying levels of surfactant on the reactive uptake of N 2 O 5 to aqueous aerosol

Abstract: . Recent observations have detected surface active organics in atmospheric aerosols. We have studied the reaction of N2O5 on aqueous natural seawater and NaCl aerosols as a function of sodium dodecyl sulfate (SDS) concentration to test the effect of varying levels of surfactant on gas-aerosol reaction rates. SDS was chosen as a proxy for naturally occurring long chain monocarboxylic acid molecules, such as palmitic or stearic acid, because of its solubility in water and well-characterized surface properties. Experiments were performed using a newly constructed aerosol flow tube coupled to a chemical ionization mass spectrometer for monitoring the gas phase, and a differential mobility analyzer/condensation particle counter for determining aerosol surface area. We find that the presence of ~3.5wt% SDS in the aerosol, which corresponds to a monolayer surface coverage of ~2×1014 molecules cm-2, suppresses the N2O5 reaction probability, γN2O5, by approximately a factor of ten, independent of relative humidity. Consistent with this observation is a similar reduction in the rate of ClNO2 product generation measured simultaneously. However, the product yield remains nearly constant under all conditions. The degree of suppression is strongly dependent on SDS content in the aerosol, with no discernable effect at 0.1wt% SDS, but significant suppression at what we predict to be submonolayer coverages with 0.3–0.6wt% SDS on NaCl and natural seawater aerosols, respectively.

Kinetics of the absorption of CO2 into mixed aqueous loaded solutions of monoethanolamine and methyldiethanolamine

Abstract: The kinetics of absorption of CO2 in loaded mixed methyldiethanolamine (MDEA) and monoethanolamine (MEA) solutions was investigated in a laboratory laminar jet apparatus. The experiments were conducted over the temperature range of 298−333 K, MDEA/MEA wt ratio of 27/03, 25/05 and 23/07, total amine concentration of 30 wt %, and CO2 loading from 0.005 to 0.15 (mol of CO2)/(mol of total amine). Physical properties such as density, viscosity, diffusivity, and solubility of the system were calculated from published data and/or models. Reaction mechanisms, namely, zwitterion and termolecular, were used to interpret the kinetic data. It was observed that the zwitterion mechanism in its original form could not predict the individual kinetic rate constants. Equally, the termolecular mechanism with water in the apparent reaction rate term also did not yield any reasonable results. A modified termolecular mechanism, which included the contribution of hydroxide ions, was able to predict the kinetics of a CO2 loaded ...

Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

Abstract: A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H2 production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H2 with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH3OH→H2COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.

Kinetic effects of hydrogen bonds on proton-coupled electron transfer from phenols

Abstract: The kinetics and mechanism of proton-coupled electron transfer (PCET) from a series of phenols to a laser flash generated [Ru(bpy)(3)](3+) oxidant in aqueous solution was investigated. The reaction followed a concerted electron-proton transfer mechanism (CEP), both for the substituted phenols with an intramolecular hydrogen bond to a carboxylate group and for those where the proton was directly transferred to water. Without internal hydrogen bonds the concerted mechanism gave a characteristic pH-dependent rate for the phenol form that followed a Marcus free energy dependence, first reported for an intramolecular PCET in Sjodin, M. et al. J. Am. Chem. Soc. 2000, 122, 3932-3962 and now demonstrated also for a bimolecular oxidation of unsubstituted phenol. With internal hydrogen bonds instead, the rate was no longer pH-dependent, because the proton was transferred to the carboxylate base. The results suggest that while a concerted reaction has a relatively high reorganization energy (lambda), this may be significantly reduced by the hydrogen bonds, allowing for a lower barrier reaction path. It is further suggested that this is a general mechanism by which proton-coupled electron transfer in radical enzymes and model complexes may be promoted by hydrogen bonding. This is different from, and possibly in addition to, the generally suggested effect of hydrogen bonds on PCET in enhancing the proton vibrational wave function overlap between the reactant and donor states. In addition we demonstrate how the mechanism for phenol oxidation changes from a stepwise electron transfer-proton transfer with a stronger oxidant to a CEP with a weaker oxidant, for the same series of phenols. The hydrogen bonded CEP reaction may thus allow for a low energy barrier path that can operate efficiently at low driving forces, which is ideal for PCET reactions in biological systems.

Application of in-situ attenuated total reflection-Fourier transform infrared spectroscopy for the understanding of complex reaction mechanism and kinetics: formic acid oxidation on a Pt film electrode at elevated temperatures.

Abstract: The potential of in-situ Fourier transform infrared (FTIR) spectroscopy measurements in an attenuated total reflection configuration (ATR-FTIRS) for the evaluation of reaction pathways, elementary reaction steps, and their kinetics is demonstrated for formic acid electrooxidation on a Pt film electrode. Quantitative kinetic information on two elementary steps, formic acid dehydration and COad oxidation, and on the contributions of the related pathways in the dual path reaction mechanism are derived from IR spectroscopic signals in simultaneous electrochemical and ATR-FTIRS measurements over a wide temperature range (25−80 °C). Linearly and multiply bonded COad and bridge-bonded formate are the only formic acid related stable reaction intermediates detected. With increasing temperature, the steady-state IR signal of COad increases, while that of formate decreases. Reaction rates for COad formation via formic acid dehydration and for COad oxidation as well as the activation energies of these processes were ...