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Diffusion Limitation (diffusion + limitation)
Selected AbstractsHigh-Resolution Single-Turnover Mapping Reveals Intraparticle Diffusion Limitation in Ti-MCM-41-Catalyzed Epoxidation,ANGEWANDTE CHEMIE, Issue 5 2010Cremer, Gert De Katalyse in neuem Licht: Mithilfe hochauflösender Fluoreszenzmikroskopie gelang es erstmals, Transportphänomene und deren Rolle in der Katalyse auf Einzelpartikelebene zu kartieren. Der Thiele-Modul konnte partikelweise in nur einem einzigen Experiment gemessen werden, und er beweist das Vorliegen von Diffusionsbeschränkungen bei der Ti-MCM-41-katalysierten Epoxidierung eines fluoreszierenden Reportermoleküls (siehe Bild; TBHP=tert -Butylhydroperoxid). [source] Modeling of Diffusion Limitations in Bulk RAFT PolymerizationMACROMOLECULAR THEORY AND SIMULATIONS, Issue 7 2006A. David Peklak Abstract Summary: The impact of diffusion limitations on RAFT polymerizations is investigated in this work. In particular, two models are compared: one accounting for diffusion limitations by using average chain lengths, the other accounting for the entire CLD. It is shown that such a description is necessary to correctly predict the kinetics of polymerization processes, as well as the evolution of average chain length and polydispersity. For properly selected study cases, differing conversion curves are obtained above 40% monomer conversion, if only average values of the CLD are considered. The same is valid for the calculation of the polydispersity, which starts differing above 80% conversion. Finally, for given conditions of diffusion limitations, it is found that an ideal polydispersity can be defined and it is shown that the polydispersity tends to this characteristic value during the entire evolution of the polymerization process. as a function of f for various values of . [source] Red Cell Pulmonary Transit Times Through the Healthy Human LungEXPERIMENTAL PHYSIOLOGY, Issue 2 2003G. S. Zavorsky It has previously been postulated that rapid red cell capillary transit through the human lung plays a role in the mechanism of diffusion limitation in some endurance athletes. Methodological limitations currently prevent researchers from directly measuring pulmonary capillary transit times in humans during exercise; however, first pass radionuclide cardiography allows direct measurement of red blood cell (RBC) transit times through the whole lung at various exercise intensities. We examined the relationship between mean whole lung red cell pulmonary transit times (cardiopulmonary transit times or CPTT) and different levels of flow in 88 healthy humans (76 males, 12 females) from several studies (mean age 31 years). The pooled data suggest that the relationship between CPTT and cardiac index (CI), beginning at rest and progressing through to maximum exercise demonstrates that CPTT reaches its minimum value when CI is about 8.1 l m2 min,1 (2.5-3 times the CI value at rest), and does not significantly change with further increases in CI. Cardiopulmonary blood volume (CPBV) index also does not change significantly until CI reaches 2.5 to 3 times the CI value at rest and then increases roughly linearly after that point. Consequently, the systematic increase in CPBV index with increasing pulmonary blood flow between 8.1 and 20 l m2 min,1 displays an adaptive response of the cardiopulmonary system by augmenting CPBV (and perhaps pulmonary capillary blood volume through distension and recruitment) to offset the reduction in CPTT, as no significant difference in mean CPTT is observed between these levels of flow (P > 0.05). Therefore, these data demonstrate that CPBV does not reach maximum capacity during strenuous or maximum exercise. This does not support the principle of quarter-power allometric scaling for flow when explaining modifications during exercise. Therefore, we speculate that the observed relationships between CPTT, CBPV index and flow may prevent mean CPTT (and perhaps mean pulmonary capillary transit times) from decreasing below the threshold time required for oxygenation. [source] New Stack Design of Micro-tubular SOFCs for Portable Power SourcesFUEL CELLS, Issue 6 2008T. Suzuki Abstract Micro-tubular solid oxide fuel cells (SOFCs) have high thermal stability and higher volumetric power density, which are considered to be ideal features for portable power sources and auxiliary power units for automobile. Here, we report a new stack design using anode supported micro-tubular SOFCs with 2,mm diameter using Gd doped CeO2 (GDC) electrolyte, NiO-GDC anode and (La, Sr)(Co, Fe)O3 (LSCF)-GDC cathode. The new stack consists of three bundles with five tubular cells, sealing layers and interconnects and fuel manifolds. The performance of the stack whose volume is 1,cm3 was shown to be 2.8,V OCV and maximum power output of 1.5,W at 500,°C, applying air only by natural convection. The results also showed strong dependence of the fuel flow rates on the stack performance, which was correlated to the gas diffusion limitation. [source] Lipid biomarker and carbon isotopic signatures for stromatolite-forming, microbial mat communities and Phormidium cultures from Yellowstone National ParkGEOBIOLOGY, Issue 1 2004Linda L. Jahnke ABSTRACT The molecular and isotopic compositions of lipid biomarkers from cultured filamentous cyanobacteria (Phormidium, also known as Leptolyngbya) have been used to investigate the community and trophic structure of photosynthetic mats from alkaline hot springs of the Lower Geyser Basin at Yellowstone National Park. We studied a shallow-water coniform mat from Octopus Spring (OS) and a submerged, tufted mat from Fountain Paint Pots (FPP) and found that 2-methylhopanepolyols and mid-chain branched methylalkanes were diagnostic for cyanobacteria, whereas abundant wax esters were representative of the green non-sulphur bacterial population. The biomarker composition of cultured Phormidium -isolates varied, but was generally representative of the bulk mat composition. The carbon isotopic fractionation for biomass relative to dissolved inorganic carbon (DIC; ,CO2) for cultures grown with 1% CO2 ranged from 21.4 to 26.1 and was attenuated by diffusion limitation associated with filament aggregation (i.e. cell clumping). Isotopic differences between biomass and lipid biomarkers, and between lipid classes, depended on the cyanobacterial strain, but was positively correlated with overall fractionation. Acetogenic lipids (alkanes and fatty acids) were generally more depleted than isoprenoids (phytol and hopanoids). The ,13CTOC for OS and FPP mats were somewhat heavier than for cultures (,16.9 and ,23.6, respectively), which presumably reflects the lower availability of DIC in the natural environment. The isotopic dispersions among cyanobacterial biomarkers, biomass and DIC reflected those established for culture experiments. The 7-methyl- and 7,11-dimethylheptadecanes were from 9 to 11 depleted relative to the bulk organic carbon, whereas 2-methylhopanols derived from the oxidation-reduction of bacteriohopanepolyol were enriched relative to branched alkanes by approximately 5,7. These isotopic relationships survived with depth and indicated that the relatively heavy isotopic composition of the OS mat resulted from diffusion limitation. This study supports the suggestion that culture studies can establish valid isotopic relationships for interpretation of trophic structure in modern and ancient microbial ecosystems. [source] Kinetics and mechanism of myristic acid and isopropyl alcohol esterification reaction with homogeneous and heterogeneous catalystsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2008Tuncer Yalçinyuva The reaction of myristic acid (MA) and isopropyl alcohol (IPA) was carried out by using both homogeneous and heterogeneous catalysts. For a homogeneously catalyzed system, the experimental data have been interpreted with a second order, using the power-law kinetic model, and a good agreement between the experimental data and the model has been obtained. In this approach, it was assumed that a protonated carboxylic acid is a possible reaction intermediate. After a mathematical model was proposed, reaction rate constants were computed by the Polymath* program. For a heterogeneously catalyzed system, interestingly, no pore diffusion limitation was detected. The influences of initial molar ratios, catalyst loading and type, temperature, and water amount in the feed have been examined, as well as the effects of catalyst size for heterogeneous catalyst systems. Among used catalysts, p -toluene sulfonic acid (p -TSA) gave highest reaction rates. Kinetic parameters such as activation energy and frequency factor were determined from model fitting. Experimental K values were found to be 0.54 and 1.49 at 60°C and 80°C, respectively. Furthermore, activation energy and frequency factor at forward were calculated as 54.2 kJ mol,1 and 1828 L mol,1 s,1, respectively. © 2008 Wiley Periodicals, Inc. 40: 136,144, 2008 [source] Solid-solid reactions in series: A modeling and experimental studyAICHE JOURNAL, Issue 9 2009A. K. Suresh Abstract Reactions among particulate solid phases are important and abundant in many materials, chemical, and metallurgical process industries. Many of these are reaction networks, and not single-step reactions as normally assumed. There is no theoretical framework available for the analysis of such systems, and single-reaction models derived from the gas,solid literature continue to be used. Formation of cement clinker in the rotary cement kiln is a prime example of the genre, in which mechanistic aspects play an important role in determining energy efficiency and the composition and nature of the phases that form. In the present study, we formulate a model within the ambit of the "shrinking core" class of models, for reactions in series among solid phases. The model shows the presence of one or two moving fronts in the reacting particle, depending on the relative rates of the processes involved. A single Thiele-type parameter controls the model behavior, at once describing the relative rates of the intermediate formation and consumption processes, and the diffusion-reaction competition for the product formation step. The model has been shown to reduce to the well known single reaction models at the limits of low and high values of the Thiele parameter. Experimental data have been obtained on the calcia-alumina system, an important one in cement manufacture, in the temperature range 1150,1250°C. The model has been fitted to these data and the kinetic parameters determined. The comparison bears out the salient features of the theory, and shows that a degree of diffusion limitation exists for the intermediate conversion step under these conditions. The diffusivity values estimated are in the range of 10,19 to 10,18 m2/s and agree with values found in the literature for similar systems. The rate constant for the intermediate conversion step is of the order of 10,6 s,1. This being among the first such determinations, this value awaits confirmation from other studies. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Recent data on the number of active centers and propagation rate constants in olefin polymerization with supported ZN catalystsMACROMOLECULAR SYMPOSIA, Issue 1 2004V.A. Zakharov Abstract Data on the number of active centers (Cp) and propagation rate constants (Kp) have been obtained by means of polymerization quenching with 14CO of propylene and ethylene polymerization with supported titanium-magnesium catalysts (TMC) with different composition. In the case of propylene polymerization the Cp and Kp values have been measured separately for isospecific, aspecific and low stereospecific centers. Effects of MgCl2 support, internal and external donors are discussed on the basis of data obtained. Data on the strong effect of diffusion limitation at ethylene polymerization with number of TMC have been obtained and a set of methods have been used to exclude this effect. Data on Cp and Kp values at ethylene polymerization with low stereospecific and highly stereospecific catalysts are presented. [source] Glucose Oxidation Catalyzed by Liposomal Glucose Oxidase in the Presence of Catalase-Containing LiposomesBIOTECHNOLOGY PROGRESS, Issue 3 2006Makoto Yoshimoto A catalase-containing liposome (CAL) was prepared and characterized in terms of stability during storage and catalysis of the decomposition of hydrogen peroxide (H2O2) that was initially added or produced in the oxidation of glucose catalyzed by the glucose oxidase-containing liposomes (GOL). The reactors used were a test tube and an external loop airlift bubble column as the static liquid and circulating liquid flow systems, respectively. The free catalase (CA) at low concentrations was unstable during storage at 4 °C as a result of dissociation of the tetrameric CA subunits. On the other hand, the deactivation of the CA activity in the CAL was depressed because of the high CA concentration in the CAL liposome. The CAL effectively catalyzed the repeated decompositions at 25 °C with 10 mM H2O2 added initially, whereas the free CA was significantly deactivated during the repeated reactions. The high stability of the CAL was attributed to the moderately depressed reactivity, which was essentially derived from the diffusion limitation of the CAL membrane to H2O2 in the liquid bulk. In the GOL-catalyzed prolonged oxidation of 10 mM glucose at 40 °C in the static liquid in a test tube, both the free CA and CAL could continuously catalyze the decomposition of H2O2 produced. This was because the glucose oxidation rate was small due to the limited reactivity of the GOL to glucose with its low permeability through the GOL membrane. In the glucose oxidation catalyzed by the GOL with the free CA or the CAL in the airlift, much larger oxidation rates were observed compared to those in the test tube because the permeability of the GOL membrane to glucose was increased in the gas-liquid two phase flow in the airlift. The GOL/CAL system in the airlift operated in an acidic condition, which was preferable to the GO activity, gave the largest oxidation rate with negligible accumulation of the H2O2 produced. On the other hand, the GOL/free CA system gave an oxidation rate smaller than that of the GOL/CAL system even under the acidic condition due to an unfavorable interaction of the free CA molecules with the GOL membranes leading to the decreased reactivity of the GOL. [source] Immobilization of ,-Galactosidase on Fibrous Matrix by Polyethyleneimine for Production of Galacto-Oligosaccharides from LactoseBIOTECHNOLOGY PROGRESS, Issue 2 2002Nedim Albayrak The production of galacto-oligosaccharides (GOS) from lactose by Aspergillus oryzae ,-galactosidase immobilized on cotton cloth was studied. A novel method of enzyme immobilization involving PEI,enzyme aggregate formation and growth of aggregates on individual fibrils of cotton cloth leading to multilayer immobilization of the enzyme was developed. A large amount of enzyme was immobilized (250 mg/g support) with about 90,95% efficiency. A maximum GOS production of 25,26% (w/w) was achieved at near 50% lactose conversion from 400 g/L of lactose at pH 4.5 and 40 °C. Tri- and tetrasaccharides were the major types of GOS formed, accounting for about 70% and 25% of the total GOS produced in the reactions, respectively. Temperature and pH affected not only the reaction rate but also GOS yield to some extend. A reaction pH of 6.0 increased GOS yield by as much as 10% compared with that of pH 4.5 while decreased the reaction rate of immobilized enzyme. The cotton cloth as the support matrix for enzyme immobilization did not affect the GOS formation characteristics of the enzyme under the same reaction conditions, suggesting diffusion limitation was negligible in the packed bed reactor and the enzyme carrier. Increase in the thermal stability of PEI-immobilized enzyme was also observed. The half-life for the immobilized enzyme on cotton cloth was close to 1 year at 40 °C and 21 days at 50 °C. Stable, continuous operation in a plug-flow reactor was demonstrated for about 3 days without any apparent problem. A maximum GOS production of 26% (w/w) of total sugars was attained at 50% lactose conversion with a feed containing 400 g/L of lactose at pH 4.5 and 40 °C. The corresponding reactor productivity was 6 kg/L/h, which is several-hundred-fold higher than those previously reported. [source] Kinetics of cadmium accumulation in periphyton under freshwater conditions,ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 10 2009Philippe Bradac Abstract The aim of the present study was to investigate the kinetics of cadmium (Cd) accumulation (total and intracellular) in periphyton under freshwater conditions in a short-term microcosm experiment. Periphyton was precolonized in artificial flow-through channels supplied with natural freshwater and then exposed for 26.4 h to nominal Cd concentrations of 5 and 20 nM added to natural freshwater. Labile Cd in water determined with diffusion gradient in thin films was 60 to 69% of total dissolved Cd in the exposure channels and 11% in the control channel. Intracellular Cd concentrations in periphyton increased rapidly and linearly during the first 71 min. Initial intracellular uptake rates were 0.05 and 0.18 nmol of Cd/g of dry weight × min in the 5 nM and 20 nM exposures, respectively. The subsequent intracellular uptake was slower, approaching steady state at the end of Cd exposure. Uptake kinetics of Cd was slower when compared to experiments with planktonic algal cultures, probably due to diffusion limitations. Intracellular Cd uptake during the entire exposure was modeled with a nonlinear, one-compartment model from which uptake and clearance rate constants, as well as bioconcentration factors, were obtained. The release of Cd from periphyton after the end of Cd exposure was slow when compared to the initial uptake rates. [source] Synthesis of carvacrol by Friedel,Crafts alkylation of o -cresol with isopropanol using superacidic catalyst UDCaT-5JOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 10 2009Ganapati D. Yadav Abstract BACKGROUND: Alkylation of o -cresol with propylene or isopropyl alcohol (IPA) over solid acid catalysts results in the formation of carvacrol, which finds potential applications in the synthesis of fine chemicals, intermediates, specialty chemicals, flavours and fragrances. RESULTS: The present work covers evaluation of novel mesoporous superacidic catalysts namely UDCaT-4, UDCaT-5 and UDCaT-6 in the greener synthesis of carvacrol. The catalysts are modified versions of zirconia showing high catalytic activity, stability and reusability. The catalytic activity increases in the following order: UDCaT-5 > UDCaT-4 > UDCaT-6 > sulfated zirconia. The process was optimized and a mathematical model developed to describe the reaction pathway in liquid phase. Carvacrol could be efficiently obtained with a selectivity up to 82% at an isopropanol conversion of 98% after 2 h over UDCaT-5 at 180 °C. CONCLUSION: The reaction is free from any external mass transfer as well as intraparticle diffusion limitations and is intrinsically kinetically controlled. An overall second-order kinetic equation was used to fit the experimental data. The activation energy was found to be 19.2 kcal/mol. The reaction was carried out without any solvent in order to make the process cleaner and greener. Copyright © 2009 Society of Chemical Industry [source] Dendronized Polymers via Macromonomer Route in Supercritical Carbon DioxideMACROMOLECULAR RAPID COMMUNICATIONS, Issue 19 2008Liborio Ivano Costa Abstract Radical polymerizations from third to fifth generation macromonomers were conducted in supercritical carbon dioxide (scCO2). It was found that all monomers were not soluble in such a medium, and reactions occurred in the CO2 -swollen monomer matrices. Despite the expected severe diffusion limitations, very high conversions and molecular weights were obtained. It is believed that the plasticization effect induced by the CO2 plays a key role in these surprising findings. Scanning force microscopical analyses confirmed that mainly linear dendronized polymers were obtained and therefore chain transfer to polymer is virtually irrelevant. [source] Modeling of Diffusion Limitations in Bulk RAFT PolymerizationMACROMOLECULAR THEORY AND SIMULATIONS, Issue 7 2006A. David Peklak Abstract Summary: The impact of diffusion limitations on RAFT polymerizations is investigated in this work. In particular, two models are compared: one accounting for diffusion limitations by using average chain lengths, the other accounting for the entire CLD. It is shown that such a description is necessary to correctly predict the kinetics of polymerization processes, as well as the evolution of average chain length and polydispersity. For properly selected study cases, differing conversion curves are obtained above 40% monomer conversion, if only average values of the CLD are considered. The same is valid for the calculation of the polydispersity, which starts differing above 80% conversion. Finally, for given conditions of diffusion limitations, it is found that an ideal polydispersity can be defined and it is shown that the polydispersity tends to this characteristic value during the entire evolution of the polymerization process. as a function of f for various values of . [source] C4 photosynthesis in a single C3 cell is theoretically inefficient but may ameliorate internal CO2 diffusion limitations of C3 leavesPLANT CELL & ENVIRONMENT, Issue 8 2003S. VON CAEMMERER ABSTRACT Attempts are being made to introduce C4 photosynthetic characteristics into C3 crop plants by genetic manipulation. This research has focused on engineering single-celled C4 -type CO2 concentrating mechanisms into C3 plants such as rice. Herein the pros and cons of such approaches are discussed with a focus on CO2 diffusion, utilizing a mathematical model of single-cell C4 photosynthesis. It is shown that a high bundle sheath resistance to CO2 diffusion is an essential feature of energy-efficient C4 photosynthesis. The large chloroplast surface area appressed to the intercellular airspace in C3 leaves generates low internal resistance to CO2 diffusion, thereby limiting the energy efficiency of a single-cell C4 concentrating mechanism, which relies on concentrating CO2 within chloroplasts of C3 leaves. Nevertheless the model demonstrates that the drop in CO2 partial pressure, pCO2, that exists between intercellular airspace and chloroplasts in C3 leaves at high photosynthetic rates, can be reversed under high irradiance when energy is not limiting. The model shows that this is particularly effective at lower intercellular pCO2. Such a system may therefore be of benefit in water-limited conditions when stomata are closed and low intercellular pCO2 increases photorespiration. [source] Dye-affinity hollow-fibres and their lysozyme adsorption,desorption characteristicsPOLYMER INTERNATIONAL, Issue 10 2001Serap, enel Abstract Dye-affinity adsorption is increasingly used for protein separation. Hollow-fibres have advantages as adsorbents in comparison to conventional bead supports because they are not compressible and can eliminate internal diffusion limitations. The aim of this study was to explore in detail the performance of polyamide hollow-fibres to which Reactive Green HE-4BD was attached for adsorption of lysozyme. The hollow-fibre was characterized by scanning electron microscopy. These dye-carrying hollow-fibres (26.3,µmol,g,1) were used in the lysozyme adsorption,elution studies. The effect of initial concentration of lysozyme and medium pH on the adsorption efficiency of dye-attached hollow-fibres was studied in a batch system. The non-specific adsorption of lysozyme on the polyamide hollow-fibres was 1.8,mg,g,1. Reactive Green HE-4BD attachment significantly increased the lysozyme adsorption up to 41.1,mg,g,1. Langmuir adsorption model was found to be applicable in interpreting lead adsorption by Reactive Green HE-4BD attached hollow fibres. Significant amount of the adsorbed lysozyme (up to 95%) was eluted in 1,h in the elution medium containing 1.0,M NaSCN at pH 8.0. In order to determine the effects of adsorption conditions on possible conformational changes of lysozyme structure, fluorescence spectrophotometry was employed. We concluded that polyamide dye-affinity hollow-fibres can be applied for lysozyme adsorption without causing any significant conformational changes. Repeated adsorption,elution processes showed that these dye-attached hollow-fibres are suitable for lysozyme adsorption. © 2001 Society of Chemical Industry [source] Rate equations for the fischer-tropsch reaction on a promoted iron catalystTHE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, Issue 5 2001Montazer Rahmati Abstract Intrinsic rates for the Fischer-Tropsch synthesis reaction over a promoted iron catalyst fabricated at the Research Institute of the Petroleum Industry (RIPI) have been obtained in the temperature range of 290°C to 310°C, pressure range of 1500 to 2300 kPa, molar hydrogen to carbon monoxide ratio of 0.76 to 1.82, and a space velocity of 3300 h,1 under conditions of constant catalyst activity. To this end, the initial reaction rates have been measured at constant temperature (±1°C) in the absence of diffusion limitations, and power-law equations have been fitted in terms of the hydrogen and carbon monoxide partial pressures for the reaction rates. Des vitesses intrinsèques pour la réaction de synthèse de Fischer-Tropsch sur un catalyseur de fer activé fabriqué à l'Institut de recherche de l'industrie du pétrole (RIPI) ont été obtenues pour des températures entre 290°C et 310°C, des pressions entre 1500 et 2300 kPa, un rapport hydrogène molaire/oxyde de carbone entre 0.76 et 1.82 et une vitesse spatiale de 3300 h,1 avec une activité constante du catalyseur. À cette fin, les vitesses de réaction initiales ont été mesurées à température constante (±1°C) en l'absence de limitations par la diffusion, et des équations de loi de puissance ont été calées par rapport aux pressions partieiles de l'hydrogène et de l'oxyde de carbone pour les vitesses de réaction. [source] | ||||||||||||||||