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Reaction Progress (reaction + progress)
Selected AbstractsReaction progress related to indentation structures at glaucophane/glaucophane contacts in an impure marble from Syros, GreeceJOURNAL OF METAMORPHIC GEOLOGY, Issue 8 2006A. OKAMOTO Abstract Microstructures of brittle mineral grains embedded in a ductile matrix provide information on the influence of stress concentration on reaction progress during metamorphism. Under non-hydrostatic conditions, contrasts of mechanical properties between minerals possibly cause stress concentrations at specific grain boundaries, which may result in a localization of subsequent reactions. In an impure marble from Syros, Greece, glaucophane grains occurring in a calcite matrix commonly impinge on other glaucophane grains to form concavo-convex boundary contacts. The geometrical relationship between grain boundary and growth zoning within glaucophane grains indicates that indentation and dissolution occurred preferentially at the glaucophane/glaucophane contacts in response to compression normal to the foliation. In contrast, idioblastic surfaces of glaucophane were preserved at glaucophane/calcite boundaries, indicating that stress concentrated at glaucophane/glaucophane contacts. The retrograde minerals (winchite, albite and biotite) that were formed by consuming glaucophane are observed not only at the extensive site, but also at the ,compressive' site where indentation occurred. The precipitation of retrograde minerals at the extensive sites was accompanied by glaucophane dissolution at the indentation stage. In contrast, the formation of retrograde minerals at the ,compressive' site indicates that retrograde replacement preferentially proceeded at the indented sites even after stress relaxation. Such a localization of the replacement suggests that the formation of damaged zones around glaucophane/glaucophane contacts induced by stress concentration would have provided the preferential sites for glaucophane breakdown at the later stage. [source] Progress of actinolite-forming reactions in mafic schists during retrograde metamorphism: an example from the Sanbagawa metamorphic belt in central Shikoku, JapanJOURNAL OF METAMORPHIC GEOLOGY, Issue 5 2005A. OKAMOTO Abstract Hydration reactions are direct evidence of fluid,rock interaction during regional metamorphism. In this study, hydration reactions to produce retrograde actinolite in mafic schists are investigated to evaluate the controlling factors on the reaction progress. Mafic schists in the Sanbagawa belt contain amphibole coexisting with epidote, chlorite, plagioclase and quartz. Amphibole typically shows two types of compositional zoning from core to rim: barroisite , hornblende , actinolite in the high-grade zone, and winchite , actinolite in the low-grade zone. Both types indicate that amphibole grew during the exhumation stage of the metamorphic belt. Microstructures of amphibole zoning and mass-balance relations suggest that: (1) the actinolite-forming reactions proceeded at the expense of the preexisting amphibole; and (2) the breakdown reaction of hornblende consumed more H2O fluid than that of winchite, when one mole of preexisting amphibole was reacted. Reaction progress is indicated by the volume fraction of actinolite to total amphibole, Yact, with the following details: (1) reaction proceeded homogeneously in each mafic layer; (2) the extent of the hornblende breakdown reaction is commonly low (Yact < 0.5), but it increases drastically in the high-grade part of the garnet zone (Yact,>,0.7); and (3) the extent of the winchite breakdown reaction is commonly high (Yact,>,0.7). Many microcracks are observed within hornblende, and the extent of hornblende breakdown reaction is correlated with the size reduction of the hornblende core. Brittle fracturing of hornblende may have enhanced retrograde reaction progress by increasing of influx of H2O and the surface area of hornblende. In contrast to high-grade rocks, the winchite breakdown reaction is well advanced in the low-grade rocks, where reaction progress is not associated with brittle fracturing of winchite. The high extent of the reaction in the low-grade rocks may be due to small size of winchite before the reaction. [source] Screening of Different Titanium (IV) Catalysts in the Synthesis of Poly(ethylene terephthalate)MACROMOLECULAR REACTION ENGINEERING, Issue 6 2008Fatemeh Ahmadnian Abstract The polycondensation of bis(hydroxyethylene) terephthalate and its oligomers to PET catalyzed by different chelated and non-chelated titanium catalysts in a lab-scale stirred-tank reactor and differential scanning calorimeter were investigated. Different titanium compounds showed different activity and selectivity. The nature of catalyst ligands plays an important role in catalyst efficiency. Non-chelated titanium derivatives were more active and less selective. Reaction progress is characterized by an initial inhibition period depending on the type of catalyst. The original titanium compounds used are precursors and are probably activated by a ligand exchange reaction. [source] Substitution- and Elimination-Free Phosphorylation of Functionalized Alcohols Catalyzed by Oxidomolybdenum TetrachlorideADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1 2010Cheng-Yuan Liu Abstract Among 14 oxidometallic species examined for catalytic phosphorylation of the tested alcohols, oxidomolybdenum tetrachloride (MoOCl4) was found to be the most efficient with a negligible background reaction mediated by triethylamine (Et3N). The new catalytic protocol can be applied to the chemoselective phosphorylations of primary, secondary and tertiary alcohols as well as the substitution-free phosphorylations of allylic, propargylic, and benzylic alcohols. Functionalized alcohols bearing acetonide, tetrahydropyranyl ether, tert -butyldimethylsilyl ether, or ester group are also amenable to the new catalytic protocol. The most difficult scenarios involve substitution-free phosphorylations of 1-phenylethanol and 1-(2-naphthyl)ethanol which can be effected in 95 and 90% yields, respectively. ESI-MS, IR, 1H, and 31P,NMR spectroscopic analyses of the reaction progress suggest the intermediacy of an alkoxyoxidomolybdenum trichloride-triethylamine adduct such as [(RO)Mo(O)Cl3 -Et3N] to be responsible for the catalytic turnover. [source] Moisture curing kinetics of isocyanate ended urethane quasi-prepolymers monitored by IR spectroscopy and DSCJOURNAL OF APPLIED POLYMER SCIENCE, Issue 2 2008Ana Luísa Daniel-da-Silva Abstract The study of the kinetics of the curing of isocyanate quasi-prepolymers with water was performed by infrared spectroscopy and differential scanning calorimetry. The influence of the free isocyanate content, polyol functionality, and of the addition of an amine catalyst (2,2,-dimorpholinediethylether) in the reaction kinetics and morphology of the final poly(urethane urea) was analyzed. A second-order autocatalyzed model was successfully applied to reproduce the curing process under isothermal curing conditions, until gelation occurred. A kinetic model-free approach was used to find the dependence of the effective activation energy (Ea) with the extent of cure, when the reaction was performed under nonisothermal conditions. The dependence of Ea with the reaction progress was different depending on the initial composition of the quasi-prepolymer, which reveals the complexity of the curing process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008 [source] Experimental dehydration kinetics of serpentinite using pore volumometryJOURNAL OF METAMORPHIC GEOLOGY, Issue 4 2007S. LLANA-FÚNEZ Abstract A series of dehydration experiments was carried out on both intact rock and cold-pressed powdered samples of serpentinite at temperatures in the range 535,610 °C, 100,170 °C above the onset of the breakdown temperature of 435 °C. Pore water pressures near 120 MPa were servo-controlled using a pore volumometer that also allowed dehydration reaction progress to be monitored through measurement of the amount of evolved water. Effective hydrostatic confining pressures were varied between 0 and 113 MPa. The reaction rate of intact specimens of initially near-zero porosity was constant up to 50,80% reaction progress at any given temperature, but decreased progressively as transformation approached completion. Water expulsion rates were not substantially affected by elevation of effective pressures that remained insufficient to cause major pore collapse. An Arrhenius relation links reaction rate to temperature with an activation enthalpy of 429 ± 201 and 521 ± 52 kJ mol,1 for powdered and intact specimens, respectively. Microstructural study of intact specimens showed extensive nucleation beginning at pre-existing cracks, veins and grain boundaries, and progressing into the interior of the lizardite grains. Extrapolation of these data towards equilibrium temperature provides an upper bound on the kinetics of this reaction in nature. [source] Reaction progress related to indentation structures at glaucophane/glaucophane contacts in an impure marble from Syros, GreeceJOURNAL OF METAMORPHIC GEOLOGY, Issue 8 2006A. OKAMOTO Abstract Microstructures of brittle mineral grains embedded in a ductile matrix provide information on the influence of stress concentration on reaction progress during metamorphism. Under non-hydrostatic conditions, contrasts of mechanical properties between minerals possibly cause stress concentrations at specific grain boundaries, which may result in a localization of subsequent reactions. In an impure marble from Syros, Greece, glaucophane grains occurring in a calcite matrix commonly impinge on other glaucophane grains to form concavo-convex boundary contacts. The geometrical relationship between grain boundary and growth zoning within glaucophane grains indicates that indentation and dissolution occurred preferentially at the glaucophane/glaucophane contacts in response to compression normal to the foliation. In contrast, idioblastic surfaces of glaucophane were preserved at glaucophane/calcite boundaries, indicating that stress concentrated at glaucophane/glaucophane contacts. The retrograde minerals (winchite, albite and biotite) that were formed by consuming glaucophane are observed not only at the extensive site, but also at the ,compressive' site where indentation occurred. The precipitation of retrograde minerals at the extensive sites was accompanied by glaucophane dissolution at the indentation stage. In contrast, the formation of retrograde minerals at the ,compressive' site indicates that retrograde replacement preferentially proceeded at the indented sites even after stress relaxation. Such a localization of the replacement suggests that the formation of damaged zones around glaucophane/glaucophane contacts induced by stress concentration would have provided the preferential sites for glaucophane breakdown at the later stage. [source] Progress of actinolite-forming reactions in mafic schists during retrograde metamorphism: an example from the Sanbagawa metamorphic belt in central Shikoku, JapanJOURNAL OF METAMORPHIC GEOLOGY, Issue 5 2005A. OKAMOTO Abstract Hydration reactions are direct evidence of fluid,rock interaction during regional metamorphism. In this study, hydration reactions to produce retrograde actinolite in mafic schists are investigated to evaluate the controlling factors on the reaction progress. Mafic schists in the Sanbagawa belt contain amphibole coexisting with epidote, chlorite, plagioclase and quartz. Amphibole typically shows two types of compositional zoning from core to rim: barroisite , hornblende , actinolite in the high-grade zone, and winchite , actinolite in the low-grade zone. Both types indicate that amphibole grew during the exhumation stage of the metamorphic belt. Microstructures of amphibole zoning and mass-balance relations suggest that: (1) the actinolite-forming reactions proceeded at the expense of the preexisting amphibole; and (2) the breakdown reaction of hornblende consumed more H2O fluid than that of winchite, when one mole of preexisting amphibole was reacted. Reaction progress is indicated by the volume fraction of actinolite to total amphibole, Yact, with the following details: (1) reaction proceeded homogeneously in each mafic layer; (2) the extent of the hornblende breakdown reaction is commonly low (Yact < 0.5), but it increases drastically in the high-grade part of the garnet zone (Yact,>,0.7); and (3) the extent of the winchite breakdown reaction is commonly high (Yact,>,0.7). Many microcracks are observed within hornblende, and the extent of hornblende breakdown reaction is correlated with the size reduction of the hornblende core. Brittle fracturing of hornblende may have enhanced retrograde reaction progress by increasing of influx of H2O and the surface area of hornblende. In contrast to high-grade rocks, the winchite breakdown reaction is well advanced in the low-grade rocks, where reaction progress is not associated with brittle fracturing of winchite. The high extent of the reaction in the low-grade rocks may be due to small size of winchite before the reaction. [source] Reaction pathways and reaction progress for the smectite-to-chlorite transformation: evidence from hydrothermally altered metabasitesJOURNAL OF METAMORPHIC GEOLOGY, Issue 1 2002D. Robinson Abstract The transformation from smectite to chlorite has been interpreted as involving either a disequilibrium chlorite/smectite mixed-layering sequence, or an equilibrated discontinuous sequence involving smectite,corrensite,chlorite. Here, analysis of the smectite to chlorite transition in different geothermal systems leads us to propose that the transformation proceeds via three contrasting reaction pathways involving (i) a continuous mixed-layer chlorite/smectite series; (ii) a discontinuous smectite,corrensite,chlorite series and (iii) a direct smectite to chlorite transition. Such contrasting pathways are not in accord with an equilibrium mineral reaction series, suggesting that these pathways record kinetically controlled reaction progress. In the geothermal systems reviewed the style of reaction pathway and degree of reaction progress is closely correlated with intensity of recrystallization, and not to differences in thermal gradients or clay grain size. This suggests a kinetic effect linked to variation in fluid/rock ratios and/or a contrast between advective or diffusive fluid transport. The mode of fluid transport provides a means by which the rates of dissolution/nucleation/growth can control the reaction style and the reaction progress of the smectite to chlorite transition. Slow rates of growth are linked to the first reaction pathway involving mixed-layering, while increasing rates of growth, relative to nucleation, promote the generation of more ordered structures and ultimately lead to the direct smectite to chlorite transition, representative of the third pathway. [source] Microwave-assisted TFA cleavage of peptides from Merrifield resinJOURNAL OF PEPTIDE SCIENCE, Issue 1 2010Alicja Kluczyk Abstract Microwave-assisted (MW) reactions are of special interest to the chemical community due to faster reaction times, cleaner reactions and higher product yields. The adaptation of MW to solid phase peptide synthesis resulted in spectacular syntheses of difficult peptides. In the case of Merrifield support, used frequently in synthesis of special peptides, the conditions used in product cleavage are not compatible with off-resin monitoring of the reaction progress. The application of MW irradiation in product removal from Merrifield resin using trifluoroacetic acid (TFA) was investigated using model tetrapeptides and the effects were compared with standard trifluoromethanesulphonic acid (TFMSA) cleavage using elemental analysis as well as chromatographic (HPLC) and spectroscopic (IR) methods. The deprotection of benzyloxycarbonyl and benzyl groups in synthetic bioactive peptides was analyzed using LC-MS and MS/MS experiments. In a 5 min microwave-assisted TFA reaction at low temperature, the majority of product is released from the resin, making the analytical scale MW-assisted procedure a method of choice in monitoring the reactions carried out on Merrifield resin due to the short reaction time and compatibility with HPLC and ESI-MS conditions. Copyright © 2009 European Peptide Society and John Wiley & Sons, Ltd. [source] Carboxyl terminated polyamide 12 chain extension by reactive extrusion using a dioxazoline coupling agent.POLYMER ENGINEERING & SCIENCE, Issue 12 2002Part II: Effects of extrusion conditions Condensation reactions between a carboxyl terminated polyamide 12 and a dioxazoline carried out by reactive extrusion have been characterized in the first part of this study. In the present paper, we focus on the influence of extrusion conditions on reaction progress. Influences of screw profile, screw speed, barrel temperature and feed rate have been established. The use of a flow computation software permitted confirmation of the importance of thermal and mechanical degradations in the condensation process. [source] Monitoring the reaction progress of a high-performance phenylethynyl-terminated poly(etherimide).POLYMER ENGINEERING & SCIENCE, Issue 5 2002Part I: Cure kinetics modeling The cure kinetics of a phenylethynyl-terminated poly(etherimide) are examined via differential scanning calorimetry (DSC) measurements. Isothermal holds at temperatures ranging from 325°C to 360°C provided the necessary information to develop reaction kinetics models using both first-order reaction kinetics and combination reaction kinetics. The first-order reaction kinetics model works well for quick estimates of degree of cure versus time over the experimental temperature range. However, significantly more accurate predictions of degree of cure versus time were provided by the combination reaction kinetics model. The lack of accuracy in the first order model is due to the fact that the reaction cannot be described by a simple order. The experimental procedures followed to obtain the cure kinetics data and the construction of the models from this data are described; the predictions of these models are compared with the experimental results. [source] Monitoring structural transformations in crystals.ACTA CRYSTALLOGRAPHICA SECTION B, Issue 6 2007Structural changes proceeding in a crystal during the Yang photocyclization of the salt 6,6-diethyl-5-oxo-5,6,7,8-tetrahydronaphthalene-2-carboxylate with (1S)-1-(4-methylphenyl)ethylamine were monitored by means of X-ray structure analysis. The course of the photoreaction was evaluated on the basis of the geometrical parameters for the pure reactant crystal. Variations in the cell constants, the product content, the geometry of the reaction centre, the orientation of molecular fragments and the geometry of hydrogen bonds were described and analyzed. It was found that the cell volume increased until 56% product content and decreased thereafter. The distance between the directly reacting C atoms was constant, ,,3.0,Å, until ,,75% reaction progress. Analysis of the distance between atoms that would participate in the formation of the second (unobserved) enantiomorph excluded the formation of such an isomer. Molecular fragments varied their orientation during the photoreaction, and the largest change was observed for the carboxylate group despite its participation in strong hydrogen bonds. The geometry of the hydrogen bonds changed during the photoreaction. The largest change was 0.17,Å for the D...A distance and 13° for the D,H...A angle. A comparison of the intra- and intermolecular parameters for the studied salt with data for other compounds undergoing the Yang photocyclization in crystals revealed a diversity of structural changes brought about by this type of photochemical reaction. [source] Monitoring structural transformations in crystals.ACTA CRYSTALLOGRAPHICA SECTION B, Issue 1 2006Structural changes taking place in a crystal during an intramolecular photochemical reaction [the Yang photocyclization of the ,-methylbenzylamine salt with 1-(4-carboxybenzoyl)-1-methyladamantane] were monitored step-by-step using X-ray structure analysis. This is the first example of such a study carried out for an intramolecular photochemical reaction. During the photoreaction, both the reactant and product molecules change their orientation, but the reactant changes more rapidly after the reaction is about 80% complete. The distance between directly reacting atoms in the reactant molecule is almost constant until about 80% reaction progress and afterwards decreases. The torsion angle defined by the reactant atoms that form the cyclobutane ring also changes in the final stages of the photoreaction. These phenomena are explained in terms of the influence of many product molecules upon a small number of reacting molecules. The adamantane portion shifts more than the remaining part of the anionic reactant species during the reaction, which is explained in terms of hydrogen bonding. The structural changes are accompanied by changes in the cell constants. The results obtained in the present study are compared with analogous results published for intermolecular reactions. [source] Evaluation of an Entropy-Based Combustion Model using Stochastic ReactorsCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 7 2008J. Leicher Abstract The entropy transport concept (ETC) presented in this paper is a novel approach to describe reaction systems such that the dynamic behavior of a chemical system can be reproduced with a minimum in independent parameters. It is shown that, for adiabatic conditions, the mixture fraction and the reaction entropy are sufficient to describe combustion processes without significant loss of information. Entropy is used as a measure of the reaction progress in this context. In order to evaluate the applicability of the ETC for combustion modeling in turbulent systems, the entropy transport concept was implemented into a stochastic reactor model. For several test cases, the results of this ETC-based reactor were compared with a reactor that directly integrates the species transport equations. [source] | |||||||||||||