WorldWideScience

Sample records for chemical reaction transfert

  1. Mass transfer. Liquid-liquid extraction with chemical reaction; Transfert de matiere. Extraction liquide-liquide avec reaction chimique

    Energy Technology Data Exchange (ETDEWEB)

    Buch, A.; Rakib, M.; Stambouli, M. [Ecole Centrale de Paris, 75 (France)

    2009-06-15

    The coupling between the mass transfer and the chemical reaction is in the heart of the processes carried out in liquid-liquid extraction called reactive extraction. This coupling is in particular used in industrial applications such as nuclear industry (Purex process..). (O.M.)

  2. Microfluidic chemical reaction circuits

    Science.gov (United States)

    Lee, Chung-cheng [Irvine, CA; Sui, Guodong [Los Angeles, CA; Elizarov, Arkadij [Valley Village, CA; Kolb, Hartmuth C [Playa del Rey, CA; Huang, Jiang [San Jose, CA; Heath, James R [South Pasadena, CA; Phelps, Michael E [Los Angeles, CA; Quake, Stephen R [Stanford, CA; Tseng, Hsian-rong [Los Angeles, CA; Wyatt, Paul [Tipperary, IE; Daridon, Antoine [Mont-Sur-Rolle, CH

    2012-06-26

    New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

  3. Chemical burn or reaction

    Science.gov (United States)

    ... this page: //medlineplus.gov/ency/article/000059.htm Chemical burn or reaction To use the sharing features on ... the burned area from pressure and friction. Minor chemical burns will generally heal without further treatment. However, if ...

  4. Laser enhanced chemical reactions

    Science.gov (United States)

    Included is the discussion of infrared diode lasers used to study time dependent dynamic events. Also, hot atom excitation of vibrational states of polyatomic molecules, bimolecular quenching and reactions of O(sup 1)D, bimolecular reaction studies of the OH + CO yields H + CO2 system, and the chemical dynamics of the reaction between chlorine atoms and deuterated cyclohexane are covered briefly.

  5. Chemical transport reactions

    CERN Document Server

    Schäfer, Harald

    2013-01-01

    Chemical Transport Reactions focuses on the processes and reactions involved in the transport of solid or liquid substances to form vapor phase reaction products. The publication first offers information on experimental and theoretical principles and the transport of solid substances and its special applications. Discussions focus on calculation of the transport effect of heterogeneous equilibria for a gas motion between equilibrium spaces; transport effect and the thermodynamic quantities of the transport reaction; separation and purification of substances by means of material transport; and

  6. Chemical kinetics of gas reactions

    CERN Document Server

    Kondrat'Ev, V N

    2013-01-01

    Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema

  7. Remittances | Transferts des migrants

    Directory of Open Access Journals (Sweden)

    2012-05-01

    Full Text Available Major Recipients of Remittances (in Million USD, 2008Principaux pays bénéficiaires des transferts des migrants (en millions USD, 2008­Migrants’ Remittances per Capita (in USD, 2008Transferts des migrants par habitant (en USD, 2008Source: World Bank, migration and remittances data.

  8. Mass Transfer with Chemical Reaction.

    Science.gov (United States)

    DeCoursey, W. J.

    1987-01-01

    Describes the organization of a graduate course dealing with mass transfer, particularly as it relates to chemical reactions. Discusses the course outline, including mathematics models of mass transfer, enhancement of mass transfer rates by homogeneous chemical reaction, and gas-liquid systems with chemical reaction. (TW)

  9. Apparent tunneling in chemical reactions

    DEFF Research Database (Denmark)

    Henriksen, Niels Engholm; Hansen, Flemming Yssing; Billing, G. D.

    2000-01-01

    A necessary condition for tunneling in a chemical reaction is that the probability of crossing a barrier is non-zero, when the energy of the reactants is below the potential energy of the barrier. Due to the non-classical nature (i.e, momentum uncertainty) of vibrational states this is, however...

  10. Siphons in chemical reaction networks.

    Science.gov (United States)

    Shiu, Anne; Sturmfels, Bernd

    2010-08-01

    Siphons in a chemical reaction system are subsets of the species that have the potential of being absent in a steady state. We present a characterization of minimal siphons in terms of primary decomposition of binomial ideals, we explore the underlying geometry, and we demonstrate the effective computation of siphons using computer algebra software. This leads to a new method for determining whether given initial concentrations allow for various boundary steady states.

  11. Experimental Demonstrations in Teaching Chemical Reactions.

    Science.gov (United States)

    Hugerat, Muhamad; Basheer, Sobhi

    2001-01-01

    Presents demonstrations of chemical reactions by employing different features of various compounds that can be altered after a chemical change occurs. Experimental activities include para- and dia-magnetism in chemical reactions, aluminum reaction with base, reaction of acid with carbonates, use of electrochemical cells for demonstrating chemical…

  12. Dynamic Reaction Figures: An Integrative Vehicle for Understanding Chemical Reactions

    Science.gov (United States)

    Schultz, Emeric

    2008-01-01

    A highly flexible learning tool, referred to as a dynamic reaction figure, is described. Application of these figures can (i) yield the correct chemical equation by simply following a set of menu driven directions; (ii) present the underlying "mechanism" in chemical reactions; and (iii) help to solve quantitative problems in a number of different…

  13. Femtosecond laser control of chemical reactions

    CSIR Research Space (South Africa)

    Du Plessis, A

    2010-08-31

    Full Text Available relative fragmentation ratios for unimolecular dissociation reactions – therefore selectively breaking bonds in a molecule. More interestingly, the same techniques can be used to provide control over chemical reactions involving two or more reactant...

  14. Chemical Reaction: Diagnosis and Towards Remedy of ...

    African Journals Online (AJOL)

    Experience and literature show that most high school students do not have the correct mental models of coefficients and subscripts in chemical reactions. To contribute towards the conceptual reconstruction of scientific mental models of coefficients and subscripts in a chemical reaction a new teaching-learning strategy is ...

  15. Modelling Students' Visualisation of Chemical Reaction

    Science.gov (United States)

    Cheng, Maurice M. W.; Gilbert, John K.

    2017-01-01

    This paper proposes a model-based notion of "submicro representations of chemical reactions". Based on three structural models of matter (the simple particle model, the atomic model and the free electron model of metals), we suggest there are two major models of reaction in school chemistry curricula: (a) reactions that are simple…

  16. Nature-Inspired Chemical Reaction Optimisation Algorithms.

    Science.gov (United States)

    Siddique, Nazmul; Adeli, Hojjat

    2017-01-01

    Nature-inspired meta-heuristic algorithms have dominated the scientific literature in the areas of machine learning and cognitive computing paradigm in the last three decades. Chemical reaction optimisation (CRO) is a population-based meta-heuristic algorithm based on the principles of chemical reaction. A chemical reaction is seen as a process of transforming the reactants (or molecules) through a sequence of reactions into products. This process of transformation is implemented in the CRO algorithm to solve optimisation problems. This article starts with an overview of the chemical reactions and how it is applied to the optimisation problem. A review of CRO and its variants is presented in the paper. Guidelines from the literature on the effective choice of CRO parameters for solution of optimisation problems are summarised.

  17. Chemical reactions in solvents and melts

    CERN Document Server

    Charlot, G

    1969-01-01

    Chemical Reactions in Solvents and Melts discusses the use of organic and inorganic compounds as well as of melts as solvents. This book examines the applications in organic and inorganic chemistry as well as in electrochemistry. Organized into two parts encompassing 15 chapters, this book begins with an overview of the general properties and the different types of reactions, including acid-base reactions, complex formation reactions, and oxidation-reduction reactions. This text then describes the properties of inert and active solvents. Other chapters consider the proton transfer reactions in

  18. Flows and chemical reactions in heterogeneous mixtures

    CERN Document Server

    Prud'homme, Roger

    2014-01-01

    This book - a sequel of previous publications 'Flows and Chemical Reactions' and 'Chemical Reactions in Flows and Homogeneous Mixtures' - is devoted to flows with chemical reactions in heterogeneous environments.  Heterogeneous media in this volume include interfaces and lines. They may be the site of radiation. Each type of flow is the subject of a chapter in this volume. We consider first, in Chapter 1, the question of the generation of environments biphasic individuals: dusty gas, mist, bubble flow.  Chapter 2 is devoted to the study at the mesoscopic scale: particle-fluid exchange of mom

  19. Chemical kinetics and reaction dynamics

    CERN Document Server

    Houston, Paul L

    2006-01-01

    This text teaches the principles underlying modern chemical kinetics in a clear, direct fashion, using several examples to enhance basic understanding. It features solutions to selected problems, with separate sections and appendices that cover more technical applications.Each chapter is self-contained and features an introduction that identifies its basic goals, their significance, and a general plan for their achievement. This text's important aims are to demonstrate that the basic kinetic principles are essential to the solution of modern chemical problems, and to show how the underlying qu

  20. Chemical Reactions at Surfaces. Final Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    None

    2003-02-21

    The Gordon Research Conference (GRC) on Chemical Reactions at Surfaces was held at Holiday Inn, Ventura, California, 2/16-21/03. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

  1. Explorations into Chemical Reactions and Biochemical Pathways.

    Science.gov (United States)

    Gasteiger, Johann

    2016-12-01

    A brief overview of the work in the research group of the present author on extracting knowledge from chemical reaction data is presented. Methods have been developed to calculate physicochemical effects at the reaction site. It is shown that these physicochemical effects can quite favourably be used to derive equations for the calculation of data on gas phase reactions and on reactions in solution such as aqueous acidity of alcohols or carboxylic acids or the hydrolysis of amides. Furthermore, it is shown that these physicochemical effects are quite effective for assigning reactions into reaction classes that correspond to chemical knowledge. Biochemical reactions constitute a particularly interesting and challenging task for increasing our understanding of living species. The BioPath.Database is a rich source of information on biochemical reactions and has been used for a variety of applications of chemical, biological, or medicinal interests. Thus, it was shown that biochemical reactions can be assigned by the physicochemical effects into classes that correspond to the classification of enzymes by the EC numbers. Furthermore, 3D models of reaction intermediates can be used for searching for novel enzyme inhibitors. It was shown in a combined application of chemoinformatics and bioinformatics that essential pathways of diseases can be uncovered. Furthermore, a study showed that bacterial flavor-forming pathways can be discovered. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Kinetic studies of elementary chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Durant, J.L. Jr. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    This program concerning kinetic studies of elementary chemical reactions is presently focussed on understanding reactions of NH{sub x} species. To reach this goal, the author is pursuing experimental studies of reaction rate coefficients and product branching fractions as well as using electronic structure calculations to calculate transition state properties and reaction rate calculations to relate these properties to predicted kinetic behavior. The synergy existing between the experimental and theoretical studies allow one to gain a deeper insight into more complex elementary reactions.

  3. Entropy Generation in a Chemical Reaction

    Science.gov (United States)

    Miranda, E. N.

    2010-01-01

    Entropy generation in a chemical reaction is analysed without using the general formalism of non-equilibrium thermodynamics at a level adequate for advanced undergraduates. In a first approach to the problem, the phenomenological kinetic equation of an elementary first-order reaction is used to show that entropy production is always positive. A…

  4. Chemical reaction due to stronger Ramachandran interaction

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 3. Chemical reaction due to stronger Ramachandran interaction. Andrew Das ... Arulsamy1. Condensed Matter Group, Institute of Interdisciplinary Science, No. 24, level-4, Block C, Lorong Bahagia, Pandamaran, 42000 Port Klang, Selangor DE, Malaysia ...

  5. Chemical reactions confined within carbon nanotubes.

    Science.gov (United States)

    Miners, Scott A; Rance, Graham A; Khlobystov, Andrei N

    2016-08-22

    In this critical review, we survey the wide range of chemical reactions that have been confined within carbon nanotubes, particularly emphasising how the pairwise interactions between the catalysts, reactants, transition states and products of a particular molecular transformation with the host nanotube can be used to control the yields and distributions of products of chemical reactions. We demonstrate that nanoscale confinement within carbon nanotubes enables the control of catalyst activity, morphology and stability, influences the local concentration of reactants and products thus affecting equilibria, rates and selectivity, pre-arranges the reactants for desired reactions and alters the relative stability of isomeric products. We critically evaluate the relative advantages and disadvantages of the confinement of chemical reactions inside carbon nanotubes from a chemical perspective and describe how further developments in the controlled synthesis of carbon nanotubes and the incorporation of multifunctionality are essential for the development of this ever-expanding field, ultimately leading to the effective control of the pathways of chemical reactions through the rational design of multi-functional carbon nanoreactors.

  6. Memory switches in chemical reaction space.

    Science.gov (United States)

    Ramakrishnan, Naren; Bhalla, Upinder S

    2008-07-18

    Just as complex electronic circuits are built from simple Boolean gates, diverse biological functions, including signal transduction, differentiation, and stress response, frequently use biochemical switches as a functional module. A relatively small number of such switches have been described in the literature, and these exhibit considerable diversity in chemical topology. We asked if biochemical switches are indeed rare and if there are common chemical motifs and family relationships among such switches. We performed a systematic exploration of chemical reaction space by generating all possible stoichiometrically valid chemical configurations up to 3 molecules and 6 reactions and up to 4 molecules and 3 reactions. We used Monte Carlo sampling of parameter space for each such configuration to generate specific models and checked each model for switching properties. We found nearly 4,500 reaction topologies, or about 10% of our tested configurations, that demonstrate switching behavior. Commonly accepted topological features such as feedback were poor predictors of bistability, and we identified new reaction motifs that were likely to be found in switches. Furthermore, the discovered switches were related in that most of the larger configurations were derived from smaller ones by addition of one or more reactions. To explore even larger configurations, we developed two tools: the "bistabilizer," which converts almost-bistable systems into bistable ones, and frequent motif mining, which helps rank untested configurations. Both of these tools increased the coverage of our library of bistable systems. Thus, our systematic exploration of chemical reaction space has produced a valuable resource for investigating the key signaling motif of bistability.

  7. Perspective: Bimolecular chemical reaction dynamics in liquids.

    Science.gov (United States)

    Orr-Ewing, Andrew J

    2014-03-07

    Bimolecular reactions in the gas phase exhibit rich and varied dynamical behaviour, but whether a profound knowledge of the mechanisms of isolated reactive collisions can usefully inform our understanding of reactions in liquid solutions remains an open question. The fluctuating environment in a liquid may significantly alter the motions of the reacting particles and the flow of energy into the reaction products after a transition state has been crossed. Recent experimental and computational studies of exothermic reactions of CN radicals with organic molecules indicate that many features of the gas-phase dynamics are retained in solution. However, observed differences may also provide information on the ways in which a solvent modifies fundamental chemical mechanisms. This perspective examines progress in the use of time-resolved infra-red spectroscopy to study reaction dynamics in liquids, discusses how existing theories can guide the interpretation of experimental data, and suggests future challenges for this field of research.

  8. Calculation of the energetics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dunning, T.H. Jr.; Harding, L.B.; Shepard, R.L.; Harrison, R.J.

    1988-01-01

    To calculate the energetics of chemical reactions we must solve the electronic Schroedinger equation for the molecular conformations of importance for the reactive encounter. Substantial changes occur in the electronic structure of a molecular system as the reaction progresses from reactants through the transition state to products. To describe these changes, our approach includes the following three elements: the use of multiconfiguration self-consistent field wave functions to provide a consistent zero-order description of the electronic structure of the reactants, transition state, and products; the use of configuration interaction techniques to describe electron correlation effects needed to provide quantitative predictions of the reaction energetics; and the use of large, optimized basis sets to provide the flexibility needed to describe the variations in the electronic distributions. With this approach we are able to study reactions involving as many as 5--6 atoms with errors of just a few kcal/mol in the predicted reaction energetics. Predictions to chemical accuracy, i.e., to 1 kcal/mol or less, are not yet feasible, although continuing improvements in both the theoretical methodology and computer technology suggest that this will soon be possible, at least for reactions involving small polyatomic species. 4 figs.

  9. Lagrangian descriptors of driven chemical reaction manifolds

    Science.gov (United States)

    Craven, Galen T.; Junginger, Andrej; Hernandez, Rigoberto

    2017-08-01

    The persistence of a transition state structure in systems driven by time-dependent environments allows the application of modern reaction rate theories to solution-phase and nonequilibrium chemical reactions. However, identifying this structure is problematic in driven systems and has been limited by theories built on series expansion about a saddle point. Recently, it has been shown that to obtain formally exact rates for reactions in thermal environments, a transition state trajectory must be constructed. Here, using optimized Lagrangian descriptors [G. T. Craven and R. Hernandez, Phys. Rev. Lett. 115, 148301 (2015), 10.1103/PhysRevLett.115.148301], we obtain this so-called distinguished trajectory and the associated moving reaction manifolds on model energy surfaces subject to various driving and dissipative conditions. In particular, we demonstrate that this is exact for harmonic barriers in one dimension and this verification gives impetus to the application of Lagrangian descriptor-based methods in diverse classes of chemical reactions. The development of these objects is paramount in the theory of reaction dynamics as the transition state structure and its underlying network of manifolds directly dictate reactivity and selectivity.

  10. Chemical Reactions at Surfaces [Conference summary report

    Energy Technology Data Exchange (ETDEWEB)

    Henderson, Michael; Gray, Nancy Ryan

    2010-04-14

    Chemical reactions at surfaces underlie some of the most important processes of today, including catalysis, energy conversion, microelectronics, human health and the environment. Understanding surface chemical reactions at a fundamental level is at the core of the field of surface science. The Gordon Research Conference on Chemical Reactions at Surfaces is one of the premiere meetings in the field. The program this year will cover a broad range of topics, including heterogeneous catalysis and surface chemistry, surfaces in environmental chemistry and energy conversion, reactions at the liquid-solid and liquid-gas interface, electronic materials growth and surface modification, biological interfaces, and electrons and photons at surfaces. An exciting program is planned, with contributions from outstanding speakers and discussion leaders from the international scientific community. The conference provides a dynamic environment with ample time for discussion and interaction. Attendees are encouraged to present posters; the poster sessions are historically well attended and stimulate additional discussions. The conference provides an excellent opportunity for junior researchers (e.g. graduate students or postdocs) to present their work and interact with established leaders in the field.

  11. MRI of chemical reactions and processes.

    Science.gov (United States)

    Britton, Melanie M

    2017-08-01

    As magnetic resonance imaging (MRI) can spatially resolve a wealth of molecular information available from nuclear magnetic resonance (NMR), it is able to non-invasively visualise the composition, properties and reactions of a broad range of spatially-heterogeneous molecular systems. Hence, MRI is increasingly finding applications in the study of chemical reactions and processes in a diverse range of environments and technologies. This article will explain the basic principles of MRI and how it can be used to visualise chemical composition and molecular properties, providing an overview of the variety of information available. Examples are drawn from the disciplines of chemistry, chemical engineering, environmental science, physics, electrochemistry and materials science. The review introduces a range of techniques used to produce image contrast, along with the chemical and molecular insight accessible through them. Methods for mapping the distribution of chemical species, using chemical shift imaging or spatially-resolved spectroscopy, are reviewed, as well as methods for visualising physical state, temperature, current density, flow velocities and molecular diffusion. Strategies for imaging materials with low signal intensity, such as those containing gases or low sensitivity nuclei, using compressed sensing, para-hydrogen or polarisation transfer, are discussed. Systems are presented which encapsulate the diversity of chemical and physical parameters observable by MRI, including one- and two-phase flow in porous media, chemical pattern formation, phase transformations and hydrodynamic (fingering) instabilities. Lastly, the emerging area of electrochemical MRI is discussed, with studies presented on the visualisation of electrochemical deposition and dissolution processes during corrosion and the operation of batteries, supercapacitors and fuel cells. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

  12. Theoretical studies of chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Schatz, G.C. [Argonne National Laboratory, IL (United States)

    1993-12-01

    This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.

  13. Flows and chemical reactions in homogeneous mixtures

    CERN Document Server

    Prud'homme, Roger

    2013-01-01

    Flows with chemical reactions can occur in various fields such as combustion, process engineering, aeronautics, the atmospheric environment and aquatics. The examples of application chosen in this book mainly concern homogeneous reactive mixtures that can occur in propellers within the fields of process engineering and combustion: - propagation of sound and monodimensional flows in nozzles, which may include disequilibria of the internal modes of the energy of molecules; - ideal chemical reactors, stabilization of their steady operation points in the homogeneous case of a perfect mixture and c

  14. Chemical Reaction Networks for Computing Polynomials.

    Science.gov (United States)

    Salehi, Sayed Ahmad; Parhi, Keshab K; Riedel, Marc D

    2017-01-20

    Chemical reaction networks (CRNs) provide a fundamental model in the study of molecular systems. Widely used as formalism for the analysis of chemical and biochemical systems, CRNs have received renewed attention as a model for molecular computation. This paper demonstrates that, with a new encoding, CRNs can compute any set of polynomial functions subject only to the limitation that these functions must map the unit interval to itself. These polynomials can be expressed as linear combinations of Bernstein basis polynomials with positive coefficients less than or equal to 1. In the proposed encoding approach, each variable is represented using two molecular types: a type-0 and a type-1. The value is the ratio of the concentration of type-1 molecules to the sum of the concentrations of type-0 and type-1 molecules. The proposed encoding naturally exploits the expansion of a power-form polynomial into a Bernstein polynomial. Molecular encoders for converting any input in a standard representation to the fractional representation as well as decoders for converting the computed output from the fractional to a standard representation are presented. The method is illustrated first for generic CRNs; then chemical reactions designed for an example are mapped to DNA strand-displacement reactions.

  15. Chemical and radiation-chemical radical reactions in lignocellulose materials

    Science.gov (United States)

    Kuzina, Svetlana I.; Shilova, Irina A.; Mikhailov, Al'fa I.

    2011-09-01

    Chemical and radiation-chemical radical reactions in lignocellulose materials were explored by 3-cm and 2-mm ESR spectroscopy. Background (intrinsic) singlet signals at g=2.003 from wood pulp and lignin and those arising during reaction of lignocellulose materials with acids and chlorine were attributed to radicals with conjugated CC bonds. The 2-mm ESR signal with 3D anisotropy of g-factor from o-semiquinone radical ions formed in reaction of lignin with NaOH was recorded for the first time. The singlet signals derived from cellulose γ-irradiated at 77 K and marked out during post-thermal reactions were assigned to radicals with conjugated bonds. In wetted cellulose, a triplet signal with αβH≅2.7 mT and imposed quadruplet structure (0.5-0.7 mT) from three γ-protons was detected at 300 K and attributed to С 4-radicals. The triplet signals derived from С 2- and С 3-radicals in pyranose cycles of cellulose exhibited higher values of αβH (3.0-3.2 mT) and lower thermal stability (up to 250 K). In radiolyzed cotton pulp, detected were ESR signals derived from formyl radicals formed upon rupture of the С 5С 6 bond in pyranose cycles. Heating up irradiated samples under О 2 was accompanied by formation of peroxide radicals. Photoinduced recombination of trapped electrons with С 1-radicals was found to proceed as a chain reaction with a kinetic length of about 25 units. Photolysis ( λ≥360 nm) of radiolyzed cellulose enhanced the disclosure of pyranose cycles and, as a result, the evolution of CO 2 by a factor of 2-2.5.

  16. Quantum dynamics of fast chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Light, J.C. [Univ. of Chicago, IL (United States)

    1993-12-01

    The aims of this research are to explore, develop, and apply theoretical methods for the evaluation of the dynamics of gas phase collision processes, primarily chemical reactions. The primary theoretical tools developed for this work have been quantum scattering theory, both in time dependent and time independent forms. Over the past several years, the authors have developed and applied methods for the direct quantum evaluation of thermal rate constants, applying these to the evaluation of the hydrogen isotopic exchange reactions, applied wave packet propagation techniques to the dissociation of Rydberg H{sub 3}, incorporated optical potentials into the evaluation of thermal rate constants, evaluated the use of optical potentials for state-to-state reaction probability evaluations, and, most recently, have developed quantum approaches for electronically non-adiabatic reactions which may be applied to simplify calculations of reactive, but electronically adiabatic systems. Evaluation of the thermal rate constants and the dissociation of H{sub 3} were reported last year, and have now been published.

  17. Law of localization in chemical reaction networks

    CERN Document Server

    Okada, Takashi

    2016-01-01

    In living cells, chemical reactions are connected by sharing their products and substrates, and form complex networks, e.g. metabolic pathways. Here we developed a theory to predict the sensitivity, i.e. the responses of concentrations and fluxes to perturbations of enzymes, from network structure alone. Responses turn out to exhibit two characteristic patterns, $localization$ and $hierarchy$. We present a general theorem connecting sensitivity with network topology that explains these characteristic patterns. Our results imply that network topology is an origin of biological robustness. Finally, we suggest a strategy to determine real networks from experimental measurements.

  18. Development of Green and Sustainable Chemical Reactions

    DEFF Research Database (Denmark)

    Taarning, Esben

    Abstract This thesis entitled Development of Green and Sustainable Chemical Reactions is divided into six chapters involving topics and projects related to green and sustainable chemistry. The chapters can be read independently, however a few concepts and some background information is introduced...... in chapter one and two which can be helpful to know when reading the subsequent chapters. The first chapter is an introduction into the fundamentals of green and sustainable chemistry. The second chapter gives an overview of some of the most promising methods to produce value added chemicals from biomass...... and only leads to small amounts of waste formation due to the all-catalytic nature of the procedure. This chapter involves the use of transition metal catalysis as well as classic organic chemistry. In chapter four, supported gold nanoparticles are used as catalysts for the aerobic oxidation of primary...

  19. Services de transfert des savoirs

    Directory of Open Access Journals (Sweden)

    Albert Simard

    2009-03-01

    Full Text Available Le présent article décrit un modèle visant à faciliter la compréhension du processus de transfert du contenu depuis sa source jusqu’à son utilisation. Un groupe de travail de Ressources naturelles Canada a étudié la nature du transfert des savoirs à l’aide d’un modèle de services, afin de découvrir et comprendre les modèles et processus sous-jacents. Les services de savoir sont des programmes qui créent et fournissent des produits organisationnels basés sur un contenu et ayant une valeur intégrée. Ces programmes sont destinés à être utilisés en interne ou transférés pour répondre aux souhaits et besoins d’un utilisateur externe. Les critères de conception du modèle sont les suivants : indépendance par rapport au contenu, concentration sur l’organisation, évolutivité, deux pilotes et deux niveaux de résolution. Le modèle est basé sur une chaîne de valeur dans laquelle la valeur est intégrée, déplacée ou extraite. Un système de services de savoir se divise en neuf étapes : générer, transformer, gérer, utiliser en interne, transférer, ajouter de la valeur, utiliser professionnellement, utiliser personnellement et évaluer. Les services de savoir sont fournis par l’intermédiaire d’un spectre de distribution allant de complexe à accessible. À chaque région du spectre de distribution correspond une série d’attributs qui influencent la manière dont les services sont fournis.This paper describes a model intended to increase understanding of how content is transferred from its source to its use. A Natural Resources Canada task group explored the nature of knowledge transfer with a services paradigm to discover and understand underlying patterns and processes. Knowledge Services are programs that produce and pro-vide content-based organizational outputs with embedded value that are intended to be used internally or transferred to meet external user wants or needs. Model design criteria

  20. Molecular Dynamics Simulations of Chemical Reactions for Use in Education

    Science.gov (United States)

    Qian Xie; Tinker, Robert

    2006-01-01

    One of the simulation engines of an open-source program called the Molecular Workbench, which can simulate thermodynamics of chemical reactions, is described. This type of real-time, interactive simulation and visualization of chemical reactions at the atomic scale could help students understand the connections between chemical reaction equations…

  1. Strategies for chemical reaction searching in SciFinder

    Science.gov (United States)

    Ridley

    2000-09-01

    The bibliographic, chemical structure, and chemical reaction databases produced by Chemical Abstracts Service allow a number of possibilities for chemical reaction searching. While these same databases may be searched through the STN network, many end-users find the intuitive software interface SciFinder simpler, but there still are issues to address. Searching may be performed through keywords, chemical structures, or chemical reactions, and the answers may vary with respect to precision and comprehension. Often combinations of search options may be needed to best solve the problem. Retrosynthetic analyses are easily performed in the chemical reaction database and can give unique insights into synthetic alternatives.

  2. Solving moment hierarchies for chemical reaction networks

    Science.gov (United States)

    Krishnamurthy, Supriya; Smith, Eric

    2017-10-01

    The study of chemical reaction networks (CRN’s) is a very active field. Earlier well-known results (Feinberg 1987 Chem. Enc. Sci. 42 2229, Anderson et al 2010 Bull. Math. Biol. 72 1947) identify a topological quantity called deficiency, for any CRN, which, when exactly equal to zero, leads to a unique factorized steady-state for these networks. No results exist however for the steady states of non-zero-deficiency networks. In this paper, we show how to write the full moment-hierarchy for any non-zero-deficiency CRN obeying mass-action kinetics, in terms of equations for the factorial moments. Using these, we can recursively predict values for lower moments from higher moments, reversing the procedure usually used to solve moment hierarchies. We show, for non-trivial examples, that in this manner we can predict any moment of interest, for CRN’s with non-zero deficiency and non-factorizable steady states.

  3. Visualization of electronic properties of molecules in chemical reactions.

    Science.gov (United States)

    Wei, S; Famini, G R

    1995-10-01

    Modern computational methods allow for the tracking of entire chemical reactions, ranging from initial reactants, through transition states, and to the final products. They also permit the computation of a variety of properties that can change as the reaction proceeds from start to finish. Visualization of these reactions is often difficult and usually limited to static displays of specific steps along the reaction paths. This article describes a program, Reaction Viewer, that we have developed to visualize a chemical reaction dynamically. The article also describes the use of this program to see the movement of electrons and other electronic effects, as well as steric ramifications during the reaction.

  4. Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry.

    Science.gov (United States)

    Rappoport, Dmitrij; Galvin, Cooper J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán

    2014-03-11

    While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reactive potential energy surfaces and are combined here with quantum chemical structure optimizations, which yield the structures and energies of the reaction intermediates and products. Application of heuristics-aided quantum chemical methodology to the formose reaction reproduces the experimentally observed reaction products, major reaction pathways, and autocatalytic cycles.

  5. Determination by transfer reaction of alpha widths in fluorine for astrophysical interest; Determination par reaction de transfert de largeurs alpha dans le fluor 19. Applications a l'astrophysique

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira Santos, F. de

    1995-04-15

    The nucleosynthesis of fluorine is not known. Several astrophysical models predict the alpha radiative capture onto N{sup 15} as the main fluorine production reaction. In the expression of the reaction rate, one parameter is missing: the alpha width of the resonance on the E = 4.377 MeV level in fluorine. A direct measurement is excluded due to the very low cross-section expected. We have determined this alpha width using a transfer reaction followed by analyses with FR-DWBA (Finite Range Distorted Wave Born Approximation) in a simple cluster alpha model. This experiment was carried out with a Li{sup 7} beam with E = 28 MeV onto a N{sup 15} gas target. The 16 first levels were studied. Spectroscopic factors were extracted for most of them. Alpha widths for unbound levels were determined. Many alpha width were compared with known values from direct reaction and the differences lie within the uncertainty range (factor 2). The alpha width for the E = 4.377 MeV level was determined ({gamma}{sub {alpha}} = 1.5*10{sup -15} MeV), its value is about 60 times weaker than the used value. The influence of our new rate was studied in AGB (Asymptotic Giant Branch) stars during thermal pulses. In this model the alteration is sensitive. (author)

  6. Prediction and Prevention of Chemical Reaction Hazards: Learning by Simulation.

    Science.gov (United States)

    Shacham, Mordechai; Brauner, Neima; Cutlip, Michael B.

    2001-01-01

    Points out that chemical hazards are the major cause of accidents in chemical industry and describes a safety teaching approach using a simulation. Explains a problem statement on exothermic liquid-phase reactions. (YDS)

  7. Visualization of chemical reaction dynamics: Toward understanding complex polyatomic reactions

    National Research Council Canada - National Science Library

    SUZUKI, Toshinori

    2013-01-01

    Polyatomic molecules have several electronic states that have similar energies. Consequently, their chemical dynamics often involve nonadiabatic transitions between multiple potential energy surfaces...

  8. Incidents of chemical reactions in cell equipment

    Energy Technology Data Exchange (ETDEWEB)

    Baldwin, N.M.; Barlow, C.R. [Uranium Enrichment Organization, Oak Ridge, TN (United States)

    1991-12-31

    Strongly exothermic reactions can occur between equipment structural components and process gases under certain accident conditions in the diffusion enrichment cascades. This paper describes the conditions required for initiation of these reactions, and describes the range of such reactions experienced over nearly 50 years of equipment operation in the US uranium enrichment program. Factors are cited which can promote or limit the destructive extent of these reactions, and process operations are described which are designed to control the reactions to minimize equipment damage, downtime, and the possibility of material releases.

  9. Semiclassical methods in chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Keshavamurthy, Srihari [Univ. of California, Berkeley, CA (United States)

    1994-12-01

    Semiclassical approximations, simple as well as rigorous, are formulated in order to be able to describe gas phase chemical reactions in large systems. We formulate a simple but accurate semiclassical model for incorporating multidimensional tunneling in classical trajectory simulations. This model is based on the existence of locally conserved actions around the saddle point region on a multidimensional potential energy surface. Using classical perturbation theory and monitoring the imaginary action as a function of time along a classical trajectory we calculate state-specific unimolecular decay rates for a model two dimensional potential with coupling. Results are in good comparison with exact quantum results for the potential over a wide range of coupling constants. We propose a new semiclassical hybrid method to calculate state-to-state S-matrix elements for bimolecular reactive scattering. The accuracy of the Van Vleck-Gutzwiller propagator and the short time dynamics of the system make this method self-consistent and accurate. We also go beyond the stationary phase approximation by doing the resulting integrals exactly (numerically). As a result, classically forbidden probabilties are calculated with purely real time classical trajectories within this approach. Application to the one dimensional Eckart barrier demonstrates the accuracy of this approach. Successful application of the semiclassical hybrid approach to collinear reactive scattering is prevented by the phenomenon of chaotic scattering. The modified Filinov approach to evaluating the integrals is discussed, but application to collinear systems requires a more careful analysis. In three and higher dimensional scattering systems, chaotic scattering is suppressed and hence the accuracy and usefulness of the semiclassical method should be tested for such systems.

  10. Chemical Looping Combustion Reactions and Systems

    Energy Technology Data Exchange (ETDEWEB)

    Sarofim, Adel; Lighty, JoAnn; Smith, Philip; Whitty, Kevin; Eyring, Edward; Sahir, Asad; Alvarez, Milo; Hradisky, Michael; Clayton, Chris; Konya, Gabor; Baracki, Richard; Kelly, Kerry

    2014-03-01

    , they performed a sensitivity analysis for velocity, height and polydispersity and compared results against literature data for experimental studies of CLC beds with no reaction. Finally, they present an optimization space using simple non-reactive configurations. In Subtask 5.3, through a series of experimental studies, behavior of a variety of oxygen carriers with different loadings and manufacturing techniques was evaluated under both oxidizing and reducing conditions. The influences of temperature, degree of carrier conversion and thermodynamic driving force resulting from the difference between equilibrium and system O{sub 2} partial pressures were evaluated through several experimental campaigns, and generalized models accounting for these influences were developed to describe oxidation and oxygen release. Conversion of three solid fuels with widely ranging reactivities was studied in a small fluidized bed system, and all but the least reactive fuel (petcoke) were rapidly converted by oxygen liberated from the CLOU carrier. Attrition propensity of a variety of carriers was also studied, and the carriers produced by freeze granulation or impregnation of preformed substrates displayed the lowest rates of attrition. Subtask 5.4 focused on gathering kinetic data for a copper-based oxygen carrier to assist with modeling of a functioning chemical looping reactor. The kinetics team was also responsible for the development and analysis of supported copper oxygen carrier material.

  11. Effect of chemical reaction on unsteady MHD free convective two ...

    African Journals Online (AJOL)

    The effect of chemical reaction on unsteady MHD free convective two immiscible fluids flow has been studied. Approximate analytical solutions to the governing equations are found for the coupled and linear differential equations using regular perturbation method. Graphs depicting the effect of chemical reaction parameter ...

  12. Stereodynamics: From elementary processes to macroscopic chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Kasai, Toshio [Department of Chemistry, National Taiwan University, Taipei 106, Taiwan (China); Graduate School of Science, Department of Chemistry, Osaka University, Toyonaka, 560-0043 Osaka (Japan); Che, Dock-Chil [Graduate School of Science, Department of Chemistry, Osaka University, Toyonaka, 560-0043 Osaka (Japan); Tsai, Po-Yu [Department of Chemistry, National Taiwan University, Taipei 106, Taiwan (China); Department of Chemistry, National Chung Hsing University, Taichung 402, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan (China); Lin, King-Chuen [Department of Chemistry, National Taiwan University, Taipei 106, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan (China); Palazzetti, Federico [Scuola Normale Superiore, Pisa (Italy); Dipartimento di Chimica Biologia e Biotecnologie, Università di Perugia, 06123 Perugia (Italy); Aquilanti, Vincenzo [Dipartimento di Chimica Biologia e Biotecnologie, Università di Perugia, 06123 Perugia (Italy); Istituto di Struttura della Materia, Consiglio Nazionale delle Ricerche, Roma (Italy); Instituto de Fisica, Universidade Federal da Bahia, Salvador (Brazil)

    2015-12-31

    This paper aims at discussing new facets on stereodynamical behaviors in chemical reactions, i.e. the effects of molecular orientation and alignment on reactive processes. Further topics on macroscopic processes involving deviations from Arrhenius behavior in the temperature dependence of chemical reactions and chirality effects in collisions are also discussed.

  13. Miniaturized continuous flow reaction vessels: influence on chemical reactions

    NARCIS (Netherlands)

    Brivio, M.; Verboom, Willem; Reinhoudt, David

    2006-01-01

    This review offers an overview of the relatively young research area of continuous flow lab-on-a-chip for synthetic applications. A short introduction on the basic aspects of lab-on-a-chip is given in the first part. Subsequently, the effects of downscaling reaction vessels as well as the advantages

  14. Computed potential energy surfaces for chemical reactions

    Science.gov (United States)

    Walch, Stephen P.; Levin, Eugene

    1993-01-01

    A new global potential energy surface (PES) is being generated for O(P-3) + H2 yields OH + H. This surface is being fit using the rotated Morse oscillator method, which was used to fit the previous POL-CI surface. The new surface is expected to be more accurate and also includes a much more complete sampling of bent geometries. A new study has been undertaken of the reaction N + O2 yields NO + O. The new studies have focused on the region of the surface near a possible minimum corresponding to the peroxy form of NOO. A large portion of the PES for this second reaction has been mapped out. Since state to state cross sections for the reaction are important in the chemistry of high temperature air, these studies will probably be extended to permit generation of a new global potential for reaction.

  15. Chemical tailoring of teicoplanin with site-selective reactions.

    Science.gov (United States)

    Pathak, Tejas P; Miller, Scott J

    2013-06-05

    Semisynthesis of natural product derivatives combines the power of fermentation with orthogonal chemical reactions. Yet, chemical modification of complex structures represents an unmet challenge, as poor selectivity often undermines efficiency. The complex antibiotic teicoplanin eradicates bacterial infections. However, as resistance emerges, the demand for improved analogues grows. We have discovered chemical reactions that achieve site-selective alteration of teicoplanin. Utilizing peptide-based additives that alter reaction selectivities, certain bromo-teicoplanins are accessible. These new compounds are also scaffolds for selective cross-coupling reactions, enabling further molecular diversification. These studies enable two-step access to glycopeptide analogues not available through either biosynthesis or rapid total chemical synthesis alone. The new compounds exhibit a spectrum of activities, revealing that selective chemical alteration of teicoplanin may lead to analogues with attenuated or enhanced antibacterial properties, in particular against vancomycin- and teicoplanin-resistant strains.

  16. An autonomous organic reaction search engine for chemical reactivity

    Science.gov (United States)

    Dragone, Vincenza; Sans, Victor; Henson, Alon B.; Granda, Jaroslaw M.; Cronin, Leroy

    2017-06-01

    The exploration of chemical space for new reactivity, reactions and molecules is limited by the need for separate work-up-separation steps searching for molecules rather than reactivity. Herein we present a system that can autonomously evaluate chemical reactivity within a network of 64 possible reaction combinations and aims for new reactivity, rather than a predefined set of targets. The robotic system combines chemical handling, in-line spectroscopy and real-time feedback and analysis with an algorithm that is able to distinguish and select the most reactive pathways, generating a reaction selection index (RSI) without need for separate work-up or purification steps. This allows the automatic navigation of a chemical network, leading to previously unreported molecules while needing only to do a fraction of the total possible reactions without any prior knowledge of the chemistry. We show the RSI correlates with reactivity and is able to search chemical space using the most reactive pathways.

  17. CW CO2 Laser Induced Chemical Reactions

    Science.gov (United States)

    Pola, Joseph

    1989-05-01

    CW CO2 laser driven reactions between sulfur hexafluoride and carbon oxide, carbon suboxide, carbonyl sulfide and carbon disulfide proceed at subatmospheric pressures and yield fluorinated carbon compounds and sulfur tetrafluoride. CW CO2 laser driven reactions of organic compounds in the presence of energy-conveying sulfur hexafluoride show reaction course different from that normally observed due to elimination of reactor hot surface effects. The examples concern the decomposition of polychlorohydrocarbons, 2-nitropropane, tert.-butylamine, allyl chloride, spirohexane, isobornyl acetate and the oxidation of haloolefins. CW CO2 laser induced fragmentation of 1-methyl-l-silacyclobutanes and 4-silaspiro(3.4)octane in the presence of sulfur hexafluoride is an effective way for preparation and deposition of stable organosilicon polymers.

  18. Extracting Chemical Reactions from Biological Literature

    Science.gov (United States)

    2014-05-16

    reactions is difficult and requires  a significant amount of trial and  error  as well as domain expertise. Hand­built rules have been successful in the...overview of the extraction process starting with a sentence from an abstract. The sentence is first  parsed  grammatically  into a syntax tree and labeled...reaction but there is a label true negative pattern does not extract a reaction and there is no label Table 5: Definitions of true positive, false

  19. Charge Exchange and Chemical Reactions with Trapped Th$^{3+}$

    CERN Document Server

    Churchill, L R; Chapman, M S

    2010-01-01

    We have measured the reaction rates of trapped, buffer gas cooled Th$^{3+}$ and various gases and have analyzed the reaction products using trapped ion mass spectrometry techniques. Ion trap lifetimes are usually limited by reactions with background molecules, and the high electron affinity of multiply charged ions such as Th$^{3+}$ make them more prone to loss. Our results show that reactions of Th$^{3+}$ with carbon dioxide, methane, and oxygen all occur near the classical Langevin rate, while reaction rates with argon, hydrogen, and nitrogen are orders of magnitude lower. Reactions of Th$^{3+}$ with oxygen and methane proceed primarily via charge exchange, while simultaneous charge exchange and chemical reaction occurs between Th$^{3+}$ and carbon dioxide. Loss rates of Th$^{3+}$ in helium are consistent with reaction with impurities in the gas. Reaction rates of Th$^{3+}$ with nitrogen and argon depend on the internal electronic configuration of the Th$^{3+}$.

  20. Formal balancing of chemical reaction networks

    NARCIS (Netherlands)

    van der Schaft, Abraham; Rao, S.; Jayawardhana, B.

    2016-01-01

    In this paper we recall and extend the main results of Van der Schaft, Rao, Jayawardhana (2015) concerning the use of Kirchhoff’s Matrix Tree theorem in the explicit characterization of complex-balanced reaction networks and the notion of formal balancing. The notion of formal balancing corresponds

  1. Simulations et optimisation des transferts thermochimiques dans un réacteur solide-gaz

    Science.gov (United States)

    Forestier, A.; Forges, P.; Amouroux, M.

    1997-07-01

    This paper deals with optimization of heat pipe in a solid-gas chemical heatpump. The core of such a system, namely a reactor, contains a porous solid able to react with a gas coming from an evaporator. The latter chemical reaction gives off heat. Conversely, if we supply the reactive media with heat, the previous chemical reaction occurs in the endothermic way and the gas so desorbed goes to a condensor. Two networks of gravitational heat pipes perform the energetical transfers between exchangers and porous media relies. The main goal of this work is to make an optimization of these transfers in shifting both dimension and localization of the exchangers. To carry out such a problem, we obviously need the knowledge of temperature and reaction advancement during any absorption or desorption process. We were face with the choice of an apt-method to figure out the governing non-linear partial differential equations axe available in the literature. We implemented first the finite difference technique but we were quickly compeled into using an advanced numerical method, namely the finite element method. A comparison between these two approaches has allowed to get the most adaptative numerical tool as regards to the optimization problem set. Cet article présente des résultats d'optimisation d'échangeurs dans un réacteur thermochimique. Ce dernier contient un solide poreux capable de réagir exothermiquement avec un gaz réactif venant d'un évaporateur. Inversement, s'il reçoit un apport de chaleur, la réaction précédente se produit dans le sens endothermique et le gaz désorbé est renvoyé vers un condenseur. Les transferts énergétiques entre les échangeurs de chaleur et le solide poreux sont assurés par des caloducs gravitationnels. Le principal objectif de cet article consiste à optimiser ces transferts en jouant sur le dimensionnement et la localisation de ces échangeurs. Ce problème d'optimisation nécessite bien entendu, dans un premier temps, la

  2. CHEMICAL REACTION: DIAGNOSIS AND TOWARDS REMEDY OF ...

    African Journals Online (AJOL)

    Preferred Customer

    Experience and literature show that most high school students do not have the correct mental models of coefficients and ... the combustion of hydrogen molecules, as represented by the equation. 2H2(g) + O2 (g). 2H2O(g). Ben-Zvi and his .... Simultaneous Chemical Representation in T-ZPD. • Incorporating Chemistry ...

  3. Ultrafast Dynamics of Chemical Reactions in Condensed Phase ...

    Indian Academy of Sciences (India)

    Ultrafast Dynamics of Chemical Reactions in Condensed Phase: Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond. Dipak K. Palit Radaition & Photochemistry Division Bhabha Atomic Research Centre Mumbai 400 085, India.

  4. Heterogeneously Catalysed Chemical Reactions in Carbon Dioxide Medium

    DEFF Research Database (Denmark)

    Musko, Nikolai E.

    In this PhD-study the different areas of chemical engineering, heterogeneous catalysis, supercritical fluids, and phase equilibrium thermodynamics have been brought together for selected reactions. To exploit the beneficial properties of supercritical fluids in heterogeneous catalysis, experimental......, and widely available reaction medium for many practical and industrial applications has drastically increased. Particularly attractive are heterogeneously catalysed chemical reactions. The beneficial use of CO2 is attributed to its unique properties at dense and supercritical states (at temperatures...... limitations in case of heterogeneous catalysis. Previous reports and the studies in the present thesis have shown that phase behaviour can play a crucial role in chemical reactions, especially when they are performed near the supercritical region of the reaction mixture. Experimental monitoring...

  5. Atomic structure of clusters through chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Riley, S.J.

    1991-01-01

    Techniques for the probing of isolated metal cluster structure through adsorbate binding patterns will be described. The saturation of clusters with reagents such as ammonia and nitrogen provides information on the number of preferred binding sites for these reagents. The dependence of this number on cluster size can suggest particular structural themes. The equilibrium reaction with water can be used to identify cluster sizes having especially enhanced binding for the water molecule. Again, the sequence of cluster sizes showing such enhancement can point to specific cluster structure. The reaction with oxygen can identify cluster sizes having particularly high ionization potentials, and these can be compared to simple models for the electronic structure of metal clusters. Representative applications of these probes to iron, cobalt, nickel, and copper clusters will be discussed. 5 figs.

  6. Theoretical Chemical Reaction for Herb Medicine

    OpenAIRE

    Sung-Mo Choi; Byeong-U Kim

    2002-01-01

    Objective : This study was designed to show the possible functional groups from the herb medicine in boiling water. Results : The results are summarized as follows: 1. the new functional groups can be synthesized in water solution for herb medicine. 2. The boiling water solution may change the poison materials into harmless materials. 3. The multiplication, the offset, the contradiction, etc. in terms of mixed herb medicine can be explainable by these reactions. 4. After finding the new m...

  7. Electronic dissipation processes during chemical reactions on surfaces

    CERN Document Server

    Stella, Kevin

    2012-01-01

    Hauptbeschreibung Every day in our life is larded with a huge number of chemical reactions on surfaces. Some reactions occur immediately, for others an activation energy has to be supplied. Thus it happens that though a reaction should thermodynamically run off, it is kinetically hindered. Meaning the partners react only to the thermodynamically more stable product state within a mentionable time if the activation energy of the reaction is supplied. With the help of catalysts the activation energy of a reaction can be lowered. Such catalytic processes on surfaces are widely used in industry. A

  8. Chemical modifications and reactions in DNA nanostructures

    DEFF Research Database (Denmark)

    Gothelf, Kurt Vesterager

    2017-01-01

    DNA nanotechnology has the power to form self-assembled and well-defined nanostructures, such as DNA origami, where the relative positions of each atom are known with subnanometer precision. Our ability to synthesize oligonucleotides with chemical modifications in almost any desired position...... provides rich opportunity to incorporate molecules, biomolecules, and a variety of nanomaterials in specific positions on DNA nanostructures. Several standard modifications for oligonucleotides are available commercially, such as dyes, biotin, and chemical handles, and such modified oligonucleotides can...... be applied directly for integration in DNA nanostructures. In another approach, various molecules and nanomaterials have been functionalized with DNA for incorporation in DNA nanostructures by hybridization to staple strands extending from the origami structure. Multiple copies of functionalities...

  9. Quantum Chemical Approach to Estimating the Thermodynamics of Metabolic Reactions

    Science.gov (United States)

    Jinich, Adrian; Rappoport, Dmitrij; Dunn, Ian; Sanchez-Lengeling, Benjamin; Olivares-Amaya, Roberto; Noor, Elad; Even, Arren Bar; Aspuru-Guzik, Alán

    2014-11-01

    Thermodynamics plays an increasingly important role in modeling and engineering metabolism. We present the first nonempirical computational method for estimating standard Gibbs reaction energies of metabolic reactions based on quantum chemistry, which can help fill in the gaps in the existing thermodynamic data. When applied to a test set of reactions from core metabolism, the quantum chemical approach is comparable in accuracy to group contribution methods for isomerization and group transfer reactions and for reactions not including multiply charged anions. The errors in standard Gibbs reaction energy estimates are correlated with the charges of the participating molecules. The quantum chemical approach is amenable to systematic improvements and holds potential for providing thermodynamic data for all of metabolism.

  10. Physical Chemistry Chemical Kinetics and Reaction Mechanism

    CERN Document Server

    Trimm, Harold H

    2011-01-01

    Physical chemistry covers diverse topics, from biochemistry to materials properties to the development of quantum computers. Physical chemistry applies physics and math to problems that interest chemists, biologists, and engineers. Physical chemists use theoretical constructs and mathematical computations to understand chemical properties and describe the behavior of molecular and condensed matter. Their work involves manipulations of data as well as materials. Physical chemistry entails extensive work with sophisticated instrumentation and equipment as well as state-of-the-art computers. This

  11. The Heck reaction in the production of fine chemicals

    NARCIS (Netherlands)

    Vries, Johannes G. de

    2001-01-01

    An overview is given of the use of the Heck reaction for the production of fine chemicals. Five commercial products have been identified that are produced on a scale in excess of 1 ton/year. The herbicide Prosulfuron™ is produced via a Matsuda reaction of 2-sulfonatobenzenediazonium on

  12. Raman Spectral Determination of Chemical Reaction Rate Characteristics

    Science.gov (United States)

    Balakhnina, I. A.; Brandt, N. N.; Mankova, A. A.; Chikishev, A. Yu.; Shpachenko, I. G.

    2017-09-01

    The feasibility of using Raman spectroscopy to determine chemical reaction rates and activation energies has been demonstrated for the saponification of ethyl acetate. The temperature dependence of the reaction rate was found in the range from 15 to 45°C.

  13. Non-isothermal gas absorption with reversible chemical reaction

    NARCIS (Netherlands)

    Vas Bhat, R.D.; Swaaij, W.P.M. van; Benes, N.E.; Kuipers, J.A.M.; Versteeg, G.F.

    1997-01-01

    A fundamental description of non-isothermal mass transfer accompanied by a single reversible chemical reaction has been presented. The description is based on the Higbie penetration theory. Arrhenius type dependence of solubility, reaction rates and diffusivities on temperature has been assumed.

  14. Non-isothermal gas absorption with reversible chemical reaction.

    NARCIS (Netherlands)

    Vas bhat, R.D.; van Swaaij, Willibrordus Petrus Maria; Benes, Nieck Edwin; Kuipers, J.A.M.; Versteeg, Geert

    1997-01-01

    A fundamental description of non-isothermal mass transfer accompanied by a single reversible chemical reaction has been presented. The description is based on the Higbie penetration theory. Arrhenius type dependence of solubility, reaction rates and diffusivities on temperature has been assumed.

  15. Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks

    Science.gov (United States)

    Cloonan, Carrie A.; Nichol, Carolyn A.; Hutchinson, John S.

    2011-01-01

    Chemical reaction kinetics and equilibrium are essential core concepts of chemistry but are challenging topics for many students, both at the high school and undergraduate university level. Visualization at the molecular level is valuable to aid understanding of reaction kinetics and equilibrium. This activity provides a discovery-based method to…

  16. Quantum Chemical Approach to Estimating the Thermodynamics of Metabolic Reactions

    OpenAIRE

    Adrian Jinich; Dmitrij Rappoport; Ian Dunn; Benjamin Sanchez-Lengeling; Roberto Olivares-Amaya; Elad Noor; Arren Bar Even; Alán Aspuru-Guzik

    2014-01-01

    Thermodynamics plays an increasingly important role in modeling and engineering metabolism. We present the first nonempirical computational method for estimating standard Gibbs reaction energies of metabolic reactions based on quantum chemistry, which can help fill in the gaps in the existing thermodynamic data. When applied to a test set of reactions from core metabolism, the quantum chemical approach is comparable in accuracy to group contribution methods for isomerization and group transfe...

  17. Theoretical Chemical Reaction for Herb Medicine

    Directory of Open Access Journals (Sweden)

    Sung-Mo Choi

    2002-12-01

    Full Text Available Objective : This study was designed to show the possible functional groups from the herb medicine in boiling water. Results : The results are summarized as follows: 1. the new functional groups can be synthesized in water solution for herb medicine. 2. The boiling water solution may change the poison materials into harmless materials. 3. The multiplication, the offset, the contradiction, etc. in terms of mixed herb medicine can be explainable by these reactions. 4. After finding the new medicinal substances for the specific disease, we can synthesize, modify, and mass produce those for that disease.

  18. Modelling Chemical Reasoning to Predict and Invent Reactions.

    Science.gov (United States)

    Segler, Marwin H S; Waller, Mark P

    2017-05-02

    The ability to reason beyond established knowledge allows organic chemists to solve synthetic problems and invent novel transformations. Herein, we propose a model that mimics chemical reasoning, and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outperforms a rule-based expert system in the reaction prediction task for 180 000 randomly selected binary reactions. The data-driven model generalises even beyond known reaction types, and is thus capable of effectively (re-)discovering novel transformations (even including transition metal-catalysed reactions). Our model enables computers to infer hypotheses about reactivity and reactions by only considering the intrinsic local structure of the graph and because each single reaction prediction is typically achieved in a sub-second time frame, the model can be used as a high-throughput generator of reaction hypotheses for reaction discovery. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Results of the 2010 Survey on Teaching Chemical Reaction Engineering

    Science.gov (United States)

    Silverstein, David L.; Vigeant, Margot A. S.

    2012-01-01

    A survey of faculty teaching the chemical reaction engineering course or sequence during the 2009-2010 academic year at chemical engineering programs in the United States and Canada reveals change in terms of content, timing, and approaches to teaching. The report consists of two parts: first, a statistical and demographic characterization of the…

  20. On the network thermodynamics of mass action chemical reaction networks

    NARCIS (Netherlands)

    Schaft, A.J. van der; Rao, S.; Jayawardhana, B.

    In this paper we elaborate on the mathematical formulation of mass action chemical reaction networks as recently given in van der Schaft, Rao, Jayawardhana (2012). We show how the reference chemical potentials define a specific thermodynamical equilibrium, and we discuss the port-Hamiltonian

  1. A robustness screen for the rapid assessment of chemical reactions.

    Science.gov (United States)

    Collins, Karl D; Glorius, Frank

    2013-07-01

    In contrast to the rapidity with which scientific information is published, the application of new knowledge often remains slow, and we believe this to be particularly true of newly developed synthetic organic chemistry methodology. Consequently, methods to assess and identify robust chemical reactions are desirable, and would directly facilitate the application of newly reported synthetic methodology to complex synthetic problems. Here, we describe a simple process for assessing the likely scope and limitations of a chemical reaction beyond the idealized reaction conditions initially reported. Using simple methods and common analytical techniques we demonstrate a rapid assessment of an established chemical reaction, and also propose a simplified analysis that may be reported alongside new synthetic methodology.

  2. ReactionMap: an efficient atom-mapping algorithm for chemical reactions.

    Science.gov (United States)

    Fooshee, David; Andronico, Alessio; Baldi, Pierre

    2013-11-25

    Large databases of chemical reactions provide new data-mining opportunities and challenges. Key challenges result from the imperfect quality of the data and the fact that many of these reactions are not properly balanced or atom-mapped. Here, we describe ReactionMap, an efficient atom-mapping algorithm. Our approach uses a combination of maximum common chemical subgraph search and minimization of an assignment cost function derived empirically from training data. We use a set of over 259,000 balanced atom-mapped reactions from the SPRESI commercial database to train the system, and we validate it on random sets of 1000 and 17,996 reactions sampled from this pool. These large test sets represent a broad range of chemical reaction types, and ReactionMap correctly maps about 99% of the atoms and about 96% of the reactions, with a mean time per mapping of 2 s. Most correctly mapped reactions are mapped with high confidence. Mapping accuracy compares favorably with ChemAxon's AutoMapper, versions 5 and 6.1, and the DREAM Web tool. These approaches correctly map 60.7%, 86.5%, and 90.3% of the reactions, respectively, on the same data set. A ReactionMap server is available on the ChemDB Web portal at http://cdb.ics.uci.edu .

  3. Single-molecule chemical reaction reveals molecular reaction kinetics and dynamics.

    Science.gov (United States)

    Zhang, Yuwei; Song, Ping; Fu, Qiang; Ruan, Mingbo; Xu, Weilin

    2014-06-25

    Understanding the microscopic elementary process of chemical reactions, especially in condensed phase, is highly desirable for improvement of efficiencies in industrial chemical processes. Here we show an approach to gaining new insights into elementary reactions in condensed phase by combining quantum chemical calculations with a single-molecule analysis. Elementary chemical reactions in liquid-phase, revealed from quantum chemical calculations, are studied by tracking the fluorescence of single dye molecules undergoing a reversible redox process. Statistical analyses of single-molecule trajectories reveal molecular reaction kinetics and dynamics of elementary reactions. The reactivity dynamic fluctuations of single molecules are evidenced and probably arise from either or both of the low-frequency approach of the molecule to the internal surface of the SiO2 nanosphere or the molecule diffusion-induced memory effect. This new approach could be applied to other chemical reactions in liquid phase to gain more insight into their molecular reaction kinetics and the dynamics of elementary steps.

  4. Automatic NMR-based identification of chemical reaction types in mixtures of co-occurring reactions.

    Directory of Open Access Journals (Sweden)

    Diogo A R S Latino

    Full Text Available The combination of chemoinformatics approaches with NMR techniques and the increasing availability of data allow the resolution of problems far beyond the original application of NMR in structure elucidation/verification. The diversity of applications can range from process monitoring, metabolic profiling, authentication of products, to quality control. An application related to the automatic analysis of complex mixtures concerns mixtures of chemical reactions. We encoded mixtures of chemical reactions with the difference between the (1H NMR spectra of the products and the reactants. All the signals arising from all the reactants of the co-occurring reactions were taken together (a simulated spectrum of the mixture of reactants and the same was done for products. The difference spectrum is taken as the representation of the mixture of chemical reactions. A data set of 181 chemical reactions was used, each reaction manually assigned to one of 6 types. From this dataset, we simulated mixtures where two reactions of different types would occur simultaneously. Automatic learning methods were trained to classify the reactions occurring in a mixture from the (1H NMR-based descriptor of the mixture. Unsupervised learning methods (self-organizing maps produced a reasonable clustering of the mixtures by reaction type, and allowed the correct classification of 80% and 63% of the mixtures in two independent test sets of different similarity to the training set. With random forests (RF, the percentage of correct classifications was increased to 99% and 80% for the same test sets. The RF probability associated to the predictions yielded a robust indication of their reliability. This study demonstrates the possibility of applying machine learning methods to automatically identify types of co-occurring chemical reactions from NMR data. Using no explicit structural information about the reactions participants, reaction elucidation is performed without structure

  5. Automatic NMR-Based Identification of Chemical Reaction Types in Mixtures of Co-Occurring Reactions

    Science.gov (United States)

    Latino, Diogo A. R. S.; Aires-de-Sousa, João

    2014-01-01

    The combination of chemoinformatics approaches with NMR techniques and the increasing availability of data allow the resolution of problems far beyond the original application of NMR in structure elucidation/verification. The diversity of applications can range from process monitoring, metabolic profiling, authentication of products, to quality control. An application related to the automatic analysis of complex mixtures concerns mixtures of chemical reactions. We encoded mixtures of chemical reactions with the difference between the 1H NMR spectra of the products and the reactants. All the signals arising from all the reactants of the co-occurring reactions were taken together (a simulated spectrum of the mixture of reactants) and the same was done for products. The difference spectrum is taken as the representation of the mixture of chemical reactions. A data set of 181 chemical reactions was used, each reaction manually assigned to one of 6 types. From this dataset, we simulated mixtures where two reactions of different types would occur simultaneously. Automatic learning methods were trained to classify the reactions occurring in a mixture from the 1H NMR-based descriptor of the mixture. Unsupervised learning methods (self-organizing maps) produced a reasonable clustering of the mixtures by reaction type, and allowed the correct classification of 80% and 63% of the mixtures in two independent test sets of different similarity to the training set. With random forests (RF), the percentage of correct classifications was increased to 99% and 80% for the same test sets. The RF probability associated to the predictions yielded a robust indication of their reliability. This study demonstrates the possibility of applying machine learning methods to automatically identify types of co-occurring chemical reactions from NMR data. Using no explicit structural information about the reactions participants, reaction elucidation is performed without structure elucidation of the

  6. Chemical Looping Combustion Reactions and Systems

    Energy Technology Data Exchange (ETDEWEB)

    Sarofim, Adel; Lighty, JoAnn; Smith, Philip; Whitty, Kevin; Eyring, Edward; Sahir, Asad; Alvarez, Milo; Hradisky, Michael; Clayton, Chris; Konya, Gabor; Baracki, Richard; Kelly, Kerry

    2011-07-01

    Chemical Looping Combustion (CLC) is one promising fuel-combustion technology, which can facilitate economic CO2 capture in coal-fired power plants. It employs the oxidation/reduction characteristics of a metal, or oxygen carrier, and its oxide, the oxidizing gas (typically air) and the fuel source may be kept separate. This work focused on two classes of oxygen carrier, one that merely undergoes a change in oxidation state, such as Fe3O4/Fe2O3 and one that is converted from its higher to its lower oxidation state by the release of oxygen on heating, i.e., CuO/Cu2O. This topical report discusses the results of four complementary efforts: (1) the development of process and economic models to optimize important design considerations, such as oxygen carrier circulation rate, temperature, residence time; (2) the development of high-performance simulation capabilities for fluidized beds and the collection, parameter identification, and preliminary verification/uncertainty quantification (3) the exploration of operating characteristics in the laboratory-scale bubbling bed reactor, with a focus on the oxygen carrier performance, including reactivity, oxygen carrying capacity, attrition resistance, resistance to deactivation, cost and availability (4) the identification of mechanisms and rates for the copper, cuprous oxide, and cupric oxide system using thermogravimetric analysis.

  7. Context-Driven Exploration of Complex Chemical Reaction Networks.

    Science.gov (United States)

    Simm, Gregor N; Reiher, Markus

    2017-12-12

    The construction of a reaction network containing all relevant intermediates and elementary reactions is necessary for the accurate description of chemical processes. In the case of a complex chemical reaction (involving, for instance, many reactants or highly reactive species), the size of such a network may grow rapidly. Here, we present a computational protocol that constructs such reaction networks in a fully automated fashion steered in an intuitive, graph-based fashion through a single graphical user interface. Starting from a set of initial reagents new intermediates are explored through intra- and intermolecular reactions of already explored intermediates or new reactants presented to the network. This is done by assembling reactive complexes based on heuristic rules derived from conceptual electronic-structure theory and exploring the corresponding approximate reaction path. A subsequent path refinement leads to a minimum-energy path which connects the new intermediate to the existing ones to form a connected reaction network. Tree traversal algorithms are then employed to detect reaction channels and catalytic cycles. We apply our protocol to the formose reaction to study different pathways of sugar formation and to rationalize its autocatalytic nature.

  8. An Efficient Chemical Reaction Optimization Algorithm for Multiobjective Optimization.

    Science.gov (United States)

    Bechikh, Slim; Chaabani, Abir; Ben Said, Lamjed

    2015-10-01

    Recently, a new metaheuristic called chemical reaction optimization was proposed. This search algorithm, inspired by chemical reactions launched during collisions, inherits several features from other metaheuristics such as simulated annealing and particle swarm optimization. This fact has made it, nowadays, one of the most powerful search algorithms in solving mono-objective optimization problems. In this paper, we propose a multiobjective variant of chemical reaction optimization, called nondominated sorting chemical reaction optimization, in an attempt to exploit chemical reaction optimization features in tackling problems involving multiple conflicting criteria. Since our approach is based on nondominated sorting, one of the main contributions of this paper is the proposal of a new quasi-linear average time complexity quick nondominated sorting algorithm; thereby making our multiobjective algorithm efficient from a computational cost viewpoint. The experimental comparisons against several other multiobjective algorithms on a variety of benchmark problems involving various difficulties show the effectiveness and the efficiency of this multiobjective version in providing a well-converged and well-diversified approximation of the Pareto front.

  9. Investigation of Electric Arc Furnace Chemical Reactions and stirring effect

    OpenAIRE

    Deng, Lei

    2012-01-01

    Chemical energy plays a big role in the process of modern Electric Arc Furnace (EAF). The objective of this study is to compare the results of chemical reaction enthalpies calculated by four different methods. In general, the “PERRY-NIST-JANAF method” is used to calculate the chemical energies. However, this method heavily depend on heat capacities of the substances which have to be deduced from  “Perry’s Chemical Engineers’ Handbook” and “NIST-JANAF Thermochemical Tables”, even the calculati...

  10. The thermodynamic natural path in chemical reaction kinetics

    Directory of Open Access Journals (Sweden)

    Moishe garfinkle

    2000-01-01

    Full Text Available The Natural Path approach to chemical reaction kinetics was developed to bridge the considerable gap between the Mass Action mechanistic approach and the non-mechanistic irreversible thermodynamic approach. The Natural Path approach can correlate empirical kinetic data with a high degree precision, as least equal to that achievable by the Mass-Action rate equations, but without recourse mechanistic considerations. The reaction velocities arising from the particular rate equation chosen by kineticists to best represent the kinetic behavior of a chemical reaction are the natural outcome of the Natural Path approach. Moreover, by virtue of its thermodynamic roots, equilibrium thermodynamic functions can be extracted from reaction kinetic data with considerable accuracy. These results support the intrinsic validity of the Natural Path approach.

  11. Common side reactions of the glycosyl donor in chemical glycosylation.

    Science.gov (United States)

    Christensen, Helle M; Oscarson, Stefan; Jensen, Henrik H

    2015-05-18

    Chemical glycosylation is central to carbohydrate chemistry and is generally recognised as a challenging reaction. This review describes the most reoccurring side reactions of glycosyl donors in glycosylation and how scientists have attempted to explain their observations and in some cases succeeded in solving a particular encountered problem. The topics covered are donor hydrolysis, elimination to form glycals, intermolecular aglycon transfer of thioglycosides and glycosyl imidate rearrangement. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Computation of mixing and chemical reaction in stirred vessels

    Science.gov (United States)

    Ziman, H.; Middleton, J. C.

    1991-05-01

    Chemical reactions carried out in stirred vessels in industrial practice are commonly complex in that they have several steps which, for example, may complete for a reactant and form different products from it. Usually, one of these products is desired whereas the other is a waste product giving rise to extra costs of recycling or disposal. In some cases, the rate and pattern of mixing in the vessel influences the reaction selectivity to the desired product. One example of this occurs when one of the competing reactions is fast (its rate being mixing-controlled), while the other is slower. In such cases, it is found that the only successful predictive design or scale-up method available is to model the mixing process in detail and superpose the reaction kinetics, using computational fluid dynamics. This paper presents a suitable computational procedure, which first calculates the three-dimensional flow field in a stirred vessel, then solves the equations describing the mixing and chemical reactions that will occur at each place and time in that calculated flow field. Special attention is given to formulating the concentration transport equations in a manner that is efficient and simple to apply to various reaction schemes. The approach adopted uses the concepts of mixture fraction and reaction extent, and enables the program to handle almost any reaction scheme without any additional programming. Macro- and micromixing regimes are included. In the latter case, consideration is given to the interaction of turbulence and the local reaction rate, using a simple model based on a local mixing time scale. Example calculations are presented that show the ability of the method to calculate mixing times and reaction yields. Experiments with a competitive reaction scheme are described and their results compared with computed predictions, in a regime in which the traditional rules of thumb for scale-up are unsuccessful.

  13. Universality and chaoticity in ultracold K+KRb chemical reactions

    Science.gov (United States)

    Croft, J. F. E.; Makrides, C.; Li, M.; Petrov, A.; Kendrick, B. K.; Balakrishnan, N.; Kotochigova, S.

    2017-07-01

    A fundamental question in the study of chemical reactions is how reactions proceed at a collision energy close to absolute zero. This question is no longer hypothetical: quantum degenerate gases of atoms and molecules can now be created at temperatures lower than a few tens of nanokelvin. Here we consider the benchmark ultracold reaction between, the most-celebrated ultracold molecule, KRb and K. We map out an accurate ab initio ground-state potential energy surface of the K2Rb complex in full dimensionality and report numerically-exact quantum-mechanical reaction dynamics. The distribution of rotationally resolved rates is shown to be Poissonian. An analysis of the hyperspherical adiabatic potential curves explains this statistical character revealing a chaotic distribution for the short-range collision complex that plays a key role in governing the reaction outcome.

  14. Researches on Preliminary Chemical Reactions in Spark-Ignition Engines

    Science.gov (United States)

    Muehlner, E.

    1943-01-01

    Chemical reactions can demonstrably occur in a fuel-air mixture compressed in the working cylinder of an Otto-cycle (spark ignition) internal-combustion engine even before the charge is ignited by the flame proceeding from the sparking plug. These are the so-called "prelinminary reactions" ("pre-flame" combustion or oxidation), and an exact knowledge of their characteristic development is of great importance for a correct appreciation of the phenomena of engine-knock (detonation), and consequently for its avoidance. Such reactions can be studied either in a working engine cylinder or in a combustion bomb. The first method necessitates a complicated experimental technique, while the second has the disadvantage of enabling only a single reaction to be studied at one time. Consequently, a new series of experiments was inaugurated, conducted in a motored (externally-driven) experimental engine of mixture-compression type, without ignition, the resulting preliminary reactions being detectable and measurable thermometrically.

  15. Effects of incomplete mixing on chemical reactions under flow heterogeneities.

    Science.gov (United States)

    Perez, Lazaro; Hidalgo, Juan J.; Dentz, Marco

    2016-04-01

    Evaluation of the mixing process in aquifers is of primary importance when assessing attenuation of pollutants. In aquifers different hydraulic and chemical properties can increase mixing and spreading of the transported species. Mixing processes control biogeochemical transformations such as precipitation/dissolution reactions or degradation reactions that are fast compared to mass transfer processes. Reactions are local phenomena that fluctuate at the pore scale, but predictions are often made at much larger scales. However, aquifer heterogeities are found at all scales and generates flow heterogeneities which creates complex concentration distributions that enhances mixing. In order to assess the impact of spatial flow heterogeneities at pore scale we study concentration profiles, gradients and reaction rates using a random walk particle tracking (RWPT) method and kernel density estimators to reconstruct concentrations and gradients in two setups. First, we focus on a irreversible bimolecular reaction A+B → C under homogeneous flow to distinguish phenomena of incomplete mixing of reactants from finite-size sampling effects. Second, we analise a fast reversible bimolecular chemical reaction A+B rightleftharpoons C in a laminar Poiseuille flow reactor to determine the difference between local and global reaction rates caused by the incomplete mixing under flow heterogeneities. Simulation results for the first setup differ from the analytical solution of the continuum scale advection-dispersion-reaction equation studied by Gramling et al. (2002), which results in an overstimation quantity of reaction product (C). In the second setup, results show that actual reaction rates are bigger than the obtained from artificially mixing the system by averaging the concentration vertically. - LITERATURE Gramling, C. M.,Harvey, C. F., Meigs, and L. C., (2002). Reactive transport in porous media: A comparison of model prediction with laboratory visualization, Environ. Sci

  16. Reaction diffusion and solid state chemical kinetics handbook

    CERN Document Server

    Dybkov, V I

    2010-01-01

    This monograph deals with a physico-chemical approach to the problem of the solid-state growth of chemical compound layers and reaction-diffusion in binary heterogeneous systems formed by two solids; as well as a solid with a liquid or a gas. It is explained why the number of compound layers growing at the interface between the original phases is usually much lower than the number of chemical compounds in the phase diagram of a given binary system. For example, of the eight intermetallic compounds which exist in the aluminium-zirconium binary system, only ZrAl3 was found to grow as a separate

  17. Chemical Reaction Engineering: Current Status and Future Directions.

    Science.gov (United States)

    Dudukovic, M. P.

    1987-01-01

    Describes Chemical Reaction Engineering (CRE) as the discipline that quantifies the interplay of transport phenomena and kinetics in relating reactor performance to operating conditions and input variables. Addresses the current status of CRE in both academic and industrial settings and outlines future trends. (TW)

  18. Performing chemical reactions in virtual capillary of surface tension ...

    Indian Academy of Sciences (India)

    We have also successfully carried out some well-known chemical reactions in these fluidic channels to demonstrate the usefulness of these wall-less microchannels. The confined flow path of liquid was achieved on the basis of extreme differences in hydrophobic and hydrophilic characters of the surface. The flow paths ...

  19. Molecular codes in biological and chemical reaction networks.

    Directory of Open Access Journals (Sweden)

    Dennis Görlich

    Full Text Available Shannon's theory of communication has been very successfully applied for the analysis of biological information. However, the theory neglects semantic and pragmatic aspects and thus cannot directly be applied to distinguish between (bio- chemical systems able to process "meaningful" information from those that do not. Here, we present a formal method to assess a system's semantic capacity by analyzing a reaction network's capability to implement molecular codes. We analyzed models of chemical systems (martian atmosphere chemistry and various combustion chemistries, biochemical systems (gene expression, gene translation, and phosphorylation signaling cascades, an artificial chemistry, and random reaction networks. Our study suggests that different chemical systems possess different semantic capacities. No semantic capacity was found in the model of the martian atmosphere chemistry, the studied combustion chemistries, and highly connected random networks, i.e. with these chemistries molecular codes cannot be implemented. High semantic capacity was found in the studied biochemical systems and in random reaction networks where the number of second order reactions is twice the number of species. We conclude that our approach can be applied to evaluate the information processing capabilities of a chemical system and may thus be a useful tool to understand the origin and evolution of meaningful information, e.g. in the context of the origin of life.

  20. Combined effects of radiation and chemical reaction on MHD flow ...

    African Journals Online (AJOL)

    Influence of radiation and chemical reaction on MHD flow past a moving plate with Hall current is studied here. Earlier, we (2016) have studied unsteady MHD flow in porous media over exponentially accelerated plate with variable wall temperature and mass transfer along with Hall current. To study further, we are changing ...

  1. Computer simulation of chemical reactions in porous materials

    Science.gov (United States)

    Turner, Christoffer Heath

    Understanding reactions in nanoporous materials from a purely experimental perspective is a difficult task. Measuring the chemical composition of a reacting system within a catalytic material is usually only accomplished through indirect methods, and it is usually impossible to distinguish between true chemical equilibrium and metastable states. In addition, measuring molecular orientation or distribution profiles within porous systems is not easily accomplished. However, molecular simulation techniques are well-suited to these challenges. With appropriate simulation techniques and realistic molecular models, it is possible to validate the dominant physical and chemical forces controlling nanoscale reactivity. Novel nanostructured catalysts and supports can be designed, optimized, and tested using high-performance computing and advanced modeling techniques in order to guide the search for next-generation catalysts---setting new targets for the materials synthesis community. We have simulated the conversion of several different equilibrium-limited reactions within microporous carbons and we find that the pore size, pore geometry, and surface chemistry are important factors for determining the reaction yield. The equilibrium-limited reactions that we have modeled include nitric oxide dimerization, ammonia synthesis, and the esterification of acetic acid, all of which show yield enhancements within microporous carbons. In conjunction with a yield enhancement of the esterification reaction, selective adsorption of ethyl acetate within carbon micropores demonstrates an efficient method for product recovery. Additionally, a new method has been developed for simulating reaction kinetics within porous materials and other heterogeneous environments. The validity of this technique is first demonstrated by reproducing the kinetics of hydrogen iodide decomposition in the gas phase, and then predictions are made within slit-shaped carbon pores and carbon nanotubes. The rate

  2. NATO Advanced Study Institute on Advances in Chemical Reaction Dynamics

    CERN Document Server

    Capellos, Christos

    1986-01-01

    This book contains the formal lectures and contributed papers presented at the NATO Advanced Study Institute on. the Advances in Chemical Reaction Dynamics. The meeting convened at the city of Iraklion, Crete, Greece on 25 August 1985 and continued to 7 September 1985. The material presented describes the fundamental and recent advances in experimental and theoretical aspects of, reaction dynamics. A large section is devoted to electronically excited states, ionic species, and free radicals, relevant to chemical sys­ tems. In addition recent advances in gas phase polymerization, formation of clusters, and energy release processes in energetic materials were presented. Selected papers deal with topics such as the dynamics of electric field effects in low polar solutions, high electric field perturbations and relaxation of dipole equilibria, correlation in picosecond/laser pulse scattering, and applications to fast reaction dynamics. Picosecond transient Raman spectroscopy which has been used for the elucidati...

  3. Modeling Electric Double-Layers Including Chemical Reaction Effects

    DEFF Research Database (Denmark)

    Paz-Garcia, Juan Manuel; Johannesson, Björn; Ottosen, Lisbeth M.

    2014-01-01

    for symmetric and asymmetric multi-species electrolytes and is not limited to a range of surface potentials. Numerical simulations are presented, for the case of a CaCO3 electrolyte solution in contact with a surface with rate-controlled protonation/deprotonation reactions. The surface charge and potential...... are determined by the surface reactions, and therefore they depends on the bulk solution composition and concentration......A physicochemical and numerical model for the transient formation of an electric double-layer between an electrolyte and a chemically-active flat surface is presented, based on a finite elements integration of the nonlinear Nernst-Planck-Poisson model including chemical reactions. The model works...

  4. Single-molecule chemical reactions on DNA origami

    DEFF Research Database (Denmark)

    Voigt, Niels Vinther; Tørring, Thomas; Rotaru, Alexandru

    2010-01-01

    as templates for building materials with new functional properties. Relatively large nanocomponents such as nanoparticles and biomolecules can also be integrated into DNA nanostructures and imaged. Here, we show that chemical reactions with single molecules can be performed and imaged at a local position...... on a DNA origami scaffold by atomic force microscopy. The high yields and chemoselectivities of successive cleavage and bond-forming reactions observed in these experiments demonstrate the feasibility of post-assembly chemical modification of DNA nanostructures and their potential use as locally......DNA nanotechnology and particularly DNA origami, in which long, single-stranded DNA molecules are folded into predetermined shapes, can be used to form complex self-assembled nanostructures. Although DNA itself has limited chemical, optical or electronic functionality, DNA nanostructures can serve...

  5. Flow-Injection Responses of Diffusion Processes and Chemical Reactions

    DEFF Research Database (Denmark)

    Andersen, Jens Enevold Thaulov

    2000-01-01

    The technique of Flow-injection Analysis (FIA), now aged 25 years, offers unique analytical methods that are fast, reliable and consuming an absolute minimum of chemicals. These advantages together with its inherent feasibility for automation warrant the future applications of FIA as an attractiv...... be used in the resolution of FIA profiles to obtain information about the content of interference’s, in the study of chemical reaction kinetics and to measure absolute concentrations within the FIA-detector cell....... manifold may be characterised by a diffusion coefficient that depends on flow rate, denoted as the kinematic diffusion coefficient. The description was applied to systems involving species of chromium, both in the case of simple diffusion and in the case of chemical reactions. It is suggested that it may...

  6. Diabatic models with transferrable parameters for generalized chemical reactions

    Science.gov (United States)

    Reimers, Jeffrey R.; McKemmish, Laura K.; McKenzie, Ross H.; Hush, Noel S.

    2017-05-01

    Diabatic models applied to adiabatic electron-transfer theory yield many equations involving just a few parameters that connect ground-state geometries and vibration frequencies to excited-state transition energies and vibration frequencies to the rate constants for electron-transfer reactions, utilizing properties of the conical-intersection seam linking the ground and excited states through the Pseudo Jahn-Teller effect. We review how such simplicity in basic understanding can also be obtained for general chemical reactions. The key feature that must be recognized is that electron-transfer (or hole transfer) processes typically involve one electron (hole) moving between two orbitals, whereas general reactions typically involve two electrons or even four electrons for processes in aromatic molecules. Each additional moving electron leads to new high-energy but interrelated conical-intersection seams that distort the shape of the critical lowest-energy seam. Recognizing this feature shows how conical-intersection descriptors can be transferred between systems, and how general chemical reactions can be compared using the same set of simple parameters. Mathematical relationships are presented depicting how different conical-intersection seams relate to each other, showing that complex problems can be reduced into an effective interaction between the ground-state and a critical excited state to provide the first semi-quantitative implementation of Shaik’s “twin state” concept. Applications are made (i) demonstrating why the chemistry of the first-row elements is qualitatively so different to that of the second and later rows, (ii) deducing the bond-length alternation in hypothetical cyclohexatriene from the observed UV spectroscopy of benzene, (iii) demonstrating that commonly used procedures for modelling surface hopping based on inclusion of only the first-derivative correction to the Born-Oppenheimer approximation are valid in no region of the chemical

  7. Students' Understandings of Chemical Bonds and the Energetics of Chemical Reactions.

    Science.gov (United States)

    Boo, Hong Kwen

    1998-01-01

    Investigates Grade 12 students' understandings of the nature of chemical bonds and the energetics elicited across five familiar chemical reactions following a course of instruction. Discusses the many ways in which students can misconstruct concepts and principles. Contains 63 references. (DDR)

  8. Chemical research on red pigments after adverse reactions to tattoo.

    Science.gov (United States)

    Tammaro, A; Toniolo, C; Giulianelli, V; Serafini, M; Persechino, S

    2016-03-01

    Currently, the incidence of tattooing is on the rise compared to the past, especially among adolescents, and it leads to the urgency of monitoring the security status of tattooing centers, as well as to inform people about the risks of tattoo practice. In our clinical experience, 20% of tattooed patients presented adverse reactions, like allergic contact dermatitis, psoriasis with Koebner's phenomena and granulomatous reactions, with the latter most prevalent and most often related to red pigment. Adverse reactions to tattoo pigments, especially the red one, are well known and described in literature. Great attention has to be focused on the pigments used, especially for the presence of new substances, often not well known. For this reason, we decided to perform a study on 12 samples of red tattoo ink, obtained by patients affected by different cutaneous reactions in the site of tattoo, to analyze their chemical composition.

  9. Reaction of mutualistic and granivorous ants to ulex elaiosome chemicals.

    Science.gov (United States)

    Gammans, Nicola; Bullock, James M; Gibbons, Hannah; Schönrogge, Karsten

    2006-09-01

    It has been proposed that chemicals on plant elaiosomes aid seed detection by seed-dispersing ants. We hypothesized that the chemical interaction between ants and elaiosomes is more intimate than a generic attraction, and that elaiosome chemicals will attract mutualistic but not granivorous ant species. We investigated this by using two gorse species, Ulex minor and U. europaeus, and two associated ant species from European heathlands, the mutualist Myrmica ruginodis and the granivore Tetramorium caespitum. Behavioral studies were conducted with laboratory nests and foraging arenas. Both ants will take Ulex seeds, but while M. ruginodis showed increased antennation toward ether extracts of elaiosome surface chemicals compared with controls, T. caespitum showed no response. Elaiosome extracts were separated into seven lipid fractions. M. ruginodis showed increased antennation only toward the diglyceride fractions of both Ulex species, whereas T. caespitum showed no consistent reaction. This indicates that M. ruginodis can detect the elaiosome by responding to its surface chemicals, but T. caespitum is unresponsive to these chemicals. Responses to surface chemicals could increase the rate of seed detection in the field, and so these results suggest that Ulex elaiosomes produce chemicals that facilitate attraction of mutualistic rather than granivorous ant species. This could reduce seed predation and increase Ulex fitness.

  10. Laser studies of chemical reaction and collision processes

    Energy Technology Data Exchange (ETDEWEB)

    Flynn, G. [Columbia Univ., New York, NY (United States)

    1993-12-01

    This work has concentrated on several interrelated projects in the area of laser photochemistry and photophysics which impinge on a variety of questions in combustion chemistry and general chemical kinetics. Infrared diode laser probes of the quenching of molecules with {open_quotes}chemically significant{close_quotes} amounts of energy in which the energy transferred to the quencher has, for the first time, been separated into its vibrational, rotational, and translational components. Probes of quantum state distributions and velocity profiles for atomic fragments produced in photodissociation reactions have been explored for iodine chloride.

  11. Potential for exothermic chemical reactions in waste tanks

    Energy Technology Data Exchange (ETDEWEB)

    Van Tuyl, H.H.

    1983-02-03

    The potential for exothermic chemical reactions in waste tanks at Hanford is discussed. Organic chemicals have been added to Hanford waste tanks, particularly as ferrocyanides and when processing sludges at B Plant. Recent planned or ongoing activities involving stored wastes have possibly increased the potential for reaction of these wastes with nitrate salts in the waste tanks. Risk evaluations appear to be deficient in assessing the consequences of a deflagration, and in determining the probability of either a deflagration or detonation. The present question is whether current plans and recent safety-related documentation have given proper consideration to the available information about organic compounds in waste tanks. The principal organic additions to Hanford waste tanks are 1200 tonnes of organic carbon'' and 500 tonnes of Ni{sub 2}Fe(CN){sub 6}. 13 refs.

  12. Simulation of underexpanded supersonic jet flows with chemical reactions

    Directory of Open Access Journals (Sweden)

    Fu Debin

    2014-06-01

    Full Text Available To achieve a detailed understanding of underexpanded supersonic jet structures influenced by afterburning and other flow conditions, the underexpanded turbulent supersonic jet with and without combustions are investigated by computational fluid dynamics (CFD method. A program based on a total variation diminishing (TVD methodology capable of predicting complex shocks is created to solve the axisymmetric expanded Navier–Stokes equations containing transport equations of species. The finite-rate ratio model is employed to handle species sources in chemical reactions. CFD solutions indicate that the structure of underexpanded jet is typically influenced by the pressure ratio and afterburning. The shock reflection distance and maximum value of Mach number in the first shock cell increase with pressure ratio. Chemical reactions for the rocket exhaust mostly exist in the mixing layer of supersonic jet flows. This tends to reduce the intensity of shocks existing in the jet, responding to the variation of thermal parameters.

  13. Study of the {sup 18}F(p,{alpha}){sup 15}O reaction by transfer reaction for application to {gamma}-ray emission from Novae; Etude de la reaction {sup 18}F(p,{alpha}){sup 15}O par reaction de transfert pour application a l'emission {gamma} des Novae

    Energy Technology Data Exchange (ETDEWEB)

    Sereville, N. de

    2003-12-15

    The gamma emission from novae at/or below 511 keV is due to the annihilation of the positrons produced in the beta + decay of F{sup 18}. The interpretation of this emission through observations made by the Integral satellite for instance, requires a good knowledge of F{sup 18} nucleosynthesis. The reaction rate of the F{sup 18}(p,{alpha})O{sup 15} is the least known because of 2 resonances corresponding to the levels 6.419 and 6.449 MeV of Ne{sup 19} whose proton widths are completely unknown. We have determined these proton widths via the study of one-nucleon transfer reaction D(F{sup 18},p{alpha})N{sup 15} populating equivalent levels in F{sup 19}. We have used a 14 MeV F{sup 18} radioactive beam on a CD{sub 2} target for inverse kinematics studies and the multi-track silicon detector LEDA. A DWBA (Distorted Wave Bound Approximation) has enabled us to determine the proton width of both resonances and has showed that they have an impact in the calculation of the reaction rate. A thorough study of the remaining uncertainties of the reaction rate has been undertaken, particularly for those concerning interferences between these resonances and a higher resonance of Ne{sup 19}. The reaction rate that we have obtained is very similar to the previous rate used but now it rests on a more solid basis.

  14. Computational Study on Chemical Reaction Mechanisms of Octafluorocarbon Molecules

    Science.gov (United States)

    Choi, Heechol; Song, Mi-Young; Yoon, Jung-Sik; Plasma Fundamental Technology Research Team

    2015-09-01

    Saturated or unsaturated octafluorocarbons(OFCs) have been used extensively in dry etching processes due to their relatively low global warming potential and their high CF2 radical levels in commercial plasma treatments. Many experimental and theoretical studies of these species have been performed for useful information about physical and chemical properties of OFCs. However, direct experimental studies of these chemicals are difficult because of their high reactivity in plasma state and high-level theoretical approaches such as G3(MP2) and CCSD(T)/CBS need huge computational cost. Recently, it has been shown that the ωB97X-D/aVTZ method is strongly recommended as the best practical density functional theory(DFT) for rigorous and extensive studies of OFCs because of its high performance and reliability for van der Waals interactions. All the feasible isomerization and dissociation paths of OFCs were investigated at ωB97X-D/aVTZ and rate constants of their chemical reactions were computed by using variational transition-state theory(VTST) for a deep insight into OFCs' reaction mechanisms. Fates and roles of OFCs and their fragments in plasma phases could be clearly explained based on the obtained reaction mechanisms. This work was supported by R&D Program of ``Plasma Convergence & Fundamental Research'' through NFRI of Korea funded by the Government funds.

  15. Laser-initiated chemical reactions in carbon suspensions.

    Energy Technology Data Exchange (ETDEWEB)

    McGrath, T. E.; Diebold, G. J.; Bartels, D. M.; Crowell, R. A.; Chemistry; Brown Univ.

    2002-10-31

    We report on laser-initiated chemical reactions in colloidal carbon suspensions. Irradiation of carbon particles ranging in size from 13 to 75 nm in diameter suspended in water, toluene, and benzene with high power nanosecond, picosecond, and femtosecond laser pulses leads to the formation of a number of gaseous hydrocarbons as well as a series of liquid-phase products. In the product gas above irradiated carbon suspensions in water, H{sub 2} and CO, the main reaction products of the carbon-steam reaction, and numerous hydrocarbons ranging from C{sub 1}-C{sub 4} were detected. Irradiation of particulate carbon in toluene and benzene gave H{sub 2} as the main gas product with small amounts of C{sub 1}-C{sub 3} hydrocarbons. Bibenzyl and biphenyl were found as the main liquid products produced in toluene and benzene suspensions, respectively, but with numerous polycyclic aromatic hydrocarbons in smaller concentrations. The amount of products generated by pulsed laser irradiation is shown to depend on particle size and concentration, as well as the laser fluence and pulse width. The chemical reactions reported take place under conditions characterized by extremely high temperatures and pressures of short duration.

  16. Chemical dynamics in the gas phase: Time-dependent quantum mechanics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gray, S.K. [Argonne National Laboratory, IL (United States)

    1993-12-01

    A major goal of this research is to obtain an understanding of the molecular reaction dynamics of three and four atom chemical reactions using numerically accurate quantum dynamics. This work involves: (i) the development and/or improvement of accurate quantum mechanical methods for the calculation and analysis of the properties of chemical reactions (e.g., rate constants and product distributions), and (ii) the determination of accurate dynamical results for selected chemical systems, which allow one to compare directly with experiment, determine the reliability of the underlying potential energy surfaces, and test the validity of approximate theories. This research emphasizes the use of recently developed time-dependent quantum mechanical methods, i.e. wave packet methods.

  17. [Recent results in research on oscillatory chemical reactions].

    Science.gov (United States)

    Poros, Eszter; Kurin-Csörgei, Krisztina

    2014-01-01

    The mechanisms of the complicated periodical phenomenas in the nature (e.g. hearth beat, sleep cycle, circadian rhythms, etc) could be understood with using the laws of nonlinear chemical systems. In this article the newest result in the research of the subfield of nonlinear chemical dynamics aimed at constructing oscillatory chemical reactions, which are novel either in composition or in configuration, are presented. In the introductory part the concept of chemical periodicity is defined, then the forms as it can appear in time and space and the methods of their study are discussed. Detailed description of the experimental work that has resulted in two significant discoveries is provided. A method was developed to design pH-oscillators which are capable of operating under close conditions. The batch pH-oscillators are more convenient to use in some proposed applications than the equivalent CSTR variant. A redox oscillator that is new in composition was found. The permanganate oxidation of some amino acids was shown to take place according to oscillatory kinetics in a narrow range of the experimental parameters. The KMnO4 - glycine - Na2HPO4 system represents the first example in the family of manganese based oscillators where amino acids is involved. In the conclusion formal analogies between the simple chemical and some more complicated biological oscillatory phenomena are mentioned and the possibility of modeling periodic processes with the use of information gained from the studies of chemical oscillations is pointed out.

  18. Chemical reactions occurring during direct solar reduction of CO2.

    Science.gov (United States)

    Lyma, J L; Jensen, R J

    2001-09-28

    At high temperatures carbon dioxide may absorb solar radiation and react to form carbon monoxide and molecular oxygen. The CO, so produced, may be converted by well-established means to a combustible fuel, such as methanol. We intend to make a future demonstration of the solar reduction of CO2 based on these processes. This paper, however, addresses only the problem of preserving, or even enhancing, the initial photolytic CO by quenching the hot gas with colder H2O or CO2. We present model calculations with a reaction mechanism used extensively in other calculations. If a CO2 gas stream is heated and photolyzed by intense solar radiation and then allowed to cool slowly, it will react back to the initial CO2 by a series of elementary chemical reactions. The back reaction to CO2 can be terminated with the rapid addition of CO2, water, or a mixture. Calculations show that a three-fold quench with pure CO2 will stop the reactions and preserve over 90% of the initial photolytic CO. We find that water has one of two effects. It can either increase the CO level, or it can catalyze the recombination of O and CO to CO2. The gas temperature is the determining factor. If the quench gas is not sufficient to keep the temperature below approximately 1100 K, a chain-branching reaction dominates and the reaction to CO2 occurs. If the temperature stays below that level a chain terminating reaction dominates and the CO is increased. The former case occurs below approximately a fourfold quench with a water/CO2 mixture. The later case occurs when the quench is greater than fourfold. We conclude that CO2, H2O, or a mixture may quench the hot gas stream photolyzed by solar radiation and preserve the photolytic CO.

  19. Anaphylactic reactions to low-molecular weight chemicals

    Directory of Open Access Journals (Sweden)

    Daria Nowak

    2015-02-01

    Full Text Available Low-molecular weight chemicals (haptens include a large group of chemical compounds occurring in work environment, items of everyday use (cleaning products, clothing, footwear, gloves, furniture, jewelry (earrings, bracelets, drugs, especially in cosmetics. They cause type IV hypersensitive reactions. During the induction phase of delayed-type hypersensitivity, haptens form complexes with skin proteins. After internalization through antigen presenting cells, they are bound to MHC class II molecules. Next, they are exposed against specific T-lymphocytes, what triggers activation of Th1 cells mainly. After repeating exposition to that hapten, during effector phase, Th1 induce production of cytokines affecting non-specific inflammatory cells. Usually, it causes contact dermatitis. However, occasionally incidence of immediate generalized reactions after contact with some kinds of haptens is noticed. A question arises, how the hapten does induce symptoms which are typical for anaphylaxis, and what contributes to amplification of this mechanism. It seems that this phenomenon arises from pathomechanism occurring in contact urticaria syndrome in which an anaphylactic reaction may be caused either by contact of sensitized skin with protein antigens, high-molecular weight allergens, or haptens. One of the hypotheses indicates the leading role of basophiles in this process. Their contact with haptens, may cause to release mediators of immediate allergic reaction (histamine, eicosanoids and to produce cytokines corresponding to Th2 cells profile. Furthermore, Th17 lymphocytes secreting pro-inflammatory interleukin-17 might be engaged into amplifying hypersensitivity into immediate reactions and regulatory T-cells may play role in the process, due to insufficient control of the activity of effector cells.

  20. Chemical reaction optimization for solving shortest common supersequence problem.

    Science.gov (United States)

    Khaled Saifullah, C M; Rafiqul Islam, Md

    2016-10-01

    Shortest common supersequence (SCS) is a classical NP-hard problem, where a string to be constructed that is the supersequence of a given string set. The SCS problem has an enormous application of data compression, query optimization in the database and different bioinformatics activities. Due to NP-hardness, the exact algorithms fail to compute SCS for larger instances. Many heuristics and meta-heuristics approaches were proposed to solve this problem. In this paper, we propose a meta-heuristics approach based on chemical reaction optimization, CRO_SCS that is designed inspired by the nature of the chemical reactions. For different optimization problems like 0-1 knapsack, quadratic assignment, global numeric optimization problems CRO algorithm shows very good performance. We have redesigned the reaction operators and a new reform function to solve the SCS problem. The outcomes of the proposed CRO_SCS algorithm are compared with those of the enhanced beam search (IBS_SCS), deposition and reduction (DR), ant colony optimization (ACO) and artificial bee colony (ABC) algorithms. The length of supersequence, execution time and standard deviation of all related algorithms show that CRO_SCS gives better results on the average than all other algorithms. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Chemical reaction network approaches to Biochemical Systems Theory.

    Science.gov (United States)

    Arceo, Carlene Perpetua P; Jose, Editha C; Marin-Sanguino, Alberto; Mendoza, Eduardo R

    2015-11-01

    This paper provides a framework to represent a Biochemical Systems Theory (BST) model (in either GMA or S-system form) as a chemical reaction network with power law kinetics. Using this representation, some basic properties and the application of recent results of Chemical Reaction Network Theory regarding steady states of such systems are shown. In particular, Injectivity Theory, including network concordance [36] and the Jacobian Determinant Criterion [43], a "Lifting Theorem" for steady states [26] and the comprehensive results of Müller and Regensburger [31] on complex balanced equilibria are discussed. A partial extension of a recent Emulation Theorem of Cardelli for mass action systems [3] is derived for a subclass of power law kinetic systems. However, it is also shown that the GMA and S-system models of human purine metabolism [10] do not display the reactant-determined kinetics assumed by Müller and Regensburger and hence only a subset of BST models can be handled with their approach. Moreover, since the reaction networks underlying many BST models are not weakly reversible, results for non-complex balanced equilibria are also needed. Copyright © 2015 Elsevier Inc. All rights reserved.

  2. Isothermal Reactor for Continuous Flow Microwave-Assisted Chemical Reaction

    Science.gov (United States)

    Matsuzawa, Mitsuhiro; Togashi, Shigenori; Hasebe, Shinji

    An isothermal reactor in which reaction solutions can be controlled at constant temperature under constant microwave irradiation was developed. This is useful for investigating microwave effects on chemical reactions that are not observed under conventional heating conditions. We devised a structure in which a heat-transfer medium with a low dielectric loss factor, which hardly absorbs any microwaves, flowed outside a spiral reaction tube and designed the basic structure of the reactor using electromagnetic simulation to optimize the energy absorption rate. The conditions for increasing the temperature controlling ability of the reactor were also investigated theoretically and experimentally by taking into consideration the influences of three elements: the velocity of the internal fluid, the material for the tube, and the velocity of the external fluid. The velocity of the external fluid had the greatest influence on temperature controlling ability and the material for the tube had the least influence under the experimental conditions. The overall heat transfer coefficient was about 3.9×102 W/(m2·K) when water flowed through the quartz reaction tube at 7.1 mm/s and the external fluid flowed outside the tube at 44 mm/s. We also tested and confirmed that the temperature of water used as internal fluid could be controlled to within ±1.5 K at 309.3 K when microwaves at 26 W were irradiated into the reactor, whereas the temperature of water was over 373 K and boiled without the heat-transfer medium flowing outside the reaction tube using a conventional method of microwave heating. In addition, we investigated microwave effects on Suzuki-Miyaura coupling reaction using the developed isothermal reactor and we confirmed that the temperatures were controlled well in the reactor. The yields obtained by microwave heating were almost the same as that obtained by oil-bath heating.

  3. Chemical characteristics of mineral trioxide aggregate and its hydration reaction

    Science.gov (United States)

    2012-01-01

    Mineral trioxide aggregate (MTA) was developed in early 1990s and has been successfully used for root perforation repair, root end filling, and one-visit apexification. MTA is composed mainly of tricalcium silicate and dicalcium silicate. When MTA is hydrated, calcium silicate hydrate (CSH) and calcium hydroxide is formed. Formed calcium hydroxide interacts with the phosphate ion in body fluid and form amorphous calcium phosphate (ACP) which finally transforms into calcium deficient hydroxyapatite (CDHA). These mineral precipitate were reported to form the MTA-dentin interfacial layer which enhances the sealing ability of MTA. Clinically, the use of zinc oxide euginol (ZOE) based materials may retard the setting of MTA. Also, the use of acids or contact with excessive blood should be avoided before complete set of MTA, because these conditions could adversely affect the hydration reaction of MTA. Further studies on the chemical nature of MTA hydration reaction are needed. PMID:23429542

  4. Chemical characteristics of mineral trioxide aggregate and its hydration reaction.

    Science.gov (United States)

    Chang, Seok-Woo

    2012-11-01

    Mineral trioxide aggregate (MTA) was developed in early 1990s and has been successfully used for root perforation repair, root end filling, and one-visit apexification. MTA is composed mainly of tricalcium silicate and dicalcium silicate. When MTA is hydrated, calcium silicate hydrate (CSH) and calcium hydroxide is formed. Formed calcium hydroxide interacts with the phosphate ion in body fluid and form amorphous calcium phosphate (ACP) which finally transforms into calcium deficient hydroxyapatite (CDHA). These mineral precipitate were reported to form the MTA-dentin interfacial layer which enhances the sealing ability of MTA. Clinically, the use of zinc oxide euginol (ZOE) based materials may retard the setting of MTA. Also, the use of acids or contact with excessive blood should be avoided before complete set of MTA, because these conditions could adversely affect the hydration reaction of MTA. Further studies on the chemical nature of MTA hydration reaction are needed.

  5. Modelling of structural effects on chemical reactions in turbulent flows

    Energy Technology Data Exchange (ETDEWEB)

    Gammelsaeter, H.R.

    1997-12-31

    Turbulence-chemistry interactions are analysed using algebraic moment closure for the chemical reaction term. The coupling between turbulence and chemical length and time scales generate a complex interaction process. This interaction process is called structural effects in this work. The structural effects are shown to take place on all scales between the largest scale of turbulence and the scales of the molecular motions. The set of equations describing turbulent correlations involved in turbulent reacting flows are derived. Interactions are shown schematically using interaction charts. Algebraic equations for the turbulent correlations in the reaction rate are given using the interaction charts to include the most significant couplings. In the frame of fundamental combustion physics, the structural effects appearing on the small scales of turbulence are proposed modelled using a discrete spectrum of turbulent scales. The well-known problem of averaging the Arrhenius law, the specific reaction rate, is proposed solved using a presumed single variable probability density function and a sub scale model for the reaction volume. Although some uncertainties are expected, the principles are addressed. Fast chemistry modelling is shown to be consistent in the frame of algebraic moment closure when the turbulence-chemistry interaction is accounted for in the turbulent diffusion. The modelling proposed in this thesis is compared with experimental data for an laboratory methane flame and advanced probability density function modelling. The results show promising features. Finally it is shown a comparison with full scale measurements for an industrial burner. All features of the burner are captured with the model. 41 refs., 33 figs.

  6. Peptide Bond Synthesis by a Mechanism Involving an Enzymatic Reaction and a Subsequent Chemical Reaction.

    Science.gov (United States)

    Abe, Tomoko; Hashimoto, Yoshiteru; Zhuang, Ye; Ge, Yin; Kumano, Takuto; Kobayashi, Michihiko

    2016-01-22

    We recently reported that an amide bond is unexpectedly formed by an acyl-CoA synthetase (which catalyzes the formation of a carbon-sulfur bond) when a suitable acid and l-cysteine are used as substrates. DltA, which is homologous to the adenylation domain of nonribosomal peptide synthetase, belongs to the same superfamily of adenylate-forming enzymes, which includes many kinds of enzymes, including the acyl-CoA synthetases. Here, we demonstrate that DltA synthesizes not only N-(d-alanyl)-l-cysteine (a dipeptide) but also various oligopeptides. We propose that this enzyme catalyzes peptide synthesis by the following unprecedented mechanism: (i) the formation of S-acyl-l-cysteine as an intermediate via its "enzymatic activity" and (ii) subsequent "chemical" S → N acyl transfer in the intermediate, resulting in peptide formation. Step ii is identical to the corresponding reaction in native chemical ligation, a method of chemical peptide synthesis, whereas step i is not. To the best of our knowledge, our discovery of this peptide synthesis mechanism involving an enzymatic reaction and a subsequent chemical reaction is the first such one to be reported. This new process yields peptides without the use of a thioesterified fragment, which is required in native chemical ligation. Together with these findings, the same mechanism-dependent formation of N-acyl compounds by other members of the above-mentioned superfamily demonstrated that all members most likely form peptide/amide compounds by using this novel mechanism. Each member enzyme acts on a specific substrate; thus, not only the corresponding peptides but also new types of amide compounds can be formed. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  7. On the chemical reaction of matter with antimatter.

    Science.gov (United States)

    Lodi Rizzini, Evandro; Venturelli, Luca; Zurlo, Nicola

    2007-06-04

    A chemical reaction between the building block antiatomic nucleus, the antiproton (p or H- in chemical notation), and the hydrogen molecular ion (H2+) has been observed by the ATHENA collaboration at CERN. The charged pair interact via the long-range Coulomb force in the environment of a Penning trap which is purpose-built to observe antiproton interactions. The net result of the very low energy collision of the pair is the creation of an antiproton-proton bound state, known as protonium (Pn), together with the liberation of a hydrogen atom. The Pn is formed in a highly excited, metastable, state with a lifetime against annihilation of around 1 micros. Effects are observed related to the temperature of the H2+ prior to the interaction, and this is discussed herein.

  8. Liquid-liquid transfer phenomena studies coupled with redox reactions: back-extraction of nitrous acid in the presence of scavengers in aqueous phase; Etude de reactions d`oxydoreduction couplees a des phenomenes de transfert liquide-liquide: cas de la desextraction de l`acide nitreux en presence de composes antinitreux en phase aqueuse

    Energy Technology Data Exchange (ETDEWEB)

    K`zerho, R

    1998-12-31

    This work deals with the investigation of redox reaction contribution to the kinetics of liquid-liquid transfer, in relation with PUREX reprocessing of spent nuclear fuel. The chemical system chosen concerns the tripping of nitrous acid from tributylphosphate organic phase into a nitric acid aqueous solution containing an `anti-nitrous` component, namely hydrazinium nitrate. According to the abundant literature, a major attention is devoted to the very important role of interfacial phenomena on the kinetics of solvent extraction with tributylphosphate. Although, a suitable experimental technique is chosen, using a constant interfacial area cell of the ARMOLLEX-type. Furthermore, the effects of the hydrodynamical and the physico-chemical parameters on the extraction rate led to the identification of the extraction regime nature: diffusional, then chemical limitation. When no `anti-nitrous` component is used, the diffusional resistance is found to be mainly located in the aqueous diffusion layer. The presence of hydrazinium nitrate into the aqueous solution has an overall accelerating effect on the rate of extraction, related to both a complete suppression of the aqueous diffusional resistance, and a very significant enhancement of the interfacial transfer of the nitrous acid, as a function of hydrazinium concentration. If the first effect could be expected because of the well known fast redox reaction in aqueous phase, the second phenomenon represents a quite original and new result which has never been explored before, to the best of our knowledge. A reaction mechanism is postulated and validated, taking into account the reactive effect of hydrazinium on the interfacial step. In order to support the drawn general patterns, different complementary studies were attempted. When hydroxyl-ammonium nitrate is used, a surprising interfacial transfer blockage is observed, pointing out the extreme performance and specificity of the common hydrazinium component. (author) 99

  9. Single-collision studies of energy transfer and chemical reaction

    Energy Technology Data Exchange (ETDEWEB)

    Valentini, J.J. [Columbia Univ., New York, NY (United States)

    1993-12-01

    The research focus in this group is state-to-state dynamics of reaction and energy transfer in collisions of free radicals such as H, OH, and CH{sub 3} with H{sub 2}, alkanes, alcohols and other hydrogen-containing molecules. The motivation for the work is the desire to provide a detailed understanding of the chemical dynamics of prototype reactions that are important in the production and utilization of energy sources, most importantly in combustion. The work is primarily experimental, but with an important and growing theoretical/computational component. The focus of this research program is now on reactions in which at least one of the reactants and one of the products is polyatomic. The objective is to determine how the high dimensionality of the reactants and products differentiates such reactions from atom + diatom reactions of the same kinematics and energetics. The experiments use highly time-resolved laser spectroscopic methods to prepare reactant states and analyze the states of the products on a single-collision time scale. The primary spectroscopic tool for product state analysis is coherent anti-Stokes Raman scattering (CARS) spectroscopy. CARS is used because of its generality and because the extraction of quantum state populations from CARS spectra is straightforward. The combination of the generality and easy analysis of CARS makes possible absolute cross section measurements (both state-to-state and total), a particularly valuable capability for characterizing reactive and inelastic collisions. Reactant free radicals are produced by laser photolysis of appropriate precursors. For reactant vibrational excitation stimulated Raman techniques are being developed and implemented.

  10. Chemical reactions modulated by mechanical stress: extended Bell theory.

    Science.gov (United States)

    Konda, Sai Sriharsha M; Brantley, Johnathan N; Bielawski, Christopher W; Makarov, Dmitrii E

    2011-10-28

    A number of recent studies have shown that mechanical stress can significantly lower or raise the activation barrier of a chemical reaction. Within a common approximation due to Bell [Science 200, 618 (1978)], this barrier is linearly dependent on the applied force. A simple extension of Bell's theory that includes higher order corrections in the force predicts that the force-induced change in the activation energy will be given by -FΔR - ΔχF(2)∕2. Here, ΔR is the change of the distance between the atoms, at which the force F is applied, from the reactant to the transition state, and Δχ is the corresponding change in the mechanical compliance of the molecule. Application of this formula to the electrocyclic ring-opening of cis and trans 1,2-dimethylbenzocyclobutene shows that this extension of Bell's theory essentially recovers the force dependence of the barrier, while the original Bell formula exhibits significant errors. Because the extended Bell theory avoids explicit inclusion of the mechanical stress or strain in electronic structure calculations, it allows a computationally efficient characterization of the effect of mechanical forces on chemical processes. That is, the mechanical susceptibility of any reaction pathway is described in terms of two parameters, ΔR and Δχ, both readily computable at zero force.

  11. Plasma-chemical reactions: low pressure acetylene plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Benedikt, J [Faculty for Physics and Astronomy, Research Group Reactive Plasmas, Ruhr-Universitaet Bochum, Universitaetsstr. 150, 44780 Bochum (Germany)

    2010-02-03

    Reactive plasmas are a well-known tool for material synthesis and surface modification. They offer a unique combination of non-equilibrium electron and ion driven plasma chemistry, energetic ions accelerated in the plasma sheath at the plasma-surface interface, high fluxes of reactive species towards surfaces and a friendly environment for thermolabile objects. Additionally, small negatively charged clusters can be generated, because they are confined in the positive plasma potential. Plasmas in hydrocarbon gases, and especially in acetylene, are a good example for the discussion of different plasma-chemical processes. These plasmas are involved in a plethora of possible applications ranging from fuel conversion to formation of single wall carbon nanotubes. This paper provides a concise overview of plasma-chemical reactions (PCRs) in low pressure reactive plasmas and discusses possible experimental and theoretical methods for the investigation of their plasma chemistry. An up-to-date summary of the knowledge about low pressure acetylene plasmas is given and two particular examples are discussed in detail: (a) Ar/C{sub 2}H{sub 2} expanding thermal plasmas with electron temperatures below 0.3 eV and with a plasma chemistry initiated by charge transfer reactions and (b) radio frequency C{sub 2}H{sub 2} plasmas, in which the energetic electrons mainly control PCRs. (topical review)

  12. Community Detection Using Dual-Representation Chemical Reaction Optimization.

    Science.gov (United States)

    Chang, Honghao; Feng, Zuren; Ren, Zhigang

    2017-12-01

    Many complex networks have been shown to have community structures. Detecting those structures is very important for understanding the organization and function of networks. Because this problem is NP-hard, it is appropriate to resort to evolutionary algorithms. Chemical reaction optimization (CRO) is a novel evolutionary algorithm inspired by the interactions among molecules during chemical reactions. In this paper, we propose a CRO variant named dual-representation CRO (DCRO) to address the community detection problem. DCRO encodes a solution in two representations: one is locus-based and the other is vector-based. The former representation can ensure the validity of a solution and fits for diversification search, and the latter is convenient for intensification search. We thus design two operators for CRO based on these two representations. Their cooperation enables DCRO to achieve a good balance between exploration and exploitation. Experimental results on synthetic and real-life networks show that DCRO can find community structures close to the actual ones and is capable of achieving solutions comparable to several state-of-the-art methods.

  13. Anthropogenic reaction parameters--the missing link between chemical intuition and the available chemical space.

    Science.gov (United States)

    Keserű, György M; Soós, Tibor; Kappe, C Oliver

    2014-08-07

    How do skilled synthetic chemists develop good intuitive expertise? Why can we only access such a small amount of the available chemical space-both in terms of the reactions used and the chemical scaffolds we make? We argue here that these seemingly unrelated questions have a common root and are strongly interdependent. We performed a comprehensive analysis of organic reaction parameters dating back to 1771 and discovered that there are several anthropogenic factors that limit reaction parameters and thus the scope of synthetic chemistry. Nevertheless, many of the anthropogenic limitations such as narrow parameter space and the opportunity for rapid and clear feedback on the progress of reactions appear to be crucial for the acquisition of valid and reliable chemical intuition. In parallel, however, all of these same factors represent limitations for the exploration of available chemistry space and we argue that these are thus at least partly responsible for limited access to new chemistries. We advocate, therefore, that the present anthropogenic boundaries can be expanded by a more conscious exploration of "off-road" chemistry that would also extend the intuitive knowledge of trained chemists.

  14. Machine learning of chemical reactivity from databases of organic reactions.

    Science.gov (United States)

    Carrera, Gonçalo V S M; Gupta, Sunil; Aires-de-Sousa, João

    2009-07-01

    Databases of chemical reactions contain knowledge about the reactivity of specific reagents. Although information is in general only explicitly available for compounds reported to react, it is possible to derive information about substructures that do not react in the reported reactions. Both types of information (positive and negative) can be used to train machine learning techniques to predict if a compound reacts or not with a specific reagent. The whole process was implemented with two databases of reactions, one involving BuNH2 as the reagent, and the other NaCNBH3. Negative information was derived using MOLMAP molecular descriptors, and classification models were developed with Random Forests also based on MOLMAP descriptors. MOLMAP descriptors were based exclusively on calculated physicochemical features of molecules. Correct predictions were achieved for approximately 90% of independent test sets. While NaCNBH3 is a selective reducing reagent widely used in organic synthesis, BuNH2 is a nucleophile that mimics the reactivity of the lysine side chain (involved in an initiating step of the mechanism leading to skin sensitization).

  15. Chemical Reactions Using a Non-Equilibrium Wigner Function Approach

    Directory of Open Access Journals (Sweden)

    Ramón F. Álvarez-Estrada

    2016-10-01

    Full Text Available A three-dimensional model of binary chemical reactions is studied. We consider an ab initio quantum two-particle system subjected to an attractive interaction potential and to a heat bath at thermal equilibrium at absolute temperature T > 0 . Under the sole action of the attraction potential, the two particles can either be bound or unbound to each other. While at T = 0 , there is no transition between both states, such a transition is possible when T > 0 (due to the heat bath and plays a key role as k B T approaches the magnitude of the attractive potential. We focus on a quantum regime, typical of chemical reactions, such that: (a the thermal wavelength is shorter than the range of the attractive potential (lower limit on T and (b ( 3 / 2 k B T does not exceed the magnitude of the attractive potential (upper limit on T. In this regime, we extend several methods previously applied to analyze the time duration of DNA thermal denaturation. The two-particle system is then described by a non-equilibrium Wigner function. Under Assumptions (a and (b, and for sufficiently long times, defined by a characteristic time scale D that is subsequently estimated, the general dissipationless non-equilibrium equation for the Wigner function is approximated by a Smoluchowski-like equation displaying dissipation and quantum effects. A comparison with the standard chemical kinetic equations is made. The time τ required for the two particles to transition from the bound state to unbound configurations is studied by means of the mean first passage time formalism. An approximate formula for τ, in terms of D and exhibiting the Arrhenius exponential factor, is obtained. Recombination processes are also briefly studied within our framework and compared with previous well-known methods.

  16. Chemical reaction interface mass spectrometry with high efficiency nebulization.

    Science.gov (United States)

    Jorabchi, Kaveh; Kahen, Kaveh; Lecchi, Paolo; Montaser, Akbar

    2005-08-15

    A high efficiency nebulizer (HEN) coupled to a heated spray chamber and a membrane desolvator is used for liquid sample introduction in chemical reaction interface mass spectrometry (CRIMS). Compared to the conventional thermospray nebulizer operated at solvent flow rate of 1 mL/min, the HEN provides small droplets at lower flow rates (10-100 microL/min), improving the desolvation and analyte transport efficiency. As a result, the sensitivity for carbon detection by CRIMS is improved by a factor of 4. The new arrangement offers an easy-to-use and robust interface, facilitating the availability of a variety of liquid chromatographic techniques to the CRIMS. Separation and detection of labeled peptides in a mixture of unlabeled biopolymers is illustrated at a solvent flow rate of 45 microL/min as an example of new possibilities offered by the improved liquid introduction interface.

  17. Miscible viscous fingering involving production of gel by chemical reactions

    Science.gov (United States)

    Nagatsu, Yuichiro; Hoshino, Kenichi

    2015-11-01

    We have experimentally investigated miscible viscous fingering with chemical reactions producing gel. Here, two systems were employed. In one system, sodium polyacrylate (SPA) solution and aluminum ion (Al3 +) solution were used as the more and less viscous liquids, respectively. In another system, SPA solution and ferric ion (Fe3 +) solution were used as the more and less viscous liquids, respectively. In the case of Al3 +, displacement efficiency was smaller than that in the non-reactive case, whereas in the case of Fe3 +, the displacement efficiency was larger. We consider that the difference in change of the patterns in the two systems will be caused by the difference in the properties of the gels. Therefore, we have measured the rheological properties of the gels by means of a rheometer. We discuss relationship between the VF patterns and the rheological measurement.

  18. Mass transfer in porous media with heterogeneous chemical reaction

    Directory of Open Access Journals (Sweden)

    Souza S.M.A.G.Ulson de

    2003-01-01

    Full Text Available In this paper, the modeling of the mass transfer process in packed-bed reactors is presented and takes into account dispersion in the main fluid phase, internal diffusion of the reactant in the pores of the catalyst, and surface reaction inside the catalyst. The method of volume averaging is applied to obtain the governing equation for use on a small scale. The local mass equilibrium is assumed for obtaining the one-equation model for use on a large scale. The closure problems are developed subject to the length-scale constraints and the model of a spatially periodic porous medium. The expressions for effective diffusivity, hydrodynamic dispersion, total dispersion and the Darcy's law permeability tensors are presented. Solution of the set of final equations permits the variations of velocity and concentration of the chemical species along the packed-bed reactors to be obtained.

  19. Mass Accommodation and Chemical Reaction at Gas-Liquid Interfaces

    Science.gov (United States)

    Kolb, C. E.; Williams, L. R.; Jayne, J. T.; Worsnop, D. R.; Davidovits, P.

    2006-12-01

    The uptake of trace gases by liquid surfaces is an important process that initiates the heterogeneous chemistry of liquid aerosol particles and cloud droplets. We have recently reviewed the available experimental data for liquid aqueous and aqueous/organic surfaces (1). The review highlights some inconsistencies among experimental results and between experimental results and molecular dynamics simulations. Some of these inconsistencies will be evaluated and discussed in terms of the physics of liquid interfaces, the limitations of various experimental techniques and the disparate scales of laboratory experiments and current molecular simulations (1, 2). 1. Davidovits, P., Kolb, C. E., Williams, L. R., Jayne, J. T., Worsnop, D. R., 2006, Mass Accommodation and Chemical Reactions at Gas Liquid Interfaces, Chem. Rev. 106, 1323-1354. 2. Garrett, B. C., Schenter, G. K., Morita, A., 2006, Molecular Simulations of Molecules across the Liquid/Vapor Interface of Water, Chem. Rev. 106, 1355-1374.

  20. Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks

    Energy Technology Data Exchange (ETDEWEB)

    Ziaul Huque

    2007-08-31

    This is the final technical report for the project titled 'Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks'. The aim of the project was to develop an efficient chemistry model for combustion simulations. The reduced chemistry model was developed mathematically without the need of having extensive knowledge of the chemistry involved. To aid in the development of the model, Neural Networks (NN) was used via a new network topology known as Non-linear Principal Components Analysis (NPCA). A commonly used Multilayer Perceptron Neural Network (MLP-NN) was modified to implement NPCA-NN. The training rate of NPCA-NN was improved with the GEneralized Regression Neural Network (GRNN) based on kernel smoothing techniques. Kernel smoothing provides a simple way of finding structure in data set without the imposition of a parametric model. The trajectory data of the reaction mechanism was generated based on the optimization techniques of genetic algorithm (GA). The NPCA-NN algorithm was then used for the reduction of Dimethyl Ether (DME) mechanism. DME is a recently discovered fuel made from natural gas, (and other feedstock such as coal, biomass, and urban wastes) which can be used in compression ignition engines as a substitute for diesel. An in-house two-dimensional Computational Fluid Dynamics (CFD) code was developed based on Meshfree technique and time marching solution algorithm. The project also provided valuable research experience to two graduate students.

  1. Bayesian inference of chemical kinetic models from proposed reactions

    KAUST Repository

    Galagali, Nikhil

    2015-02-01

    © 2014 Elsevier Ltd. Bayesian inference provides a natural framework for combining experimental data with prior knowledge to develop chemical kinetic models and quantify the associated uncertainties, not only in parameter values but also in model structure. Most existing applications of Bayesian model selection methods to chemical kinetics have been limited to comparisons among a small set of models, however. The significant computational cost of evaluating posterior model probabilities renders traditional Bayesian methods infeasible when the model space becomes large. We present a new framework for tractable Bayesian model inference and uncertainty quantification using a large number of systematically generated model hypotheses. The approach involves imposing point-mass mixture priors over rate constants and exploring the resulting posterior distribution using an adaptive Markov chain Monte Carlo method. The posterior samples are used to identify plausible models, to quantify rate constant uncertainties, and to extract key diagnostic information about model structure-such as the reactions and operating pathways most strongly supported by the data. We provide numerical demonstrations of the proposed framework by inferring kinetic models for catalytic steam and dry reforming of methane using available experimental data.

  2. Detection of bond formations by DNA-programmed chemical reactions and PCR amplification.

    Science.gov (United States)

    Li, Yizhou; Zhang, Mingda; Zhang, Chi; Li, Xiaoyu

    2012-10-04

    A system capable of performing both DNA-templated chemical reactions and detection of bond formations is reported. Photocleavable DNA templates direct reactions. Products from bond-forming events re-ligate original templates, amplifiable by PCR, therefore distinguishing bond formation from background. This system provides a novel approach for discovering potential new chemical reactions.

  3. CH 1 Introduction to Chemistry. Study Guide to Minicourse I - 13 Chemical Reaction Principles.

    Science.gov (United States)

    Schlenker, Richard

    Provided is a study guide for an introductory minicourse to the principles of chemical reactions. This written text is designed to accompany a series of audio tapes and 35mm slides which the student studies at his own pace. The course presents chemical kinetics, reaction mechanisms, reaction rates, and equilibrium. (SL)

  4. Chemical reaction in MHD flow past a vertical plate with mass ...

    African Journals Online (AJOL)

    Chemical reaction plays an important role in MHD flow. It has industrial applications, such as design of chemical processing equipments, food processing and cooling towers etc. In the present paper, chemical reaction effect on a viscous, incompressible and electrically conducting fluid with unsteady MHD flow past an ...

  5. Mass transfer and chemical reaction in gas-liquid-liquid systems.

    NARCIS (Netherlands)

    Brilman, Derk Willem Frederik

    1998-01-01

    Gas-liquid-liquid reaction systems may be encountered in several important fields of application as e.g. hydroformylation, alkylation, carboxylation, polymerisation, hydrometallurgy, biochemical processes and fine chemicals manufacturing. However, the reaction engineering aspects of these systems

  6. Femtosecond laser control of chemical reaction of carbon monoxide and hydrogen

    CSIR Research Space (South Africa)

    Du Plessis, A

    2010-09-01

    Full Text Available relative fragmentation ratios for unimolecular dissociation reactions – therefore selectively breaking bonds in a molecule. More interestingly, the same techniques can be used to provide control over chemical reactions involving two or more reactant...

  7. Detailed Chemical Kinetic Reaction Mechanism for Biodiesel Components Methyl Stearate and Methyl Oleate

    Energy Technology Data Exchange (ETDEWEB)

    Naik, C; Westbrook, C K; Herbinet, O; Pitz, W J; Mehl, M

    2010-01-22

    New chemical kinetic reaction mechanisms are developed for two of the five major components of biodiesel fuel, methyl stearate and methyl oleate. The mechanisms are produced using existing reaction classes and rules for reaction rates, with additional reaction classes to describe other reactions unique to methyl ester species. Mechanism capabilities were examined by computing fuel/air autoignition delay times and comparing the results with more conventional hydrocarbon fuels for which experimental results are available. Additional comparisons were carried out with measured results taken from jet-stirred reactor experiments for rapeseed methyl ester fuels. In both sets of computational tests, methyl oleate was found to be slightly less reactive than methyl stearate, and an explanation of this observation is made showing that the double bond in methyl oleate inhibits certain low temperature chain branching reaction pathways important in methyl stearate. The resulting detailed chemical kinetic reaction mechanism includes more approximately 3500 chemical species and more than 17,000 chemical reactions.

  8. Capillary Action may Cool Systems and Precisely balance Chemical Reactions

    Science.gov (United States)

    Kriske, Richard

    2011-10-01

    It is well known that it takes no work for Water to rise in a Capillary tube against the force of Gravity. There is a precise balance in this system that resembles Robert Millikan's ``Oil Drop'' experiment, where mass was balanced against the electrostatic force. If at the top of the capillary tube there is evaporation, one can see that the system is cooled as another water molecule has room to move up the column. Furthermore, if the evaporation process can be controlled one photon at a time, a precise balance is created between a photon, and the height/mass of the column. If other molecules are place in the column, they can be moved up and down the column, in a chromatograph way, in a fairly precise manner, by controlling evaporation and molecular weight. If in addition to all of this, the interface of the solution against the walls of the column have Fermi levels, it can be seen as a very precise Electrochemical Device. In the situation of nanotubes, as opposed to trees and plants, these properties can be used to create measure environmental properties and to Balance Chemical Reactions. Forests, and Plants may cool themselves and their environment using this process, and using this process coupled with more energetic photons through photosynthesis.

  9. Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks

    Energy Technology Data Exchange (ETDEWEB)

    Nelson Butuk

    2005-12-01

    This is an annual technical report for the work done over the last year (period ending 9/30/2005) on the project titled ''Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks''. The aim of the project is to develop an efficient chemistry model for combustion simulations. The reduced chemistry model will be developed mathematically without the need of having extensive knowledge of the chemistry involved. To aid in the development of the model, Neural Networks (NN) will be used via a new network topology know as Non-linear Principal Components Analysis (NPCA). We report on the development of a novel procedure to speed up the training of NPCA. The same procedure termed L{sub 2}Boost can be used to increase the order of approximation of the Generalized Regression Neural Network (GRNN). It is pointed out that GRNN is a basic procedure for the emerging mesh free CFD. Also reported is an efficient simple approach of computing the derivatives of GRNN function approximation using complex variables or the Complex Step Method (CSM). The results presented demonstrate the significance of the methods developed and will be useful in many areas of applied science and engineering.

  10. Determination of 1-naphthylamine by using oscillating chemical reaction.

    Science.gov (United States)

    Gao, Jinzhang; Wei, Xiaoxia; Yang, Wu; Lv, Dongyu; Qu, Jie; Chen, Hua; Dai, Hongxia

    2007-06-01

    A simple and rapid analytical method for determining 1-naphthylamine was proposed by perturbation with different amounts of 1-naphthylamine on the classical Belousov-Zhabotinskii (B-Z) oscillating chemical system. The results show that the changes both in oscillating period and amplitude were linearly proportional to the logarithm of the concentration of 1-naphthylamine (logC) very well ranging from 7.08x10(-5) to 7.08x10(-6) molL(-1) and 7.08x10(-5) to 1.0x10(-6) molL(-1), with the corresponding regression coefficient are 0.9957 and 0.9922, respectively. For the later, a lower detection limit of 5.64x10(-9) molL(-1) was obtained. Influence of injection point, temperature and reactant variables on this oscillating system was also investigated in detailed. The results obtained were compared with other determination methods. A possible reaction mechanism was interpreted by using bromide ion selective electrode to inspect the concentration change of Br(-) ion in the oscillating process.

  11. Plasmon-assisted chemical reactions revealed by high-vacuum tip-enhanced Raman spectroscopy

    Science.gov (United States)

    Lu, Shuaicheng; Sheng, Shaoxiang; Zhang, Zhenglong; Xu, Hongxing; Zheng, Hairong

    2014-08-01

    Tip-enhanced Raman spectroscopy (TERS) is the technique that combines the nanoscale spatial resolution of a scanning probe microscope and the highly sensitive Raman spectroscopy enhanced by the surface plasmons. It is suitable for chemical analysis at nanometer scale. Recently, TERS exhibited powerful potential in analyzing the chemical reactions at nanoscale. The high sensitivity and spatial resolution of TERS enable us to learn the reaction processes more clearly. More importantly, the chemical reaction in TERS is assisted by surface plasmons, which provides us an optical method to manipulate the chemical reactions at nanoscale. Here using our home-built high-vacuum tip-enhanced Raman spectroscopy (HV-TERS) setup, we successfully observed the plasmon-assisted molecule dimerization and dissociation reactions. In HV-TERS system, under laser illumination, 4-nitrobenzenethiol (4NBT) molecules can be dimerized to p,p'-dimercaptoazobenzene (DMAB), and dissociation reaction occurs for malachite green (MG) molecules. Using our HV-TERS setup, the dynamic processes of the reactions are clearly revealed. The chemical reactions can be manipulated by controlling the plasmon intensity through changing the power of the incident laser, the tunneling current and the bias voltage. We also investigated the role of plasmonic thermal effect in the reactions by measuring both the Stokes and anti- Stokes Raman peaks. Our findings extend the applications of TERS, which can help to study the chemical reactions and understand the dynamic processes at single molecular level, and even design molecules by the plasmon-assisted chemical reactions.

  12. Chemical reaction in MHD flow past a vertical plate with mass ...

    African Journals Online (AJOL)

    Corresponding Author: e-mail: rajputneetulko@gmail.com. Abstract. Chemical reaction plays an important role in MHD flow. It has industrial applications, such as design of chemical processing equipments, food processing and cooling towers etc.

  13. Relationship between Thermodynamic Driving Force and One-Way Fluxes in Reversible Chemical Reactions

    OpenAIRE

    Beard, Daniel A.; Qian, Hong

    2006-01-01

    Chemical reaction systems operating in nonequilibrium open-system states arise in a great number of contexts, including the study of living organisms, in which chemical reactions, in general, are far from equilibrium. Here we introduce a theorem that relates forward and reverse fluxes and free energy for any chemical process operating in a steady state. This relationship, which is a generalization of equilibrium conditions to the case of a chemical process occurring in a nonequilibrium steady...

  14. Transfert thermique à travers une interface de contact intermittent en ...

    African Journals Online (AJOL)

    Dans cet article, on présente un modèle unidirectionnel pour décrire le transfert thermique à travers une interface de contact intermittent en régime thermique périodique établi. Le champ de température et le flux transféré sont gouvernés par les paramètres d'intermittence, à savoir la fréquence d'intermittence et le ...

  15. Computational molecular technology towards macroscopic chemical phenomena-molecular control of complex chemical reactions, stereospecificity and aggregate structures

    Energy Technology Data Exchange (ETDEWEB)

    Nagaoka, Masataka [Graduate School of Information Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8601 (Japan); Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), Honmachi, Kawaguchi 332-0012 (Japan); ESICB, Kyoto University, Kyodai Katsura, Nishikyo-ku, Kyoto 615-8520 (Japan)

    2015-12-31

    A new efficient hybrid Monte Carlo (MC)/molecular dynamics (MD) reaction method with a rare event-driving mechanism is introduced as a practical ‘atomistic’ molecular simulation of large-scale chemically reactive systems. Starting its demonstrative application to the racemization reaction of (R)-2-chlorobutane in N,N-dimethylformamide solution, several other applications are shown from the practical viewpoint of molecular controlling of complex chemical reactions, stereochemistry and aggregate structures. Finally, I would like to mention the future applications of the hybrid MC/MD reaction method.

  16. Computational Analyses of Complex Flows with Chemical Reactions

    Science.gov (United States)

    Bae, Kang-Sik

    The heat and mass transfer phenomena in micro-scale for the mass transfer phenomena on drug in cylindrical matrix system, the simulation of oxygen/drug diffusion in a three dimensional capillary network, and a reduced chemical kinetic modeling of gas turbine combustion for Jet propellant-10 have been studied numerically. For the numerical analysis of the mass transfer phenomena on drug in cylindrical matrix system, the governing equations are derived from the cylindrical matrix systems, Krogh cylinder model, which modeling system is comprised of a capillary to a surrounding cylinder tissue along with the arterial distance to veins. ADI (Alternative Direction Implicit) scheme and Thomas algorithm are applied to solve the nonlinear partial differential equations (PDEs). This study shows that the important factors which have an effect on the drug penetration depth to the tissue are the mass diffusivity and the consumption of relevant species during the time allowed for diffusion to the brain tissue. Also, a computational fluid dynamics (CFD) model has been developed to simulate the blood flow and oxygen/drug diffusion in a three dimensional capillary network, which are satisfied in the physiological range of a typical capillary. A three dimensional geometry has been constructed to replicate the one studied by Secomb et al. (2000), and the computational framework features a non-Newtonian viscosity model for blood, the oxygen transport model including in oxygen-hemoglobin dissociation and wall flux due to tissue absorption, as well as an ability to study the diffusion of drugs and other materials in the capillary streams. Finally, a chemical kinetic mechanism of JP-10 has been compiled and validated for a wide range of combustion regimes, covering pressures of 1atm to 40atm with temperature ranges of 1,200 K--1,700 K, which is being studied as a possible Jet propellant for the Pulse Detonation Engine (PDE) and other high-speed flight applications such as hypersonic

  17. Effect of Grain Size and Reaction Time in Characterisation of Aggregates for Alkali Silica Reaction Using Chemical Method

    Directory of Open Access Journals (Sweden)

    R.P. Pathak

    2016-04-01

    Full Text Available Concrete can deteriorate as a result of alkali aggregate reaction, an interaction between alkalis present in alkaline pore solution originating from the Portland cement and reactive minerals in certain types of aggregates. Potential reactivity of aggregates with regard to alkalis present in concrete mix can be determined by Mortar Bar method, Chemical Method and Petrographic analysis. Of these the chemical method though is quick and does not require a large quantity of material for testing yet have its own inherent limitations. It does not ensure completion of reaction as the observations are limited to 24hour only and also does not assess the effect of varying the combination of coarse and fine aggregates. A study on chemical method by allowing the reaction for a prolonged time up to 96 hours and also on different grain size ranged matrix was carried at Central Soil and Materials Research Station, New Delhi. Simultaneously the test results of the modified method are compared to the existing Mortar Bar method, Chemical Method and Petrographic analysis The outcome of the studies clearly reflects that the grain size play an important role in the reaction, the reaction time has a demarked impact on reactivity, in the cases having a high value of silica release the choice of reduction in alkalinity as an indicator of degree of reaction is not reliable, instead measuring remaining Na2O concentration in Sodium hydroxide solution after the reaction seems to be much more meaningful in justifying the silica release.

  18. Non-allergic cutaneous reactions in airborne chemical sensitivity--a population based study

    DEFF Research Database (Denmark)

    Berg, Nikolaj Drimer; Linneberg, Allan; Thyssen, Jacob Pontoppidan

    2011-01-01

    the relationship between cutaneous reactions from patch testing and self-reported severity of chemical sensitivity to common airborne chemicals. A total of 3460 individuals participating in a general health examination, Health 2006, were patch tested with allergens from the European standard series and screened...... for chemical sensitivity with a standardised questionnaire dividing the participants into four severity groups of chemical sensitivity. Both allergic and non-allergic cutaneous reactions--defined as irritative, follicular, or doubtful allergic reactions--were analysed in relationship with severity of chemical...... most severe groups of self-reported sensitivity to airborne chemicals. When adjusting for confounding, associations were weakened, and only non-allergic cutaneous reactions were significantly associated with individuals most severely affected by inhalation of airborne chemicals (odds ratio = 2.5, p = 0...

  19. Evolution of Complex Maillard Chemical Reactions, Resolved in Time.

    Science.gov (United States)

    Hemmler, Daniel; Roullier-Gall, Chloé; Marshall, James W; Rychlik, Michael; Taylor, Andrew J; Schmitt-Kopplin, Philippe

    2017-06-12

    In this study, we monitored the thermal formation of early ribose-glycine Maillard reaction products over time by ion cyclotron resonance mass spectrometry. Here, we considered sugar decomposition (caramelization) apart from compounds that could only be produced in the presence of the amino acid. More than 300 intermediates as a result of the two initial reactants were found after ten hours (100 °C) to participate in the interplay of the Maillard reaction cascade. Despite the large numerical variety the majority of intermediates follow simple and repetitive reaction patterns. Dehydration, carbonyl cleavage, and redox reactions turned out to have a large impact on the diversity the Maillard reaction causes. Although the Amadori breakdown is considered as the main Maillard reaction pathway, other reactive intermediates, often of higher molecular weight than the Amadori rearrangement product, contribute to a large extent to the multitude of intermediates we observed.

  20. Acid-Base Chemistry According to Robert Boyle: Chemical Reactions in Words as well as Symbols

    Science.gov (United States)

    Goodney, David E.

    2006-01-01

    Examples of acid-base reactions from Robert Boyle's "The Sceptical Chemist" are used to illustrate the rich information content of chemical equations. Boyle required lengthy passages of florid language to describe the same reaction that can be done quite simply with a chemical equation. Reading or hearing the words, however, enriches the student's…

  1. Introducing Stochastic Simulation of Chemical Reactions Using the Gillespie Algorithm and MATLAB: Revisited and Augmented

    Science.gov (United States)

    Argoti, A.; Fan, L. T.; Cruz, J.; Chou, S. T.

    2008-01-01

    The stochastic simulation of chemical reactions, specifically, a simple reversible chemical reaction obeying the first-order, i.e., linear, rate law, has been presented by Martinez-Urreaga and his collaborators in this journal. The current contribution is intended to complement and augment their work in two aspects. First, the simple reversible…

  2. Design criteria for extraction with chemical reaction and liquid membrane permeation

    Science.gov (United States)

    Bart, H. J.; Bauer, A.; Lorbach, D.; Marr, R.

    1988-01-01

    The design criteria for heterogeneous chemical reactions in liquid/liquid systems formally correspond to those of classical physical extraction. More complex models are presented which describe the material exchange at the individual droplets in an extraction with chemical reaction and in liquid membrane permeation.

  3. Novel chemical kinetics for a single enzyme reaction: relationship between substrate concentration and the second moment of enzyme reaction time.

    Science.gov (United States)

    Jung, Won; Yang, Seongeun; Sung, Jaeyoung

    2010-08-05

    We report a robust quadratic relation between the inverse substrate concentration and the second moment, , of the catalytic turnover time distribution for enzyme reactions. The results hold irrespective of the mechanism and dynamics of the enzyme reaction and suggest a novel single molecule experimental analysis that provides information about reaction processes of the enzyme-substrate complex and ergodicity of the enzyme reaction system, which is beyond the reach of the conventional analysis for the mean reaction time, . It turns out that - 2(2) is linear in inverse substrate concentration for an ergodic homogeneous enzyme system given that the enzyme substrate encounter is a simple rate process, and its value at the high substrate concentration limit provides direct information about if any non-Poisson reaction process of the enzyme-substrate complex. For a nonergodic heterogeneous reaction system, the corresponding quantity becomes a quadratic function of the inverse substrate concentration. This leads us to suggest an ergodicity measure for single enzyme reaction systems. We obtain a simple analytic expression of the randomness parameter for the single catalytic turnover time, which could provide a quantitative explanation about the previously reported randomness data of the beta-galactosidase enzyme. In obtaining the results, we introduce novel chemical kinetics applicable to a non-Poisson reaction network with arbitrary connectivity, as a generalization of the conventional chemical kinetics.

  4. Chemical Synthesis Accelerated by Paper Spray: The Haloform Reaction

    Science.gov (United States)

    Bain, Ryan M.; Pulliam, Christopher J.; Raab, Shannon A.; Cooks, R. Graham

    2016-01-01

    In this laboratory, students perform a synthetic reaction in two ways: (i) by traditional bulk-phase reaction and (ii) in the course of reactive paper spray ionization. Mass spectrometry (MS) is used both as an analytical method and a means of accelerating organic syntheses. The main focus of this laboratory exercise is that the same ionization…

  5. Chemical reaction model for oil and gas generation from type 1 and type 2 kerogen

    Energy Technology Data Exchange (ETDEWEB)

    Braun, R.L.; Burnham, A.K.

    1993-06-01

    A global model for the generation of oil and gas from petroleum source rocks is presented. The model consists of 13 chemical species and 10 reactions, including an alternate-pathway mechanism for kerogen pyrolysis. Reaction rate parameters and stoichiometry coefficients determined from a variety of pyrolysis data are given for both type I and type II kerogen. Use of the chemical reaction model is illustrated for typical geologic conditions.

  6. Chemical Reaction Equilibrium in Nanoporous Materials: NO Dimerization Reaction in Carbon Slit Nanopores

    Science.gov (United States)

    2006-09-01

    the Journal of Chemical Physics , vol. 124, pp. 064712-1...064712-14, 2006. Reprinted with permission from the Journal of Chemical Physics . Copyright 2006, the American Institute of Physics...A reprint from the Journal of Chemical Physics , vol. 124, pp. 064712-1–064712-14, 2006. Reprinted with permission from the Journal of Chemical Physics .

  7. Modelling of chemical reaction in foods: a multiresponse approach.

    NARCIS (Netherlands)

    Boekel, van M.A.J.S.

    1998-01-01

    The quality of foods depends on several factors. One of these factors is the occurrence of (bio)chemical changes taking place during the post-harvest period and during processing, storage and distribution. In order to optimise quality it is of utmost importance to control (bio)chemical changes as

  8. Evolution of Complex Maillard Chemical Reactions, Resolved in Time

    OpenAIRE

    Hemmler, Daniel; Roullier-Gall, Chlo?; Marshall, James W.; Rychlik, Michael; Taylor, Andrew J.; Schmitt-Kopplin, Philippe

    2017-01-01

    In this study, we monitored the thermal formation of early ribose-glycine Maillard reaction products over time by ion cyclotron resonance mass spectrometry. Here, we considered sugar decomposition (caramelization) apart from compounds that could only be produced in the presence of the amino acid. More than 300 intermediates as a result of the two initial reactants were found after ten hours (100??C) to participate in the interplay of the Maillard reaction cascade. Despite the large numerical ...

  9. Effects of Surfactants on the Rate of Chemical Reactions

    Directory of Open Access Journals (Sweden)

    B. Samiey

    2014-01-01

    Full Text Available Surfactants are self-assembled compounds that depend on their structure and electric charge can interact as monomer or micelle with other compounds (substrates. These interactions which may catalyze or inhibit the reaction rates are studied with pseudophase, cooperativity, and stoichiometric (classical models. In this review, we discuss applying these models to study surfactant-substrate interactions and their effects on Diels-Alder, redox, photochemical, decomposition, enzymatic, isomerization, ligand exchange, radical, and nucleophilic reactions.

  10. Molecule-based approach for computing chemical-reaction rates in upper atmosphere hypersonic flows.

    Energy Technology Data Exchange (ETDEWEB)

    Gallis, Michail A.; Bond, Ryan Bomar; Torczynski, John Robert

    2009-08-01

    This report summarizes the work completed during FY2009 for the LDRD project 09-1332 'Molecule-Based Approach for Computing Chemical-Reaction Rates in Upper-Atmosphere Hypersonic Flows'. The goal of this project was to apply a recently proposed approach for the Direct Simulation Monte Carlo (DSMC) method to calculate chemical-reaction rates for high-temperature atmospheric species. The new DSMC model reproduces measured equilibrium reaction rates without using any macroscopic reaction-rate information. Since it uses only molecular properties, the new model is inherently able to predict reaction rates for arbitrary nonequilibrium conditions. DSMC non-equilibrium reaction rates are compared to Park's phenomenological non-equilibrium reaction-rate model, the predominant model for hypersonic-flow-field calculations. For near-equilibrium conditions, Park's model is in good agreement with the DSMC-calculated reaction rates. For far-from-equilibrium conditions, corresponding to a typical shock layer, the difference between the two models can exceed 10 orders of magnitude. The DSMC predictions are also found to be in very good agreement with measured and calculated non-equilibrium reaction rates. Extensions of the model to reactions typically found in combustion flows and ionizing reactions are also found to be in very good agreement with available measurements, offering strong evidence that this is a viable and reliable technique to predict chemical reaction rates.

  11. RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics

    KAUST Repository

    Suleimanov, Yu.V.

    2013-03-01

    We present RPMDrate, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH 4, OH+CH4 and H+C2H6 reactions. © 2012 Elsevier B.V. All rights reserved.

  12. Sensitivity and network topology in chemical reaction systems

    Science.gov (United States)

    Okada, Takashi; Mochizuki, Atsushi

    2017-08-01

    In living cells, biochemical reactions are catalyzed by specific enzymes and connect to one another by sharing substrates and products, forming complex networks. In our previous studies, we established a framework determining the responses to enzyme perturbations only from network topology, and then proved a theorem, called the law of localization, explaining response patterns in terms of network topology. In this paper, we generalize these results to reaction networks with conserved concentrations, which allows us to study any reaction system. We also propose network characteristics quantifying robustness. We compare E. coli metabolic network with randomly rewired networks, and find that the robustness of the E. coli network is significantly higher than that of the random networks.

  13. Organoberyllium compounds and their chemical reactions. XI. Synthesis of diacetylhydrobenzoins

    Energy Technology Data Exchange (ETDEWEB)

    Lapkin, I.I.; Sinani, S.V.

    1987-08-10

    The authors previously determined that the reaction of aromatic aldehydes with acylhaloberyllium in ethyl acetate lead to the formation of stilbene. In this same vein they have found that the final products of this reaction can include not only stilbenes but also diacetylhydrobenzoin and that the product is determined by the nature of the solvent. In this paper they determine that while ethyl acetate indeed leads to the stilbene the use of an ether--diethyl or diisopropyl--leads to diacetylhydrobenzoin. NMR spectroscopy is used to ascertain the structure of the product.

  14. Dimensions du transfert adolescent et indications thérapeutiques

    Directory of Open Access Journals (Sweden)

    Laetitia Petit

    2011-12-01

    Full Text Available Nous proposons de confronter les indications thérapeutiques de dispositifs psychanalytiques durant la période adolescente - psychanalyse, psychothérapie psychanalytique, psychodrame analytique individuel. Les dispositifs psychanalytiques constituent une des possibilités d'indication, limitée par la prévalence du maniement du transfert quand la crise d'adolescence est un moment ordinaire de labilité des manifestations pathologiques de révision des états de la structure. Les entretiens préliminaires sont alors fondamentaux pour évaluer cette indication qui sera décisive, mais qui reste néanmoins temporellement dépendante de l'engagement transférentiel de l'adolescent.

  15. Researches on Preliminary Chemical Reactions in Spark-Ignition Engines

    Science.gov (United States)

    1943-06-01

    working conditions of the engine influencing the gas-state conditions in the cylinder through the varia- tion in the rate of heat exchange , but also and...and Kooymann, L. P.: Reactions chimiques ~realables dans un moteur a essence. Chaleur et Industrie, vol. 20, 1939, pp. 120-125. 39NACA Technical

  16. Theoretical studies of the dynamics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Wagner, A.F. [Argonne National Laboratory, IL (United States)

    1993-12-01

    Recent research effort has focussed on several reactions pertinent to combustion. The formation of the formyl radical from atomic hydrogen and carbon monoxide, recombination of alkyl radicals and halo-alkyl radicals with halogen atoms, and the thermal dissociation of hydrogen cyanide and acetylene have been studied by modeling. In addition, the inelastic collisions of NCO with helium have been investigated.

  17. Non-allergic cutaneous reactions in airborne chemical sensitivity--a population based study.

    Science.gov (United States)

    Berg, Nikolaj Drimer; Linneberg, Allan; Thyssen, Jacob Pontoppidan; Dirksen, Asger; Elberling, Jesper

    2011-06-01

    Multiple chemical sensitivity (MCS) is characterised by adverse effects due to exposure to low levels of chemical substances. The aetiology is unknown, but chemical related respiratory symptoms have been found associated with positive patch test. The purpose of this study was to investigate the relationship between cutaneous reactions from patch testing and self-reported severity of chemical sensitivity to common airborne chemicals. A total of 3460 individuals participating in a general health examination, Health 2006, were patch tested with allergens from the European standard series and screened for chemical sensitivity with a standardised questionnaire dividing the participants into four severity groups of chemical sensitivity. Both allergic and non-allergic cutaneous reactions--defined as irritative, follicular, or doubtful allergic reactions--were analysed in relationship with severity of chemical sensitivity. Associations were controlled for the possible confounding effects of sex, age, asthma, eczema, atopic dermatitis, psychological and social factors, and smoking habits. In unadjusted analyses we found associations between allergic and non-allergic cutaneous reactions on patch testing and the two most severe groups of self-reported sensitivity to airborne chemicals. When adjusting for confounding, associations were weakened, and only non-allergic cutaneous reactions were significantly associated with individuals most severely affected by inhalation of airborne chemicals (odds ratio = 2.5, p = 0.006). Our results suggest that individuals with self-reported chemical sensitivity show increased non-allergic cutaneous reactions based on day 2 readings of patch tests. Copyright © 2011 Elsevier GmbH. All rights reserved.

  18. X-ray Microspectroscopy and Chemical Reactions in Soil Microsites

    Energy Technology Data Exchange (ETDEWEB)

    D Hesterberg; M Duff; J Dixon; M Vepraskas

    2011-12-31

    Soils provide long-term storage of environmental contaminants, which helps to protect water and air quality and diminishes negative impacts of contaminants on human and ecosystem health. Characterizing solid-phase chemical species in highly complex matrices is essential for developing principles that can be broadly applied to the wide range of notoriously heterogeneous soils occurring at the earth's surface. In the context of historical developments in soil analytical techniques, we describe applications of bulk-sample and spatially resolved synchrotron X-ray absorption spectroscopy (XAS) for characterizing chemical species of contaminants in soils, and for determining the uniqueness of trace-element reactivity in different soil microsites. Spatially resolved X-ray techniques provide opportunities for following chemical changes within soil microsites that serve as highly localized chemical micro- (or nano-)reactors of unique composition. An example of this microreactor concept is shown for micro-X-ray absorption near edge structure analysis of metal sulfide oxidation in a contaminated soil. One research challenge is to use information and principles developed from microscale soil chemistry for predicting macroscale and field-scale behavior of soil contaminants.

  19. Performing chemical reactions in virtual capillary of surface tension ...

    Indian Academy of Sciences (India)

    poly(dimethyl siloxane) elastomers [11,12]. On the other hand, 2D microchannels are generally designed by chemically altering selective regions of a substrate surface. [13]. The fluid flow is induced and controlled in 3D microfluidic channels by several processes like pumping, electro osmosis, capillarity etc., while that in 2D ...

  20. Quantum-State Controlled Chemical Reactions of Ultracold Potassium-Rubidium Molecules

    National Research Council Canada - National Science Library

    S. Ospelkaus; K.-K. Ni; D. Wang; M. H. G. de Miranda; B. Neyenhuis; G. Queméméner; P. S. Julienne; J. L. Bohn; D. S. Jin; J. Ye

    2010-01-01

    ...? Starting with an optically trapped near-quantum-degenerate gas of polar 40 K 87 Rb molecules prepared in their absolute ground state, we report experimental evidence for exothermic atom-exchange chemical reactions...

  1. On the combined effect of the chemical reaction and a higher order ...

    African Journals Online (AJOL)

    On the combined effect of the chemical reaction and a higher order temparature profile on the velocity of a stretched vertical permeable surface in the magnetohydrodynamic (MHD) flow in the presence of heat generation and absorption.

  2. Chemical reaction on MHD flow and heat transfer of a nanofluid ...

    African Journals Online (AJOL)

    DR OKE

    Keywords: Stagnation point flow; Chemical reaction; Heat transfer; Stretching ..... combined effects of the strength of the Brownian motion and thermophoresis .... J. and Hu W., 2005, Nanofluid coolants for advanced nuclear power plants”.

  3. THERMODYNAMIC ANALYSIS OF CHEMICAL REACTIONS IN CONTACT ZONE OF METAL-NONSTICK COVERING+

    Directory of Open Access Journals (Sweden)

    D. M. Kukuj

    2010-01-01

    Full Text Available An attempt to estimate by thermodynamic method the probability of chemical reactions flowing in contact zone of metal-casting mold at production of castings of iron-carbon alloys is undertaken.

  4. LSENS, a general chemical kinetics and sensitivity analysis code for gas-phase reactions: User's guide

    Science.gov (United States)

    Radhakrishnan, Krishnan; Bittker, David A.

    1993-01-01

    A general chemical kinetics and sensitivity analysis code for complex, homogeneous, gas-phase reactions is described. The main features of the code, LSENS, are its flexibility, efficiency and convenience in treating many different chemical reaction models. The models include static system, steady, one-dimensional, inviscid flow, shock initiated reaction, and a perfectly stirred reactor. In addition, equilibrium computations can be performed for several assigned states. An implicit numerical integration method, which works efficiently for the extremes of very fast and very slow reaction, is used for solving the 'stiff' differential equation systems that arise in chemical kinetics. For static reactions, sensitivity coefficients of all dependent variables and their temporal derivatives with respect to the initial values of dependent variables and/or the rate coefficient parameters can be computed. This paper presents descriptions of the code and its usage, and includes several illustrative example problems.

  5. NATO Advanced Research Workshop on The Theory of Chemical Reaction Dynamics

    CERN Document Server

    1986-01-01

    The calculation of cross sections and rate constants for chemical reactions in the gas phase has long been a major problem in theoretical chemistry. The need for reliable and applicable theories in this field is evident when one considers the significant recent advances that have been made in developing experimental techniques, such as lasers and molecular beams, to probe the microscopic details of chemical reactions. For example, it is now becoming possible to measure cross sections for chemical reactions state selected in the vibrational­ rotational states of both reactants and products. Furthermore, in areas such as atmospheric, combustion and interstellar chemistry, there is an urgent need for reliable reaction rate constant data over a range of temperatures, and this information is often difficult to obtain in experiments. The classical trajectory method can be applied routinely to simple reactions, but this approach neglects important quantum mechanical effects such as tunnelling and resonances. For al...

  6. Search for the existence of the tetra-neutron through the He{sup 8}(d,Li{sup 6})4n nuclear reaction; Recherche de l'existence eventuelle du tetraneutron via la reaction de transfert {sup 8}He(d, {sup 6}Li)4n

    Energy Technology Data Exchange (ETDEWEB)

    Rich, E

    2005-10-15

    The He{sup 8}(d,Li{sup 6})4n reaction is studied through reverse kinematics: a radioactive beam of He{sup 8} nuclei impinges on a CD{sub 2} target. The measurement of the energy spectrum and emission angle distribution of Li{sup 6} has allowed us to determine by applying kinematics laws the excitation energy spectrum of the 4 neutrons system released in the reaction. The first chapter recalls the main features of the nucleon-nucleon interaction and reviews recent experiments on multi-neutrons. The second chapter presents the experimental setting from the production of the He{sup 8} beam at GANIL to the detection system of the reaction products via the data acquisition system. The method of the missing mass gives the mass of the 4 neutron system. The third and fourth chapters deal with the calibration of the detection system, the missing mass method is applied to the following reactions: C{sup 12}(d,Li{sup 6})Be{sup 8}, C{sup 12}(d,t)C{sup 11} and C{sup 12}(d,He{sup 3})B{sup 11}. The last chapter presents the experimental results. The analysis of the excitation energy spectrum of the 4 neutron systems shows no evidence for the existence of a bound state. We get a maximal limit of 60 {mu}b for the production cross section of a bound state. Complementary results concerning the excitation energy spectra of the di-neutron and tri-neutron released in the reactions: He{sup 8}(d,Li{sup 8})2n and He{sup 8}(d,Li{sup 7})3n are also presented. (A.C.)

  7. A semiclassical non-adiabatic theory for elementary chemical reactions

    CERN Document Server

    Aubry, Serge

    2014-01-01

    Electron Transfer (ET) reactions are modeled by the dynamics of a quantum two-level system (representing the electronic state) coupled to a thermalized bath of classical harmonic oscillators (representing the nuclei degrees of freedom). Unlike for the standard Marcus theory, the complex amplitudes of the electronic state are chosen as reaction coordinates. Then, the dynamical equations at non vanishing temperature become those of an effective Hamiltonian submitted to damping terms and their associated Langevin random forces. The advantage of this new formalism is to extend the original theory by taking into account both ionic and covalent interactions. The standard theory is recovered only when covalent interactions are neglected. Increasing these covalent interactions from zero, the energy barrier predicted by the standard theory first depresses, next vanish (or almost vanish) and for stronger covalent interactions, covalent bond formation takes place of ET. In biochemistry, the standard Marcus theory often ...

  8. Enhanced Oxidation and Solvolysis Reactions in Chemically Inert Microheterogeneous Systems.

    Science.gov (United States)

    1986-09-22

    been worked out for concentrations ranging from 8 M to S10 - 7 M. The stability of microemulsions containing sodium laurate, sodium dodecyl sulfate...Microemulsions containing sodium laurate as a surfactant enhance hydrogen peroxide decomposition by more than a factor of 103 , and research usin...aggregation (high local concentration due to the microhe- terogeneous character of the reaction medium). Stability tests with perborate will be undertaken

  9. Concept Maps as a Tool for Teaching Organic Chemical Reactions.

    Science.gov (United States)

    Šket, Barbara; Aleksij Glažar, Saša; Vogrinc, Janez

    2015-01-01

    The purpose of the research was to establish the impact of the application of a concept map in chemistry lessons on the effective solving of tasks with organic reactions content. In the first phase of the research, a concept map was produced representing the reactions of hydrocarbons, organic halogenated compounds and organic oxygen compounds, and in the second phase the produced concept map was introduced in lessons. Its impact was tested on a sample consisting of 186 students (average age of 17.8 years), who were divided into a control group (88 students) and an experimental group (98 students). Prior to the experiment, the two groups were equalised in terms of their level of development of formal logical thinking and their average grade in chemistry. A knowledge test, consisting of five problem tasks comprising multiple parts, was used as a quantitative instrument for measuring the impact of the applied concept map. The content of the knowledge test was selected on the basis of the chemistry lesson plan (reactions of organic oxygen compounds) for general upper secondary schools (in Slovenian: gimnazije). An analysis of the task solving showed statistically significant differences in the responses of the experimental group members and the control group members (experimental group M = 15.9; SD = 6.33; control group M = 13.6; SD = 7.93; p = 0.03). The produced concept map contributed to the more effective interrelation of concepts and, consequently, to more effective problem task solving.

  10. Surface chemical reactions induced by molecules electronically-excited in the gas

    DEFF Research Database (Denmark)

    Petrunin, Victor V.

    2011-01-01

    We present a model suggesting high chemical activity of electronically-excited molecules colliding with an isolator surface. Initial photochemical event is accounted for as the result of molecular evolution on the electronically-excited potential energy surface (PES), where acceleration and align...... beams inducing the reaction can be used to distinguish the new process we try to investigate from chemical reactions induced by photoexcitation within adsorbed molecules and/or gas phase photolysis....

  11. Non-allergic cutaneous reactions in airborne chemical sensitivity--a population based study

    DEFF Research Database (Denmark)

    Berg, Nikolaj Drimer; Linneberg, Allan; Thyssen, Jacob Pontoppidan

    2011-01-01

    the relationship between cutaneous reactions from patch testing and self-reported severity of chemical sensitivity to common airborne chemicals. A total of 3460 individuals participating in a general health examination, Health 2006, were patch tested with allergens from the European standard series and screened...... most severe groups of self-reported sensitivity to airborne chemicals. When adjusting for confounding, associations were weakened, and only non-allergic cutaneous reactions were significantly associated with individuals most severely affected by inhalation of airborne chemicals (odds ratio = 2.5, p = 0.......006). Our results suggest that individuals with self-reported chemical sensitivity show increased non-allergic cutaneous reactions based on day 2 readings of patch tests....

  12. One-nucleon transfer reactions induced by secondary beam of {sup 11}Be: study of the nuclear structure of the exotic nuclei {sup 11}Be and {sup 10}Li; Reactions de transfert d'un nucleon induites par un faisceau secondaire de {sup 11}Be: etude de la structure des noyaux exotiques {sup 11}Be et {sup 10}Li

    Energy Technology Data Exchange (ETDEWEB)

    Pita, S

    2000-09-01

    The structure of the neutron rich light nuclei {sup 11}Be and {sup 10}Li has been investigated by means of one nucleon transfer reactions. The experiments have been carried out at GANIL in inverse kinematics using {sup 11}Be secondary beams. The {sup 11}Be(p,d){sup 10}Be reaction bas been studied at 35.3 MeV/u. The {sup 10}Be ejectiles were analyzed by the spectrometer SPEG, and coincident deuterons were detected in the position sensitive silicon detector CHARISSA. Transfer cross sections to 0{sup +}{sub 1} and 2{sup +}{sub 1}, states in {sup 10}Be were measured up to {theta}{sub CM} = 16 deg. and compared to DWBA and CRC predictions. The effects of neutron-cure couplings on reaction form factors have been studied by solving coupled equations in the framework of a vibrational model. It is shown that the rate of core excitation {sup 10}Be{sub 2+} in the {sup 11}Be{sub gs} wave function is overestimated by a standard analysis with form factors given by the usual Separation Energy prescription. The former model predicts a rate of core excitation of 16% and leads to theoretical cross sections which are in good agreement with the experimental data. The aim of the {sup 11}Be(d,{sup 3}He){sup 10}Li experiment, realized at 37 MeV/u, was to measure the distribution of the 2s neutron strength in the unbound nucleus {sup 10}Li. The energy spectrum was deduced from the {sup 3}He energy and angle measured by the silicon strip detector array MUST. An asymmetric peak is clearly observed near the threshold, with a maximum at -S{sub n} = 130 keV. This constitutes a direct proof of the inversion of 2s and 1p{sub 1/2} shells in {sup 10}Li, which was until now a controversial question in spite of many experimental efforts. On the other band the analysis of the {sup 11}Be(d,t){sup 10}Be reaction studied in the same experiment confirms the results obtained in the {sup 11}Be(p,d){sup 10}Be reaction concerning the {sup 11}Be{sub gs} structure. This work shows the interest and feasibility

  13. Non-stationary filtration mode during chemical reactions with the gas phase

    Science.gov (United States)

    Zavialov, Ivan; Konyukhov, Andrey; Negodyaev, Sergey

    2015-04-01

    An experimental and numerical study of filtration accompanied by chemical reactions between displacing fluid and solid skeleton is considered. Glass balls (400-500 μm in diameter) were placed in 1 cm gap between two glass sheets and were used as model porous medium. The baking soda was added to the glass balls. The 70% solution of acetic acid was used as the displacer. The modeling porous medium was saturated with a mineral oil, and then 70% solution of colored acetic acid was pumped through the medium. The glass balls and a mineral oil have a similar refractive index, so the model porous medium was optically transparent. During the filtration, the gas phase was generated by the chemical reactions between the baking soda and acetic acid, and time-dependent displacement of the chemical reaction front was observed. The front of the chemical reaction was associated with the most intensive gas separation. The front moved, stopped, and then moved again to the area where it had been already. We called this process a secondary oxidation wave. To describe this effect, we added to the balance equations a term associated with the formation and disappearance of phases due to chemical reactions. The equations were supplemented by Darcy's law for multiphase filtration. Nonstationarity front propagation of the chemical reaction in the numerical experiment was observed at Damköhler numbers greater than 100. The mathematical modelling was agreed well with the experimental results.

  14. Studying chemical reactions in biological systems with MBN Explorer

    DEFF Research Database (Denmark)

    Sushko, Gennady B.; Solov'yov, Ilia A.; Verkhovtsev, Alexey V.

    2016-01-01

    The concept of molecular mechanics force field has been widely accepted nowadays for studying various processes in biomolecular systems. In this paper, we suggest a modification for the standard CHARMM force field that permits simulations of systems with dynamically changing molecular topologies....... for studying processes where rupture of chemical bonds plays an essential role, e.g., in irradiation- or collision-induced damage, and also in transformation and fragmentation processes involving biomolecular systems....

  15. Mechanism and Chemical Reaction of Fly Ash Geopolymer Cement- A Review

    OpenAIRE

    A.M. Mustafa Al Bakri; Kamarudin, H.; M. Bnhussain; I. Khairul Nizar; W.I.W. Mastura

    2011-01-01

    This paper presents the work carried out on the chemical reaction, mechanism, role of materials, applications and microstructure of fly ash geopolymer cement. Geopolymeris a type of amorphous alumino-silicate cementitious material. Geopolymer can besynthesized by polycondensation reaction of geopolymeric precursor, and alkalipolysilicates. Literature demonstrates that the exact geopolymerization mechanism is not well understood because the geopolymerization process involves a substantially fa...

  16. Femtosecond laser induced and controlled chemical reaction of carbon monoxide and hydrogen

    CSIR Research Space (South Africa)

    Du Plessis, A

    2011-07-01

    Full Text Available Results from experiments aimed at bimolecular chemical reaction control of CO and H2 at room temperature and pressure, without any catalyst, using shaped femtosecond laser pulses are presented. A stable reaction product (CO 2) was measured after...

  17. Quantum chemical investigation of the reaction of O( P2) with certain ...

    Indian Academy of Sciences (India)

    WINTEC

    Quantum chemical investigation of the reactions of O(3P2). 459. Figure 2. Optimized geometries of reactants, products, intermediates and transition states for the reaction of O(3. P2) atom with ethyl radical at the CBS–QB3 level of theory. Distances are in Å. Figure 3. Optimized geometries of reactants, products and ...

  18. Process for carrying out a chemical reaction with ionic liquid and carbon dioxide under pressure

    NARCIS (Netherlands)

    Kroon, M.C.; Shariati, A.; Florusse, L.J.; Peters, C.J.; Van Spronsen, J.; Witkamp, G.J.; Sheldon, R.A.; Gutkowski, K.I.

    2006-01-01

    The invention is directed to a process for carrying out a chemical reaction in an ionic liquid as solvent and CO2 as cosolvent, in which process reactants are reacted in a homogeneous phase at selected pressure and temperature to generate a reaction product at least containing an end-product of the

  19. Constructing and Visualizing Chemical Reaction Networks from Pi-Calculus Models

    OpenAIRE

    John, Mathias; Schulz, Hans-Jörg; Schumann, Heidrun; Uhrmacher, Adelinde; Unger, Andrea

    2012-01-01

    International audience; The pi-calculus, in particular its stochastic version the stochastic pi-calculus, is a common modeling formalism to concisely describe the chemical reactions occurring in biochemical systems. However, it remains largely unexplored how to transform a biochemical model expressed in the stochastic pi-calculus back into a set of meaningful reactions. To this end, we present a two step approach of first translating model states to reaction sets and then visualizing sequence...

  20. A Computational Approach to Extinction Events in Chemical Reaction Networks with Discrete State Spaces

    OpenAIRE

    Johnston, Matthew D.

    2017-01-01

    Recent work of M.D. Johnston et al. has produced sufficient conditions on the structure of a chemical reaction network which guarantee that the corresponding discrete state space system exhibits an extinction event. The conditions consist of a series of systems of equalities and inequalities on the edges of a modified reaction network called a domination-expanded reaction network. In this paper, we present a computational implementation of these conditions written in Python and apply the prog...

  1. Quantum chemical study of penicillin: Reactions after acylation

    Science.gov (United States)

    Li, Rui; Feng, Dacheng; Zhu, Feng

    The density functional theory methods were used on the model molecules of penicillin to determine the possible reactions after their acylation on ?-lactamase, and the results were compared with sulbactam we have studied. The results show that, the acylated-enzyme tetrahedral intermediate can evolves with opening of ?-lactam ring as well as the thiazole ring; the thiazole ring-open products may be formed via ?-lactam ring-open product or from tetrahedral intermediate directly. Those products, in imine or enamine form, can tautomerize via hydrogen migration. In virtue of the water-assisted, their energy barriers are obviously reduced.

  2. A quantum constrained kinematic model for elementary chemical reactions

    Science.gov (United States)

    McCaffery, Anthony J.; Truhins, Kaspars; Whiteley, Thomas W. J.

    1998-05-01

    The model we have termed quantum constrained kinematics and found to give an accurate account of atom-diatom inelastic scattering is tested by application to elementary atom-molecule reactive collisions. The approach emphasizes the disposal of initial relative momentum into rotational angular momentum of the product diatomic via vector relations that are constrained by the internal quantum structure of the product diatomic. We introduce the concept of vibrational momentum of the atoms in a diatomic molecule in order to treat vibrational and rotational excitation of the product species. This representation is valuable in providing a realistic picture of the motion in a heteronuclear diatomic and also indicates how the enthalpy of a reaction may be disposed in momentum terms. It may also provide criteria for assessing the likelihood of particular reaction mechanisms. Comparison of results calculated using the quantum constrained kinematic model with experimental data indicates a number of simple, transferable rule-of-thumb guides to the outcome of reactive collisions. Most probable j values and distributions are accurately predicted using readily available data in parameter-free calculations. It is found that in reactive collisions, initial velocity distributions are mapped onto those of product rotational states via an effective impact parameter distribution that is sharply peaked around the half bond length of the product diatomic molecule.

  3. Surface Nano-Structuring by Adsorption and Chemical Reactions

    Directory of Open Access Journals (Sweden)

    Ken-ichi Tanaka

    2010-08-01

    Full Text Available Nano-structuring of the surface caused by adsorption of molecules or atoms and by the reaction of surface atoms with adsorbed species are reviewed from a chemistry viewpoint. Self-assembly of adsorbed species is markedly influenced by weak mutual interactions and the local strain of the surface induced by the adsorption. Nano-structuring taking place on the surface is well explained by the notion of a quasi-molecule provided by the reaction of surface atoms with adsorbed species. Self-assembly of quasi-molecules by weak internal bonding provides quasi-compounds on a specific surface. Various nano-structuring phenomena are discussed: (i self-assembly of adsorbed molecules and atoms; (ii self-assembly of quasi-compounds; (iii formation of nano-composite surfaces; (iv controlled growth of nano-materials on composite surfaces. Nano-structuring processes are not always controlled by energetic feasibility, that is, the formation of nano-composite surface and the growth of nano-particles on surfaces are often controlled by the kinetics. The idea of the “kinetic controlled molding” might be valuable to design nano-materials on surfaces.

  4. Thin liquid films with time-dependent chemical reactions sheared by an ambient gas flow

    Science.gov (United States)

    Bender, Achim; Stephan, Peter; Gambaryan-Roisman, Tatiana

    2017-08-01

    Chemical reactions in thin liquid films are found in many industrial applications, e.g., in combustion chambers of internal combustion engines where a fuel film can develop on pistons or cylinder walls. The reactions within the film and the turbulent outer gas flow influence film stability and lead to film breakup, which in turn can lead to deposit formation. In this work we examine the evolution and stability of a thin liquid film in the presence of a first-order chemical reaction and under the influence of a turbulent gas flow. Long-wave theory with a double perturbation analysis is used to reduce the complexity of the problem and obtain an evolution equation for the film thickness. The chemical reaction is assumed to be slow compared to film evolution and the amount of reactant in the film is limited, which means that the reaction rate decreases with time as the reactant is consumed. A linear stability analysis is performed to identify the influence of reaction parameters, material properties, and environmental conditions on the film stability limits. Results indicate that exothermic reactions have a stabilizing effect whereas endothermic reactions destabilize the film and can lead to rupture. It is shown that an initially unstable film can become stable with time as the reaction rate decreases. The shearing of the film by the external gas flow leads to the appearance of traveling waves. The shear stress magnitude has a nonmonotonic influence on film stability.

  5. Autocatalytic sets and chemical organizations: modeling self-sustaining reaction networks at the origin of life

    Science.gov (United States)

    Hordijk, Wim; Steel, Mike; Dittrich, Peter

    2018-01-01

    Two related but somewhat different approaches have been proposed to formalize the notion of a self-sustaining chemical reaction network. One is the notion of collectively autocatalytic sets, formalized as RAF theory, and the other is chemical organization theory. Both formalisms have been argued to be relevant to the origin of life. RAF sets and chemical organizations are defined differently, but previously some relationships between the two have been shown. Here, we refine and explore these connections in more detail. In particular, we show that so-called closed RAFs are chemical organizations, but that the converse is not necessarily true. We then introduce and apply a procedure to show how chemical organizations can be used to find all closed RAFs within any chemical reaction system. We end with a discussion of why and how closed RAFs could be important in the context of the origin and early evolution of life.

  6. The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Tully, John C. [Yale Univ., New Haven, CT (United States)

    2017-06-10

    Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opens up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.

  7. Chemical alterations taken place during deep-fat frying based on certain reaction products: a review.

    Science.gov (United States)

    Zhang, Qing; Saleh, Ahmed S M; Chen, Jing; Shen, Qun

    2012-09-01

    Deep-fat frying at 180 °C or above is one of the most common food processing methods used for preparing of human kind foods worldwide. However, a serial of complex reactions such as oxidation, hydrolysis, isomerization, and polymerization take place during the deep-fat frying course and influence quality attributes of the final product such as flavor, texture, shelf life and nutrient composition. The influence of these reactions results from a number of their products including volatile compounds, hydrolysis products, oxidized triacylglycerol monomers, cyclic compounds, trans configuration compounds, polymers, sterol derivatives, nitrogen- and sulphur-containing heterocyclic compounds, acrylamide, etc. which are present in both frying oil and the fried food. In addition, these reactions are interacted and influenced by various impact factors such as frying oil type, frying conditions (time, temperature, fryer, etc.) and fried material type. Based on the published literatures, three main organic chemical reaction mechanisms namely hemolytic, heterolytic and concerted reaction were identified and supposed to elucidate the complex chemical alterations during deep-fat frying. However, well understanding the mechanisms of these reactions and their products under different conditions helps to control the deep-fat frying processing; therefore, producing healthy fried foods. By means of comprehensively consulting the papers which previously studied on the chemical changes occurred during deep-fat frying process, the major reaction products and corresponding chemical alterations were reviewed in this work. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

  8. Chemical Reaction Rate Coefficients from Ring Polymer Molecular Dynamics: Theory and Practical Applications.

    Science.gov (United States)

    Suleimanov, Yury V; Aoiz, F Javier; Guo, Hua

    2016-11-03

    This Feature Article presents an overview of the current status of ring polymer molecular dynamics (RPMD) rate theory. We first analyze the RPMD approach and its connection to quantum transition-state theory. We then focus on its practical applications to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rate coefficients in multifarious cases. This review serves as an important checkpoint in RPMD rate theory development, which shows that RPMD is shifting from being just one of recent novel ideas to a well-established and validated alternative to conventional techniques for calculating thermal chemical rate coefficients. We also hope it will motivate further applications of RPMD to various chemical reactions.

  9. Students' Ideas about How and Why Chemical Reactions Happen: Mapping the conceptual landscape

    Science.gov (United States)

    Yan, Fan; Talanquer, Vicente

    2015-12-01

    Research in science education has revealed that many students struggle to understand chemical reactions. Improving teaching and learning about chemical processes demands that we develop a clearer understanding of student reasoning in this area and of how this reasoning evolves with training in the domain. Thus, we have carried out a qualitative study to explore students reasoning about chemical causality and mechanism. Study participants included individuals at different educational levels, from college to graduate school. We identified diverse conceptual modes expressed by students when engaged in the analysis of different types of reactions. Main findings indicate that student reasoning about chemical reactions is influenced by the nature of the process. More advanced students tended to express conceptual modes that were more normative and had more explanatory power, but major conceptual difficulties persisted in their reasoning. The results of our study are relevant to educators interested in conceptual development, learning progressions, and assessment.

  10. Mathematical Formalism of Nonequilibrium Thermodynamics for Nonlinear Chemical Reaction Systems with General Rate Law

    Science.gov (United States)

    Ge, Hao; Qian, Hong

    2017-01-01

    This paper studies a mathematical formalism of nonequilibrium thermodynamics for chemical reaction models with N species, M reactions, and general rate law. We establish a mathematical basis for J. W. Gibbs' macroscopic chemical thermodynamics under G. N. Lewis' kinetic law of entire equilibrium (detailed balance in nonlinear chemical kinetics). In doing so, the equilibrium thermodynamics is then naturally generalized to nonequilibrium settings without detailed balance. The kinetic models are represented by a Markovian jumping process. A generalized macroscopic chemical free energy function and its associated balance equation with nonnegative source and sink are the major discoveries. The proof is based on the large deviation principle of this type of Markov processes. A general fluctuation dissipation theorem for stochastic reaction kinetics is also proved. The mathematical theory illustrates how a novel macroscopic dynamic law can emerges from the mesoscopic kinetics in a multi-scale system.

  11. Students' Dilemmas in Reaction Stoichiometry Problem Solving: Deducing the Limiting Reagent in Chemical Reactions

    Science.gov (United States)

    Chandrasegaran, A. L.; Treagust, David F.; Waldrip, Bruce G.; Chandrasegaran, Antonia

    2009-01-01

    A qualitative case study was conducted to investigate the understanding of the limiting reagent concept and the strategies used by five Year 11 students when solving four reaction stoichiometry problems. Students' written problem-solving strategies were studied using the think-aloud protocol during problem-solving, and retrospective verbalisations…

  12. Chemical Reactions of Molecules Promoted and Simultaneously Imaged by the Electron Beam in Transmission Electron Microscopy.

    Science.gov (United States)

    Skowron, Stephen T; Chamberlain, Thomas W; Biskupek, Johannes; Kaiser, Ute; Besley, Elena; Khlobystov, Andrei N

    2017-08-15

    The main objective of this Account is to assess the challenges of transmission electron microscopy (TEM) of molecules, based on over 15 years of our work in this field, and to outline the opportunities in studying chemical reactions under the electron beam (e-beam). During TEM imaging of an individual molecule adsorbed on an atomically thin substrate, such as graphene or a carbon nanotube, the e-beam transfers kinetic energy to atoms of the molecule, displacing them from equilibrium positions. Impact of the e-beam triggers bond dissociation and various chemical reactions which can be imaged concurrently with their activation by the e-beam and can be presented as stop-frame movies. This experimental approach, which we term ChemTEM, harnesses energy transferred from the e-beam to the molecule via direct interactions with the atomic nuclei, enabling accurate predictions of bond dissociation events and control of the type and rate of chemical reactions. Elemental composition and structure of the reactant molecules as well as the operating conditions of TEM (particularly the energy of the e-beam) determine the product formed in ChemTEM processes, while the e-beam dose rate controls the reaction rate. Because the e-beam of TEM acts simultaneously as a source of energy for the reaction and as an imaging tool monitoring the same reaction, ChemTEM reveals atomic-level chemical information, such as pathways of reactions imaged for individual molecules, step-by-step and in real time; structures of illusive reaction intermediates; and direct comparison of catalytic activity of different transition metals filmed with atomic resolution. Chemical transformations in ChemTEM often lead to previously unforeseen products, demonstrating the potential of this method to become not only an analytical tool for studying reactions, but also a powerful instrument for discovery of materials that can be synthesized on preparative scale.

  13. Separation of chemical reaction intermediates by metal-organic frameworks.

    Science.gov (United States)

    Centrone, Andrea; Santiso, Erik E; Hatton, T Alan

    2011-08-22

    HPLC columns custom-packed with metal-organic framework (MOF) materials are used for the separation of four small intermediates and byproducts found in the commercial synthesis of an important active pharmaceutical ingredient in methanol. In particular, two closely related amines can be separated in the methanol reaction medium using MOFs, but not with traditional C18 columns using an optimized aqueous mobile phase. Infrared spectroscopy, UV-vis spectroscopy, X-ray diffraction, and thermogravimetric analysis are used in combination with molecular dynamic simulations to study the separation mechanism for the best-performing MOF materials. It is found that separation with ZIF-8 is the result of an interplay between the thermodynamic driving force for solute adsorption within the framework pores and the kinetics of solute diffusion into the material pores, while the separation with Basolite F300 is achieved because of the specific interactions between the solutes and Fe(3+) sites. This work, and the exceptional ability to tailor the porous properties of MOF materials, points to prospects for using MOF materials for the continuous separation and synthesis of pharmaceutical compounds. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Molecular Beam Studies of Hot Atom Chemical Reactions: Reactive Scattering of Energetic Deuterium Atoms

    Science.gov (United States)

    Continetti, R. E.; Balko, B. A.; Lee, Y. T.

    1989-02-01

    A brief review of the application of the crossed molecular beams technique to the study of hot atom chemical reactions in the last twenty years is given. Specific emphasis is placed on recent advances in the use of photolytically produced energetic deuterium atoms in the study of the fundamental elementary reactions D + H{sub 2} -> DH + H and the substitution reaction D + C{sub 2}H{sub 2} -> C{sub 2}HD + H. Recent advances in uv laser and pulsed molecular beam techniques have made the detailed study of hydrogen atom reactions under single collision conditions possible.

  15. Molecular beam studies of hot atom chemical reactions: Reactive scattering of energetic deuterium atoms

    Energy Technology Data Exchange (ETDEWEB)

    Continetti, R.E.; Balko, B.A.; Lee, Y.T.

    1989-02-01

    A brief review of the application of the crossed molecular beams technique to the study of hot atom chemical reactions in the last twenty years is given. Specific emphasis is placed on recent advances in the use of photolytically produced energetic deuterium atoms in the study of the fundamental elementary reactions D + H/sub 2/ /minus/> DH + H and the substitution reaction D + C/sub 2/H/sub 2/ /minus/> C/sub 2/HD + H. Recent advances in uv laser and pulsed molecular beam techniques have made the detailed study of hydrogen atom reactions under single collision conditions possible. 18 refs., 9 figs.

  16. Surface chemical reactions induced on pyrite by ion bombardment

    Science.gov (United States)

    Ruano, Gustavo; Pomiro, Fernando; Ferrón, Julio

    2018-01-01

    Through X-ray photoemission spectroscopy (XPS), we studied the chemical changes induced in a natural crystal of pyrite (FeS2) upon exposure to 4.5 keV He+ beam. We found an important reducing effect induced by ion bombardment leading to the production of iron embedded in the pyrite matrix. Through a combination of the usual Doniach-Sunjic treatment and Factor Analysis of XPS yields, we were able of analyzing the full Fe 2p XPS signal. We could in this way distinguish Fe compounds with the same binding energy for the Fe 2p3/2 yield. Our results show that He+ bombardment disrupts the ionic environment producing S2-2 and S0, Fe2+ and Fe3+ ions, and the reduction to metallic iron. The remaining pyrite matrix does not passivate the embedded iron structures, which are readily oxidized under air exposure. The oxide formed resembled that of magnetite from the XPS point of view. Further He+ bombardment proved to be efficient to reduce the iron oxide back to iron again.

  17. An approach to quantum chemical consideration of "hydride" transfer reactions

    Directory of Open Access Journals (Sweden)

    BORIS I. DREVKO

    2004-06-01

    Full Text Available An approach to the quantum chemical study of "hydride ion" transfer has been proposed, according to which the sequences of changes in ionization potentials, enthalpies and free energies of the affinities to the hydride ion, to the hydrogen atom and to the proton of substrates molecules and their derivatives (cations, radicals, anions, are compared with the experimentally substantiated series of "hydride" mobility. It has been established that the experimental series of "hydride" mobility for six chalcogenopyrans based on "semicyclic" 1,5-diketones is in conformity with the computed ionization potentials of the molecules, and with the affinity of the corresponding radicals to the hydrogen atom involved in the transfer. The direct splitting-out of the hydride ion and the primary deprotonation of the substrates followed by the withdrawal of two electrons was elucidated to be unlikely. Feasible are the mechanisms of "hydride" mobility, the first step of which consists of electron or hydrogen atom transfer from the chalcogenopyrans molecules.

  18. Quantum theory of chemical reactions in the presence of electromagnetic fields.

    Science.gov (United States)

    Tscherbul, T V; Krems, R V

    2008-07-21

    We present a theory for rigorous quantum scattering calculations of probabilities for chemical reactions of atoms with diatomic molecules in the presence of an external electric field. The approach is based on the fully uncoupled basis set representation of the total wave function in the space-fixed coordinate frame, the Fock-Delves hyperspherical coordinates, and the adiabatic partitioning of the total Hamiltonian of the reactive system. The adiabatic channel wave functions are expanded in basis sets of hyperangular functions corresponding to different reaction arrangements, and the interactions with external fields are included in each chemical arrangement separately. We apply the theory to examine the effects of electric fields on the chemical reactions of LiF molecules with H atoms and HF molecules with Li atoms at low temperatures and show that electric fields may enhance the probability of chemical reactions and modify reactive scattering resonances by coupling the rotational states of the reactants. Our preliminary results suggest that chemical reactions of polar molecules at temperatures below 1 K can be selectively manipulated with dc electric fields and microwave laser radiation.

  19. The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled.

    Science.gov (United States)

    Göppel, Tobias; Palyulin, Vladimir V; Gerland, Ulrich

    2016-07-27

    An out-of-equilibrium physical environment can drive chemical reactions into thermodynamically unfavorable regimes. Under prebiotic conditions such a coupling between physical and chemical non-equilibria may have enabled the spontaneous emergence of primitive evolutionary processes. Here, we study the coupling efficiency within a theoretical model that is inspired by recent laboratory experiments, but focuses on generic effects arising whenever reactant and product molecules have different transport coefficients in a flow-through system. In our model, the physical non-equilibrium is represented by a drift-diffusion process, which is a valid coarse-grained description for the interplay between thermophoresis and convection, as well as for many other molecular transport processes. As a simple chemical reaction, we consider a reversible dimerization process, which is coupled to the transport process by different drift velocities for monomers and dimers. Within this minimal model, the coupling efficiency between the non-equilibrium transport process and the chemical reaction can be analyzed in all parameter regimes. The analysis shows that the efficiency depends strongly on the Damköhler number, a parameter that measures the relative timescales associated with the transport and reaction kinetics. Our model and results will be useful for a better understanding of the conditions for which non-equilibrium environments can provide a significant driving force for chemical reactions in a prebiotic setting.

  20. Chemical reaction vector embeddings: towards predicting drug metabolism in the human gut microbiome.

    Science.gov (United States)

    Mallory, Emily K; Acharya, Ambika; Rensi, Stefano E; Turnbaugh, Peter J; Bright, Roselie A; Altman, Russ B

    2018-01-01

    Bacteria in the human gut have the ability to activate, inactivate, and reactivate drugs with both intended and unintended effects. For example, the drug digoxin is reduced to the inactive metabolite dihydrodigoxin by the gut Actinobacterium E. lenta, and patients colonized with high levels of drug metabolizing strains may have limited response to the drug. Understanding the complete space of drugs that are metabolized by the human gut microbiome is critical for predicting bacteria-drug relationships and their effects on individual patient response. Discovery and validation of drug metabolism via bacterial enzymes has yielded >50 drugs after nearly a century of experimental research. However, there are limited computational tools for screening drugs for potential metabolism by the gut microbiome. We developed a pipeline for comparing and characterizing chemical transformations using continuous vector representations of molecular structure learned using unsupervised representation learning. We applied this pipeline to chemical reaction data from MetaCyc to characterize the utility of vector representations for chemical reaction transformations. After clustering molecular and reaction vectors, we performed enrichment analyses and queries to characterize the space. We detected enriched enzyme names, Gene Ontology terms, and Enzyme Consortium (EC) classes within reaction clusters. In addition, we queried reactions against drug-metabolite transformations known to be metabolized by the human gut microbiome. The top results for these known drug transformations contained similar substructure modifications to the original drug pair. This work enables high throughput screening of drugs and their resulting metabolites against chemical reactions common to gut bacteria.

  1. Mianserin affects alarm reaction to conspecific chemical alarm cues in Nile tilapia.

    Science.gov (United States)

    Barreto, Rodrigo Egydio

    2017-02-01

    In this study, I show that mianserin, a chemical with serotonin and adrenoceptor antagonist activities, increases fish vulnerability to a potential predator threat, when prey fish must deal with this threat based on conspecific chemical alarm cues. For that, I evaluated whether mianserin, diluted in the water, influences the behavioral responses of Nile tilapia (Oreochromis niloticus) to conspecific skin extract (chemical alarm cues). I found that, while mianserin did not abolished antipredator responses, this drug mitigates some components of this defensive reaction. Thus, a potential decrease in serotonin and adrenergic activities reduces the ability of dealing with predators when perceiving conspecific chemical alarm cues.

  2. Chemical reactions studied at ultra-low temperature in liquid helium clusters

    Science.gov (United States)

    Huisken, Friedrich; Krasnokutski, Serge A.

    2012-11-01

    Low-temperature reaction rates are important ingredients for astrophysical reaction networks modeling the formation of interstellar matter in molecular clouds. Unfortunately, such data is difficult to obtain by experimental means. In an attempt to study low-temperature reactions of astrophysical interest, we have investigated relevant reactions at ultralow temperature in liquid helium droplets. Being prepared by supersonic expansion of helium gas at high pressure through a nozzle into a vacuum, large helium clusters in the form of liquid droplets constitute nano-sized reaction vessels for the study of chemical reactions at ultra-low temperature. If the normal isotope 4He is used, the helium droplets are superfluid and characterized by a constant temperature of 0.37 K. Here we present results obtained for Mg, Al, and Si reacting with O2. Mass spectrometry was employed to characterize the reaction products. As it may be difficult to distinguish between reactions occurring in the helium droplets before they are ionized and ion-molecule reactions taking place after the ionization, additional techniques were applied to ensure that the reactions actually occurred in the helium droplets. This information was provided by measuring the chemiluminescence light emitted by the products, the evaporation of helium atoms by the release of the reaction heat, or by laser-spectroscopic identification of the reactants and products.

  3. The Role of Comprehensive Detailed Chemical Kinetic Reaction Mechanisms in Combustion Research

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Curran, H J; Mehl, M

    2008-07-16

    Recent developments by the authors in the field of comprehensive detailed chemical kinetic reaction mechanisms for hydrocarbon fuels are reviewed. Examples are given of how these mechanisms provide fundamental chemical insights into a range of combustion applications. Practical combustion consists primarily of chemical heat release from reactions between a fuel and an oxidizer, and computer simulations of practical combustion systems have become an essential tool of combustion research (Westbrook et al., 2005). At the heart of most combustion simulations, the chemical kinetic submodel frequently is the most detailed, complex and computationally costly part of a system model. Historically, the chemical submodel equations are solved using time-implicit numerical algorithms, due to the extreme stiffness of the coupled rate equations, with a computational cost that varies roughly with the cube of the number of chemical species in the model. While early mechanisms (c. 1980) for apparently simple fuels such as methane (Warnatz, 1980) or methanol (Westbrook and Dryer, 1979) included perhaps 25 species, current detailed mechanisms for much larger, more complex fuels such as hexadecane (Fournet et al., 2001; Ristori et al., 2001; Westbrook et al., 2008) or methyl ester methyl decanoate (Herbinet et al., 2008) have as many as 2000 or even 3000 species. Rapid growth in capabilities of modern computers has been an essential feature in this rapid growth in the size and complexity of chemical kinetic reaction mechanisms.

  4. A Hybrid Mutation Chemical Reaction Optimization Algorithm for Global Numerical Optimization

    Directory of Open Access Journals (Sweden)

    Ransikarn Ngambusabongsopa

    2015-01-01

    Full Text Available This paper proposes a hybrid metaheuristic approach that improves global numerical optimization by increasing optimal quality and accelerating convergence. This algorithm involves a recently developed process for chemical reaction optimization and two adjustment operators (turning and mutation operators. Three types of mutation operators (uniform, nonuniform, and polynomial were combined with chemical reaction optimization and turning operator to find the most appropriate framework. The best solution among these three options was selected to be a hybrid mutation chemical reaction optimization algorithm for global numerical optimization. The optimal quality, convergence speed, and statistical hypothesis testing of our algorithm are superior to those previous high performance algorithms such as RCCRO, HP-CRO2, and OCRO.

  5. A novel Chemical Reaction Optimization based Higher order Neural Network (CRO-HONN for nonlinear classification

    Directory of Open Access Journals (Sweden)

    Janmenjoy Nayak

    2015-09-01

    Full Text Available In this paper, a Chemical Reaction Optimization (CRO based higher order neural network with a single hidden layer called Pi–Sigma Neural Network (PSNN has been proposed for data classification which maintains fast learning capability and avoids the exponential increase of number of weights and processing units. CRO is a recent metaheuristic optimization algorithm inspired by chemical reactions, free from intricate operator and parameter settings such as other algorithms and loosely couples chemical reactions with optimization. The performance of the proposed CRO-PSNN has been tested with various benchmark datasets from UCI machine learning repository and compared with the resulting performance of PSNN, GA-PSNN, PSO-PSNN. The methods have been implemented in MATLAB and the accuracy measures have been tested by using the ANOVA statistical tool. Experimental results show that the proposed method is fast, steady and reliable and provides better classification accuracy than others.

  6. REACTION OF THE FEMALE BODY TO STRESS IN A CHEMICAL PROTECTIVE CLOTHING

    Directory of Open Access Journals (Sweden)

    Jiří SLABOTINSKÝ

    2016-12-01

    Full Text Available This article deals with the reaction of the female body to the use of an insulation chemical protective clothing combined with working – thermal and mental stress to which the female is exposed. The article provides a concise overview of protective chemical clothings and factors affecting their comfort; it describes the regularities corresponding to the physiological reaction, important for the body’s reaction to the use of a chemical protective clothing. Further, the article contains a description of the measurement and evaluation of physiological parameters of non-acclimated women during testing of these clothings and, finally, comparison with the results for males under the same stress which is unfavourable for women.

  7. Functionalization of Hydrogenated Chemical Vapour Deposition-Grown Graphene by On-Surface Chemical Reactions

    Czech Academy of Sciences Publication Activity Database

    Drogowska, Karolina; Kovaříček, Petr; Kalbáč, Martin

    2017-01-01

    Roč. 23, č. 17 (2017), s. 4022-4022 ISSN 1521-3765 Institutional support: RVO:61388955 Keywords : Chemical vapor deposition * Hydrogenation * Graphene Subject RIV: CF - Physical ; Theoretical Chemistry

  8. Perspective: Chemical reactions in ionic liquids monitored through the gas (vacuum)/liquid interface

    OpenAIRE

    Maier, Florian; Niedermaier, Inga; Steinrück, Hans-Peter

    2017-01-01

    This perspective analyzes the potential of X-ray photoelectron spectroscopy under ultrahigh vacuum (UHV) conditions to follow chemical reactions in ionic liquids in situ. Traditionally, only reactions occurring on solid surfaces were investigated by X-ray photoelectron spectroscopy (XPS) in situ. This was due to the high vapor pressures of common liquids or solvents, which are not compatible with the required UHV conditions. It was only recently realized that the situation is very different w...

  9. Effects of exothermic chemical reaction on the photoacoustic effect from particulate suspensions.

    Science.gov (United States)

    Park, Han Jung; Wu, Binbin; Diebold, Gerald J

    2011-03-28

    Irradiation of chemically reactive particulate suspensions by high power, pulsed laser radiation initiates reactions at the sites of the particles so that besides the absorbed optical energy, chemical energy is liberated. In addition to the release of chemical energy, chemical reaction can result in gas production both of which result in enhancement in the amplitude of the photoacoustic effect. Here we report photoacoustic and transient grating experiments with colloidal C in mixtures of H(2)O(2) with H(2)O. The inclusion of H(2)O(2) in an aqueous C suspension changes the normally endothermic reaction of C with H(2)O into the highly exothermic reaction of C with H(2)O(2) leading to both an enhanced photoacoustic effect and an increase in light emission from the suspension. As well, laser-initiated exothermic reactions in suspensions of C with CH(3)NO(2) and particulate Hg(CNO)(2) in H(2)O are shown to result in greatly enhanced photoacoustic signal amplitudes.

  10. Etude du transfert thermique entre un jet rond turbulent et une paroi ...

    African Journals Online (AJOL)

    Dans ce travail, on s\\'intéresse à l\\'étude du transfert de chaleur d\\'une plaque plane soumise à l\\'action d\\'un jet d\\'air perpendiculaire. L\\'étude de la possibilité d\\'améliorer le transfert de chaleur est effectuée en fonction des paramètres caractéristiques de l\\'interaction jet - paroi. Le problème du jet rond turbulent frappant ...

  11. The lifetime of aerosols in ambient air: Consideration of the effects of surfactants and chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Toossi, R. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Novakov, T. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    1985-01-01

    In this paper, the relatively long lifetime of droplets in atmospheric haze and fog in comparison with similar droplets of pure water is attributed to the presence of a monolayer of surfactant film and to the accumulation of soluble salts from chemical reactions. The lifetime of these droplets is a significant factor in the evaluation of the role of heterogeneous aqueous chemical reactions occurring in the troposphere. Several mechanisms of SO2 oxidation in the presence of liquid water are investigated. Finally, it is shown that soot-catalyzed oxidation of sulfur dioxide could be responsible for the high level of sulfate concentration observed in the coastal industrial areas.

  12. Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories

    Science.gov (United States)

    Gokoglu, Suleyman A.

    1988-01-01

    This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

  13. Perspective: Chemical reactions in ionic liquids monitored through the gas (vacuum)/liquid interface

    Science.gov (United States)

    Maier, F.; Niedermaier, I.; Steinrück, H.-P.

    2017-05-01

    This perspective analyzes the potential of X-ray photoelectron spectroscopy under ultrahigh vacuum (UHV) conditions to follow chemical reactions in ionic liquids in situ. Traditionally, only reactions occurring on solid surfaces were investigated by X-ray photoelectron spectroscopy (XPS) in situ. This was due to the high vapor pressures of common liquids or solvents, which are not compatible with the required UHV conditions. It was only recently realized that the situation is very different when studying reactions in Ionic Liquids (ILs), which have an inherently low vapor pressure, and first studies have been performed within the last years. Compared to classical spectroscopy techniques used to monitor chemical reactions, the advantage of XPS is that through the analysis of their core levels all relevant elements can be quantified and their chemical state can be analyzed under well-defined (ultraclean) conditions. In this perspective, we cover six very different reactions which occur in the IL, with the IL, or at an IL/support interface, demonstrating the outstanding potential of in situ XPS to gain insights into liquid phase reactions in the near-surface region.

  14. Stochastic innovation as a mechanism by which catalysts might self-assemble into chemical reaction networks.

    OpenAIRE

    Bradford, Justin A; Dill, Ken A

    2007-01-01

    We develop a computer model for how two different chemical catalysts in solution, A and B, could be driven to form AB complexes, based on the concentration gradients of a substrate or product that they share in common. If A's product is B's substrate, B will be attracted to A, mediated by a common resource that is not otherwise plentiful in the environment. By this simple physicochemical mechanism, chemical reactions could spontaneously associate to become chained together in solution. Accord...

  15. Computing multi-species chemical equilibrium with an algorithm based on the reaction extents

    DEFF Research Database (Denmark)

    Paz-Garcia, Juan Manuel; Johannesson, Björn; Ottosen, Lisbeth M.

    2013-01-01

    A mathematical model for the solution of a set of chemical equilibrium equations in a multi-species and multiphase chemical system is described. The computer-aid solution of model is achieved by means of a Newton-Raphson method enhanced with a line-search scheme, which deals with the non-negative......A mathematical model for the solution of a set of chemical equilibrium equations in a multi-species and multiphase chemical system is described. The computer-aid solution of model is achieved by means of a Newton-Raphson method enhanced with a line-search scheme, which deals with the non......-negative constrains. The residual function, representing the distance to the equilibrium, is defined from the chemical potential (or Gibbs energy) of the chemical system. Local minimums are potentially avoided by the prioritization of the aqueous reactions with respect to the heterogeneous reactions. The formation...... and release of gas bubbles is taken into account in the model, limiting the concentration of volatile aqueous species to a maximum value, given by the gas solubility constant.The reaction extents are used as state variables for the numerical method. As a result, the accepted solution satisfies the charge...

  16. Common and uncommon cytochrome P450 reactions related to metabolism and chemical toxicity.

    Science.gov (United States)

    Guengerich, F P

    2001-06-01

    Cytochrome P450 (P450) enzymes catalyze a variety of reactions and convert chemicals to potentially reactive products as well as make compounds less toxic. Most of the P450 reactions are oxidations. The majority of these can be rationalized in the context of an FeO(3+) intermediate and odd electron abstraction/rebound mechanisms; however, other iron-oxygen complexes are possible and alternate chemistries can be considered. Another issue regarding P450-catalyzed reactions is the delineation of rate-limiting steps in the catalytic cycle and the contribution to reaction selectivity. In addition to the rather classical oxidations, P450s also catalyze less generally discussed reactions including reduction, desaturation, ester cleavage, ring expansion, ring formation, aldehyde scission, dehydration, ipso attack, one-electron oxidation, coupling reactions, rearrangement of fatty acid and prostaglandin hydroperoxides, and phospholipase activity. Most of these reactions are rationalized in the context of high-valent iron-oxygen intermediates and Fe(2+) reductions, but others are not and may involve acid-base catalysis. Some of these transformations are involved in the bioactivation and detoxication of xenobiotic chemicals.

  17. Soil chemical properties affect the reaction of forest soil bacteria to drought and rewetting stress.

    Science.gov (United States)

    Chodak, Marcin; Gołębiewski, Marcin; Morawska-Płoskonka, Justyna; Kuduk, Katarzyna; Niklińska, Maria

    Reaction of soil bacteria to drought and rewetting stress may depend on soil chemical properties. The objectives of this study were to test the reaction of different bacterial phyla to drought and rewetting stress and to assess the influence of different soil chemical properties on the reaction of soil bacteria to this kind of stress. The soil samples were taken at ten forest sites and measured for pH and the contents of organic C (Corg) and total N (Nt), Zn, Cu, and Pb. The samples were kept without water addition at 20 - 30 °C for 8 weeks and subsequently rewetted to achieve moisture equal to 50 - 60 % of their maximum water-holding capacity. Prior to the drought period and 24 h after the rewetting, the structure of soil bacterial communities was determined using pyrosequencing of 16S rRNA genes. The drought and rewetting stress altered bacterial community structure. Gram-positive bacterial phyla, Actinobacteria and Firmicutes, increased in relative proportion after the stress, whereas the Gram-negative bacteria in most cases decreased. The largest decrease in relative abundance was for Gammaproteobacteria and Bacteroidetes. For several phyla the reaction to drought and rewetting stress depended on the chemical properties of soils. Soil pH was the most important soil property influencing the reaction of a number of soil bacterial groups (including all classes of Proteobacteria, Bacteroidetes, Acidobacteria, and others) to drought and rewetting stress. For several bacterial phyla the reaction to the stress depended also on the contents of Nt and Corg in soil. The effect of heavy metal pollution was also noticeable, although weaker compared to other chemical soil properties. We conclude that soil chemical properties should be considered when assessing the effect of stressing factors on soil bacterial communities.

  18. Detection of chemical weapon agents and simulants using chemical ionization reaction time-of-flight mass spectrometry.

    Science.gov (United States)

    Cordell, Rebecca L; Willis, Kerry A; Wyche, Kevin P; Blake, Robert S; Ellis, Andrew M; Monks, Paul S

    2007-11-01

    Chemical ionization reaction time-of-flight mass spectrometry (CIR-TOF-MS) has been used for the analysis of prepared mixtures of chemical weapon agents (CWAs) sarin and sulfur mustard. Detection of the CWA simulants 2-chloroethyl ethyl sulfide, triethyl phosphate, and dimethyl methyl phosphonate has also been investigated. Chemical ionization of all the agents and simulants was shown to be possible using the CIR-TOF-MS technique with a variety of reagent ions, and the sensitivity was optimized by variation of instrument parameters. The ionization process was found to be largely unaffected by sample humidity levels, demonstrating the potential suitability of the method to a range of environmental conditions, including the analysis of CWAs in air and in the breath of exposed individuals.

  19. The asymptotic solutions for boundary value problem to a convective diffusion equation with chemical reaction near a cylinder

    OpenAIRE

    Maksimova, N.V.; Akhmetov, R. G.

    2013-01-01

    The work deals with a boundary value problem for a quasilinear partial elliptical equation. The equation describes a stationary process of convective diffusion near a cylinder and takes into account the value of a chemical reaction for large Peclet numbers and for large constant of chemical reaction. The quantity the rate constant of the chemical reaction and Peclet number is assumed to have a constant value. The leading term of the asymptotics of the solution is constructed in the boundary l...

  20. Influence of heat and chemical reactions on the Sisko fluid model for ...

    African Journals Online (AJOL)

    The present article studies the effects of heat and chemical reactions on the blood flow through tapered artery with a stenosis. The model incorporates Sisko fluid representation for the blood flow through an axially non-symmetrical but radially symmetric stenosis. Symmetry of the distribution of the wall shearing stress and ...

  1. Molecular Modeling as a Self-Taught Component of a Conventional Undergraduate Chemical Reaction Engineering Course

    Science.gov (United States)

    Rothe, Erhard W.; Zygmunt, William E.

    2016-01-01

    We inserted a self-taught molecular modeling project into an otherwise conventional undergraduate chemical-reaction-engineering course. Our objectives were that students should (a) learn with minimal instructor intervention, (b) gain an appreciation for the relationship between molecular structure and, first, macroscopic state functions in…

  2. Variable elimination in chemical reaction networks with mass-action kinetics

    DEFF Research Database (Denmark)

    Feliu, Elisenda; Wiuf, C.

    2012-01-01

    We consider chemical reaction networks taken with mass-action kinetics. The steady states of such a system are solutions to a system of polynomial equations. Even for small systems the task of finding the solutions is daunting. We develop an algebraic framework and procedure for linear elimination...

  3. numerical scheme for simulating multicomponent mass transport accompanied by reversible chemical reaction sin porous media

    NARCIS (Netherlands)

    Benes, Nieck Edwin; Verzijl, Richard; Verweij, H.

    1999-01-01

    A numerical scheme is presented for computer simulation of multicomponent gas transport possibly accompanied by reversible chemical reactions in a macroporous medium, based on the dusty gas model. Using analytical solutions for simple systems it is shown that the derivation of the scheme is

  4. Using Drawing Technology to Assess Students' Visualizations of Chemical Reaction Processes

    Science.gov (United States)

    Chang, Hsin-Yi; Quintana, Chris; Krajcik, Joseph

    2014-01-01

    In this study, we investigated how students used a drawing tool to visualize their ideas of chemical reaction processes. We interviewed 30 students using thinking-aloud and retrospective methods and provided them with a drawing tool. We identified four types of connections the students made as they used the tool: drawing on existing knowledge,…

  5. Chemical reaction of hexagonal boron nitride and graphite nanoclusters in mechanical milling systems

    Energy Technology Data Exchange (ETDEWEB)

    Muramatsu, Y.; Grush, M.; Callcott, T.A. [Univ. of Tennessee, Knoxville, TN (United States)] [and others

    1997-04-01

    Synthesis of boron-carbon-nitride (BCN) hybrid alloys has been attempted extensively by many researchers because the BCN alloys are considered an extremely hard material called {open_quotes}super diamond,{close_quotes} and the industrial application for wear-resistant materials is promising. A mechanical alloying (MA) method of hexagonal boron nitride (h-BN) with graphite has recently been studied to explore the industrial synthesis of the BCN alloys. To develop the MA method for the BCN alloy synthesis, it is necessary to confirm the chemical reaction processes in the mechanical milling systems and to identify the reaction products. Therefore, the authors have attempted to confirm the chemical reaction process of the h-BN and graphite in mechanical milling systems using x-ray absorption near edge structure (XANES) methods.

  6. Use of Site-Specifically Tethered Chemical Nucleases to Study Macromolecular Reactions

    Directory of Open Access Journals (Sweden)

    Mukherjee Srabani

    2003-01-01

    Full Text Available During a complex macromolecular reaction multiple changes in molecular conformation and interactions with ligands may occur. X-ray crystallography may provide only a limited set of snapshots of these changes. Solution methods can augment such structural information to provide a more complete picture of a macromolecular reaction. We analyzed the changes in protein conformation and protein:nucleic acid interactions which occur during transcription initiation by using a chemical nuclease tethered to cysteines introduced site-specifically into the RNA polymerase of bacteriophage T7 (T7 RNAP. Changes in cleavage patterns as the polymerase steps through transcription reveal a series of structural transitions which mediate transcription initiation. Cleavage by tethered chemical nucleases is seen to be a powerful method for revealing the conformational dynamics of macromolecular reactions, and has certain advantages over cross-linking or energy transfer approaches.

  7. From simple to complex and backwards. Chemical reactions under very high pressure

    Energy Technology Data Exchange (ETDEWEB)

    Bini, Roberto [Department of Chemistry, University of Florence, Via della Lastruccia 3, 50019 Sesto Fiorentino (Italy); LENS - European Laboratory of Non linear Spectroscopy, University of Florence, Via Nello Carrara 1, 50019 Sesto Fiorentino (Italy); Ceppatelli, Matteo; Citroni, Margherita [LENS - European Laboratory of Non linear Spectroscopy, University of Florence, Via Nello Carrara 1, 50019 Sesto Fiorentino (Italy); Schettino, Vincenzo, E-mail: vincenzo.schettino@unifi.it [LENS - European Laboratory of Non linear Spectroscopy, University of Florence, Via Nello Carrara 1, 50019 Sesto Fiorentino (Italy)

    2012-04-04

    Highlights: Black-Right-Pointing-Pointer High pressure reactivity of several molecular systems. Black-Right-Pointing-Pointer Reaction kinetics and dynamics in high density conditions. Black-Right-Pointing-Pointer Key role of optical pumping and electronic excitation. Black-Right-Pointing-Pointer Perspectives for the synthesis of hydrogen. - Abstract: High pressure chemical reactions of molecular systems are discussed considering the various factors that can affect the reactivity. These include steric hindrance and geometrical constraints in the confined environment of crystals at high pressure, changes of the free energy landscape with pressure, photoactivation by two-photon absorption, local and collective effects. A classification of the chemical reactions at high pressure is attempted on the basis of the prevailing factors.

  8. A study on the improving efficiency for laser-induced chemical reaction process

    Energy Technology Data Exchange (ETDEWEB)

    Song, Kyu Seok; Cha, Hyung Ki; Yang, Ki Ho

    1998-12-01

    The laser-induced photoreaction process is a very useful technology in environmental aspects as well as atomic energy industry. In this study various factors which affect to the reaction process has been investigated for the increment of efficiency of reaction process. Palladium and silver have been chosen as samples for the reaction and the reaction processes have been monitored very carefully. For palladium nitric acid was identified as the best solvent for the reaction, while oxalic acid was the best reducing agent. As the concentration of the reducing agent increases, the reactivity of the samples were increased. When more laser energy was illuminated to the samples, reactivity increased, too. The wavelength of the laser beam used for the reaction was 3rd harmonic of Nd:YAG laser(355 nm). For silver case perchloric acid and ethanol were the best combination for the optimal reaction condition. As a result of the analysis of the reaction products, pure palladium and silver were the products, not any other forms of chemicals. (author). 12 refs., 3 tabs., 26 figs.

  9. Implementation of the chemical PbLi/water reaction in the SIMMER code

    Energy Technology Data Exchange (ETDEWEB)

    Eboli, Marica, E-mail: marica.eboli@for.unipi.it [DICI—University of Pisa, Largo Lucio Lazzarino 2, 56122 Pisa (Italy); Forgione, Nicola [DICI—University of Pisa, Largo Lucio Lazzarino 2, 56122 Pisa (Italy); Del Nevo, Alessandro [ENEA FSN-ING-PAN, CR Brasimone, 40032 Camugnano, BO (Italy)

    2016-11-01

    Highlights: • Updated predictive capabilities of SIMMER-III code. • Verification of the implemented PbLi/Water chemical reactions. • Identification of code capabilities in modelling phenomena relevant to safety. • Validation against BLAST Test No. 5 experimental data successfully completed. • Need for new experimental campaign in support of code validation on LIFUS5/Mod3. - Abstract: The availability of a qualified system code for the deterministic safety analysis of the in-box LOCA postulated accident is of primary importance. Considering the renewed interest for the WCLL breeding blanket, such code shall be multi-phase, shall manage the thermodynamic interaction among the fluids, and shall include the exothermic chemical reaction between lithium-lead and water, generating oxides and hydrogen. The paper presents the implementation of the chemical correlations in SIMMER-III code, the verification of the code model in simple geometries and the first validation activity based on BLAST Test N°5 experimental data.

  10. Required Levels of Catalysis for Emergence of Autocatalytic Sets in Models of Chemical Reaction Systems

    Directory of Open Access Journals (Sweden)

    Wim Hordijk

    2011-05-01

    Full Text Available The formation of a self-sustaining autocatalytic chemical network is a necessary but not sufficient condition for the origin of life. The question of whether such a network could form “by chance” within a sufficiently complex suite of molecules and reactions is one that we have investigated for a simple chemical reaction model based on polymer ligation and cleavage. In this paper, we extend this work in several further directions. In particular, we investigate in more detail the levels of catalysis required for a self-sustaining autocatalytic network to form. We study the size of chemical networks within which we might expect to find such an autocatalytic subset, and we extend the theoretical and computational analyses to models in which catalysis requires template matching.

  11. Dominant Overall Chemical Reaction in a Chlorine Trifluoride Silicon Nitrogen System at Atmospheric Pressure

    Science.gov (United States)

    Habuka, Hitoshi; Otsuka, Toru; Qu, Wei-Feng

    1999-11-01

    This study evaluates the overall chemical reaction in a chlorine trifluoride silicon nitrogen system at atmospheric pressure, based on the observation of the dominant chemical species in the gas phase using a quadrupole mass spectra analyzer coupled with a horizontal cold-wall single-wafer epitaxial reactor. Chlorine trifluoride gas etches the silicon surface, producing two major products, silicon tetrafluoride gas and chlorine gas, at room temperature and 530 K. The production of chlorosilanes was not observed in this study. The results obtained in this study indicate that the dominant overall chemical reaction in a chlorine trifluoride silicon nitrogen system is 3Si + 4ClF3 →3SiF4 ↑+ 2Cl2 ↑.

  12. Balanced Biochemical Reactions: A New Approach to Unify Chemical and Biochemical Thermodynamics

    Science.gov (United States)

    Sabatini, Antonio; Vacca, Alberto; Iotti, Stefano

    2012-01-01

    A novel procedure is presented which, by balancing elements and electric charge of biochemical reactions which occur at constant pH and pMg, allows assessing the thermodynamics properties of reaction ΔrG′0, ΔrH′0, ΔrS′0 and the change in binding of hydrogen and magnesium ions of these reactions. This procedure of general applicability avoids the complex calculations required by the use of the Legendre transformed thermodynamic properties of formation ΔfG′0, ΔfH′0 and ΔfS′0 hitherto considered an obligatory prerequisite to deal with the thermodynamics of biochemical reactions. As a consequence, the term “conditional” is proposed in substitution of “Legendre transformed” to indicate these thermodynamics properties. It is also shown that the thermodynamic potential G is fully adequate to give a criterion of spontaneous chemical change for all biochemical reactions and then that the use of the Legendre transformed G′ is unnecessary. The procedure proposed can be applied to any biochemical reaction, making possible to re-unify the two worlds of chemical and biochemical thermodynamics, which so far have been treated separately. PMID:22247780

  13. Balanced biochemical reactions: a new approach to unify chemical and biochemical thermodynamics.

    Science.gov (United States)

    Sabatini, Antonio; Vacca, Alberto; Iotti, Stefano

    2012-01-01

    A novel procedure is presented which, by balancing elements and electric charge of biochemical reactions which occur at constant pH and pMg, allows assessing the thermodynamics properties of reaction Δ(r)G'⁰, Δ(r)H'⁰, Δ(r)S'⁰ and the change in binding of hydrogen and magnesium ions of these reactions. This procedure of general applicability avoids the complex calculations required by the use of the Legendre transformed thermodynamic properties of formation Δ(f)G'⁰, Δ(f)H'⁰ and Δ(f)S'⁰ hitherto considered an obligatory prerequisite to deal with the thermodynamics of biochemical reactions. As a consequence, the term "conditional" is proposed in substitution of "Legendre transformed" to indicate these thermodynamics properties. It is also shown that the thermodynamic potential G is fully adequate to give a criterion of spontaneous chemical change for all biochemical reactions and then that the use of the Legendre transformed G' is unnecessary. The procedure proposed can be applied to any biochemical reaction, making possible to re-unify the two worlds of chemical and biochemical thermodynamics, which so far have been treated separately.

  14. Study of Horseradish Peroxidase Fixed on Mesoporous Materials as a Chemical Reaction Catalyst

    Science.gov (United States)

    Gao, Mengdan; Dai, Rongji

    2017-12-01

    Nanostructured mesoporous materials is a new type of porous materials, which has been widely used. It has excellent capability in enzymes immobilization, but modification on the chemical bonds of the enzyme reduce the enzymatic activity and rarely used in chemical reactions. The horseradish peroxidase was immobilized on the mesoporous materials with appropriate aperture and its activity and stability was evaluated when catalyzing the nitration reaction of amines and oxidation reaction of thiourea. The optimum mesoporous material to fix the horseradish peroxidase can be obtained by mixing polyoxyethylene - polyoxypropylene-pol, yoxyethylene(P123), 1,3,5-trimethylbenzene(TMB), and tetramethoxysilane (TMOS) at a ratio of 10:1:1, whose surface area and pore volume and pore diameter calculated by BET and BJH model were 402.903m2/g, 1.084cm2/g, 1.084cm2/g respectively. The horseradish peroxidase, immobilized on the mesoporous materials, was applied for catalyzing the nitration reaction of anilines and oxidation reaction of thiourea, produced a high product yield and can be recycled. Thus, it is a strong candidate as a catalysts for oxidation reactions, to be produced at industral scale, due to its high efficiency and low cost.

  15. Balanced biochemical reactions: a new approach to unify chemical and biochemical thermodynamics.

    Directory of Open Access Journals (Sweden)

    Antonio Sabatini

    Full Text Available A novel procedure is presented which, by balancing elements and electric charge of biochemical reactions which occur at constant pH and pMg, allows assessing the thermodynamics properties of reaction Δ(rG'⁰, Δ(rH'⁰, Δ(rS'⁰ and the change in binding of hydrogen and magnesium ions of these reactions. This procedure of general applicability avoids the complex calculations required by the use of the Legendre transformed thermodynamic properties of formation Δ(fG'⁰, Δ(fH'⁰ and Δ(fS'⁰ hitherto considered an obligatory prerequisite to deal with the thermodynamics of biochemical reactions. As a consequence, the term "conditional" is proposed in substitution of "Legendre transformed" to indicate these thermodynamics properties. It is also shown that the thermodynamic potential G is fully adequate to give a criterion of spontaneous chemical change for all biochemical reactions and then that the use of the Legendre transformed G' is unnecessary. The procedure proposed can be applied to any biochemical reaction, making possible to re-unify the two worlds of chemical and biochemical thermodynamics, which so far have been treated separately.

  16. Évaluation de l'incidence des programmes de transferts en espèces ...

    International Development Research Centre (IDRC) Digital Library (Canada)

    autonomisation des femmes en Tanzanie. Ce projet examinera la façon dont les transferts ... L'emploi dans le secteur non structuré au service de la croissance partagée en Afrique de l'Est et en Afrique australe. Le fait de comprendre pourquoi les ...

  17. Transferts intergénérationnels, vieillissement de la population et ...

    International Development Research Centre (IDRC) Digital Library (Canada)

    Les chercheurs adopteront une nouvelle approche globale, la méthodologie des comptes de transferts nationaux (National Transfer Accounts, NTA), afin de mesurer l'ensemble des flux économiques au fil du temps. Un des principaux avantages de cette méthode réside dans la prise en compte, dans ses estimations, des ...

  18. Computational organic chemistry: bridging theory and experiment in establishing the mechanisms of chemical reactions.

    Science.gov (United States)

    Cheng, Gui-Juan; Zhang, Xinhao; Chung, Lung Wa; Xu, Liping; Wu, Yun-Dong

    2015-02-11

    Understanding the mechanisms of chemical reactions, especially catalysis, has been an important and active area of computational organic chemistry, and close collaborations between experimentalists and theorists represent a growing trend. This Perspective provides examples of such productive collaborations. The understanding of various reaction mechanisms and the insight gained from these studies are emphasized. The applications of various experimental techniques in elucidation of reaction details as well as the development of various computational techniques to meet the demand of emerging synthetic methods, e.g., C-H activation, organocatalysis, and single electron transfer, are presented along with some conventional developments of mechanistic aspects. Examples of applications are selected to demonstrate the advantages and limitations of these techniques. Some challenges in the mechanistic studies and predictions of reactions are also analyzed.

  19. Fisher Information Study in Position and Momentum Spaces for Elementary Chemical Reactions.

    Science.gov (United States)

    López-Rosa, Sheila; Esquivel, Rodolfo O; Angulo, Juan Carlos; Antolín, Juan; Dehesa, Jesús S; Flores-Gallegos, Nelson

    2010-01-12

    The utility of the Fisher information measure is analyzed to detect the transition state, the stationary points of a chemical reaction, and the bond breaking/forming regions of elementary reactions such as the simplest hydrogen abstraction and the identity SN2 exchange ones. This is performed by following the intrinsic reaction path calculated at the MP2 and QCISD(T) levels of theory with a 6-311++G(3df, 2p) basis set. Selected descriptors of both position and momentum space densities are utilized to support the observations, such as the molecular electrostatic potential (MEP), the hardness, the dipole moment, along with geometrical parameters. Our results support the concept of a continuum of transient of Zewail and Polanyi for the transition state rather than a single state, which is also in agreement with reaction force analyses.

  20. Middle atmosphere heating by exothermic chemical reactions involving odd-hydrogen species

    Science.gov (United States)

    Mlynczak, Martin G.; Solomon, Susan

    1991-01-01

    The rate of heating which occurs in the middle atmosphere due to four exothermic reactions involving members of the odd-hydrogen family is calculated. The following reactions are considered: O + OH yields O2 + H; H + O2 + M yields HO2 + M; H + O3 yields OH + O2; and O + HO2 yields OH + O2. It is shown that the heating rates due to these reactions rival the oxygen-related heating rates conventionally considered in middle-atmosphere models. The conversion of chemical potential energy into molecular translational energy (heat) by these odd-hydrogen reactions is shown to be a significant energy source in the middle atmosphere that has not been previously considered.

  1. Effect of mesoscopic conservative phenomena in the dynamics of chemical reactions at the macroscopic scale

    Science.gov (United States)

    Zárate-Navarro, Marco A.; García-Sandoval, J. Paulo; Dochain, Denis; Hudon, Nicolas

    2017-11-01

    This paper studies the influence of conservative phenomena at the mesoscopic scale that affect the behavior of macroscopic variables in chemical reactions, generally understood as purely dissipative processes and whose mathematical formulation is usually derived using macroscopic variables. It is shown that conservative phenomena at the mesoscopic scale can affect the entropy production by transiently ;pulling away; the system from the thermodynamic equilibrium. Two case studies are presented to illustrate this fact: the first one is an isolated system with a single reaction including two different scenarios, a purely dissipative reaction; and a second one that considers the influence of conservative elements at the mesoscopic scale. The second case generalizes the results to multiple reactions.

  2. Minimally invasive thermotherapy method for tumor treatment based on an exothermic chemical reaction.

    Science.gov (United States)

    Deng, Zhong-Shan; Liu, Jing

    2007-01-01

    In tumor thermotherapy treatment, it is very difficult to achieve the objective of exactly killing the tumor while minimizing the injury of healthy tissues or organs surrounding the tumor. In this study, we describe a new minimally invasive thermotherapy protocol for tumor treatment using heat released from an exothermic chemical reaction, which can safely deliver a totally localized and uniform heating to exactly kill the tumor. Both in vitro and in vivo experiments were performed to test the feasibility of this thermotherapy method based on an exothermic chemical reaction. After injection of only a small amount of matched reactants into the target tissue by medical syringes, an exothermic reaction takes place, and then releases tremendous heat to elevate the temperature to its thermally lethal value. Compared with most of the currently existing thermotherapy strategies, this heating is highly localized, completely safe and uniform, which will remarkably reduce the thermal damage and mechanical trauma to the surrounding healthy tissues. This study opens the clinical possibilities for tumors to be treated in a minimally invasive way by a thermotherapy treatment based on an exothermic chemical reaction.

  3. Tutorial Review: Simulation of Oscillating Chemical Reactions Using Microsoft Excel Macros

    Directory of Open Access Journals (Sweden)

    Abdolhossein Naseri

    2016-12-01

    Full Text Available Oscillating reactions are one of the most interesting topics in chemistry and analytical chemistry. Fluctuations in concentrations of one the reacting species (usually a reaction intermediate create an oscillating chemical reaction. In oscillating systems, the reaction is far from thermodynamic equilibrium. In these systems, at least one autocatalytic step is required. Developing an instinctive feeling for how oscillating reactions work will be invaluable to future generations of chemists. Some software programs have been released for simulating oscillating systems; however, the algorithm details of such software are not transparent to chemists. In contrast, function of spreadsheet tools, like Microsoft Excel, is well understood, and the software is nearly universally available. In this work, the simulation and visualization of different oscillating systems are performed using Microsoft excel. The simple repetitive solving of the ordinary differential equation of an autocatalytic reaction (a spreadsheet row followed by time, easily automated by a subroutine (a “Macro” in Excel, readily simulates an oscillating reaction. This permits the simulation of some oscillating systems such asBelousov-Zhabotinsky. The versatility of an easily understandable computational platform further enables the simulation of the effects of linear and nonlinear parameters such as concentrations of reactants and catalyst, and kinetic constants. These parameters are readily changed to examine their effects.

  4. Unsteady Bioconvection Squeezing Flow in a Horizontal Channel with Chemical Reaction and Magnetic Field Effects

    Directory of Open Access Journals (Sweden)

    Qingkai Zhao

    2017-01-01

    Full Text Available The time-dependent mixed bioconvection flow of an electrically conducting fluid between two infinite parallel plates in the presence of a magnetic field and a first-order chemical reaction is investigated. The fully coupled nonlinear systems describing the total mass, momentum, thermal energy, mass diffusion, and microorganisms equations are reduced to a set of ordinary differential equations via a set of new similarity transformations. The detailed analysis illustrating the influences of various physical parameters such as the magnetic, squeezing, and chemical reaction parameters and the Schmidt and Prandtl numbers on the distributions of temperature and microorganisms as well as the skin friction and the Nusselt number is presented. The conclusion is drawn that the flow field, temperature, and chemical reaction profiles are significantly influenced by magnetic parameter, heat generation/absorption parameter, and chemical parameter. Some examples of potential applications of such bioconvection could be found in pharmaceutical industry, microfluidic devices, microbial enhanced oil recovery, modeling oil, and gas-bearing sedimentary basins.

  5. Solar photo-thermal catalytic reactions to produce high value chemicals

    Energy Technology Data Exchange (ETDEWEB)

    Prengle, Jr, H W; Wentworth, W E [Houston Univ., TX (United States)

    1992-04-01

    This report presents a summary of the research work accomplished to date on the utilization of solar photo-thermal energy to convert low cost chemical feedstocks into high $-value chemical products. The rationale is that the solar IR-VIS-UV spectrum is unique, supplying endothermic reaction energy as well as VIS-UV for photochemical activation. Chemical market analysis and product price distribution focused attention on speciality chemicals with prices >$1.00/lb, and a synthesis sequence of n-paraffins to aromatics to partial oxidized products. The experimental work has demonstrated that enhanced reaction effects result from VIS-UV irradiation of catalytically active V2O5/SiO2. Experiments of the past year have been on dehydrogenation and dehydrocyclization of n-paraffins to olefins and aromatics with preference for the latter. Recent results using n-hexane produced 95% conversion with 56% benzene; it is speculated that aromatic yield should reach {approximately}70% by further optimization. Pilot- and commercial-scale reactor configurations have been examined; the odds-on-favorite being a shallow fluid-bed of catalyst with incident radiation from the top. Sequencing for maximum cost effectiveness would be day-time endothermic followed by night-time exothermic reactions to produce the products.

  6. Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions

    Science.gov (United States)

    Parlett, Christopher M. A.; Isaacs, Mark A.; Beaumont, Simon K.; Bingham, Laura M.; Hondow, Nicole S.; Wilson, Karen; Lee, Adam F.

    2016-02-01

    The chemical functionality within porous architectures dictates their performance as heterogeneous catalysts; however, synthetic routes to control the spatial distribution of individual functions within porous solids are limited. Here we report the fabrication of spatially orthogonal bifunctional porous catalysts, through the stepwise template removal and chemical functionalization of an interconnected silica framework. Selective removal of polystyrene nanosphere templates from a lyotropic liquid crystal-templated silica sol-gel matrix, followed by extraction of the liquid crystal template, affords a hierarchical macroporous-mesoporous architecture. Decoupling of the individual template extractions allows independent functionalization of macropore and mesopore networks on the basis of chemical and/or size specificity. Spatial compartmentalization of, and directed molecular transport between, chemical functionalities affords control over the reaction sequence in catalytic cascades; herein illustrated by the Pd/Pt-catalysed oxidation of cinnamyl alcohol to cinnamic acid. We anticipate that our methodology will prompt further design of multifunctional materials comprising spatially compartmentalized functions.

  7. Chemical reactions of organic molecules adsorbed on ice 1. Chlorine addition to propene

    Energy Technology Data Exchange (ETDEWEB)

    Graham, J.D.; Roberts, J.T.

    2000-02-10

    Chemical reactions that are promoted or catalyzed by the surface or near surface regions of ice particles in type II polar stratospheric clouds (PSCs) have been shown to play a role in the annual sequence of events that ultimately opens the Antarctic ozone hole. A new ice-catalyzed chemical reaction is reported, namely the addition of Cl{sub 2} to the C--C double bond of propene (C{sub 3}H{sub 6}) to form 1,2-dichloropropane. The reaction, which was investigated with temperature-programmed desorption mass spectrometry (TPD), was carried out on ultrathin (10--100 monolayer thick) films of ice deposited on single-crystal metal substrates under ultrahigh vacuum. The Cl{sub 2}-addition product was identified as 1,2-dichloropropane on the basis of its fragmentation pattern in the mass spectrometer. 1,2-Dichloropropane formation occurs below 150 K, and no chlorohydrin (e.g., 2-chloro-1-propanol) evolution is ever observed. The reaction of coadsorbed propene and chlorine is very different from what occurs in aqueous solutions, where chlorohydrin formation occurs readily. Possible mechanisms of the ice-surface-catalyzed reaction are discussed.

  8. Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

  9. Fat versus Thin Threading Approach on GPUs: Application to Stochastic Simulation of Chemical Reactions

    KAUST Repository

    Klingbeil, Guido

    2012-02-01

    We explore two different threading approaches on a graphics processing unit (GPU) exploiting two different characteristics of the current GPU architecture. The fat thread approach tries to minimize data access time by relying on shared memory and registers potentially sacrificing parallelism. The thin thread approach maximizes parallelism and tries to hide access latencies. We apply these two approaches to the parallel stochastic simulation of chemical reaction systems using the stochastic simulation algorithm (SSA) by Gillespie [14]. In these cases, the proposed thin thread approach shows comparable performance while eliminating the limitation of the reaction system\\'s size. © 2006 IEEE.

  10. The use of the dusty-gas model for the description of mass transport with chemical reaction in porous media

    NARCIS (Netherlands)

    Veldsink, J.W.; Veldsink, J.W.; van Damme, Rudolf M.J.; Versteeg, Geert; van Swaaij, Willibrordus Petrus Maria

    1995-01-01

    In the present study, mass transport accompanied by chemical reactions in porous media is studied according to the Fick model and the dusty-gas model. For mass transport accompanied by a chemical reaction in catalyst structures showing a plane, line, or point of symmetry, the approximate analytical

  11. Ab initio studies of equations of state and chemical reactions of reactive structural materials

    Science.gov (United States)

    Zaharieva, Roussislava

    The motivations for the research issues addressed in this thesis are based on the needs of the aerospace structural analysis and the design community. The specific focus is related to the characterization and shock induced chemical reactions of multi-functional structural-energetic materials that are also known as the reactive structural materials and their reaction capabilities. Usually motivation for selection of aerospace structural materials is to realize required strength characteristics and favorable strength to weight ratios. The term strength implies resistance to loads experienced during the service life of the structure, including resistance to fatigue loads, corrosion and other extreme conditions. Thus, basically the structural materials are single function materials that resist loads experienced during the service life of the structure. However, it is desirable to select materials that are capable of offering more than one basic function of strength. Very often, the second function is the capability to provide functions of sensing and actuation. In this thesis, the second function is different. The second function is the energetic characteristics. Thus, the choice of dual functions of the material are the structural characteristics and energetic characteristics. These materials are also known by other names such as the reactive material structures or dual functional structural energetic materials. Specifically the selected reactive materials include mixtures of selected metals and metal oxides that are also known as thermite mixtures, reacting intermetallic combinations and oxidizing materials. There are several techniques that are available to synthesize these structural energetic materials or reactive material structures and new synthesis techniques constitute an open research area. The focus of this thesis, however, is the characterization of chemical reactions of reactive material structures that involve two or more solids (or condensed matter). The

  12. SCRIPDB: a portal for easy access to syntheses, chemicals and reactions in patents

    Science.gov (United States)

    Heifets, Abraham; Jurisica, Igor

    2012-01-01

    The patent literature is a rich catalog of biologically relevant chemicals; many public and commercial molecular databases contain the structures disclosed in patent claims. However, patents are an equally rich source of metadata about bioactive molecules, including mechanism of action, disease class, homologous experimental series, structural alternatives, or the synthetic pathways used to produce molecules of interest. Unfortunately, this metadata is discarded when chemical structures are deposited separately in databases. SCRIPDB is a chemical structure database designed to make this metadata accessible. SCRIPDB provides the full original patent text, reactions and relationships described within any individual patent, in addition to the molecular files common to structural databases. We discuss how such information is valuable in medical text mining, chemical image analysis, reaction extraction and in silico pharmaceutical lead optimization. SCRIPDB may be searched by exact chemical structure, substructure or molecular similarity and the results may be restricted to patents describing synthetic routes. SCRIPDB is available at http://dcv.uhnres.utoronto.ca/SCRIPDB. PMID:22067445

  13. An overview of chemical processes that damage cellular DNA: spontaneous hydrolysis, alkylation, and reactions with radicals.

    Science.gov (United States)

    Gates, Kent S

    2009-11-01

    The sequence of heterocyclic bases on the interior of the DNA double helix constitutes the genetic code that drives the operation of all living organisms. With this said, it is not surprising that chemical modification of cellular DNA can have profound biological consequences. Therefore, the organic chemistry of DNA damage is fundamentally important to diverse fields including medicinal chemistry, toxicology, and biotechnology. This review is designed to provide a brief overview of the common types of chemical reactions that lead to DNA damage under physiological conditions.

  14. Chemical Characterization of Secondary Organic Aerosol Formed from Atmospheric Aqueous-phase Reactions of Phenolic Compounds

    Science.gov (United States)

    Yu, L.; Smith, J.; Anastasio, C.; Zhang, Q.

    2012-12-01

    Phenolic compounds, which are released in significant amounts from biomass burning, may undergo fast aqueous-phase reactions to form secondary organic aerosol (SOA) in the atmosphere. Understanding the aqueous-phase reaction mechanisms of these compounds and the composition of their reaction products is thus important for constraining SOA sources and predicting organic aerosol properties in models. In this study, we investigate the aqueous-phase reactions of three phenols (phenol, guaiacol and syringol) with two oxidants - excited triplet states (3C*) of non-phenolic aromatic carbonyls and hydroxyl radical (OH). By employing four analytical methods including high-resolution aerosol mass spectrometry, total organic carbon analysis, ion chromatography, and liquid chromatography-mass spectrometry, we thoroughly characterize the chemical compositions of the low volatility reaction products of phenols and propose formation mechanisms based on this information. Our results indicate that phenolic SOA is highly oxygenated, with O/C ratios in the range of 0.83-1.03, and that the SOA of phenol is usually more oxidized than those of guaiacol and syringol. Among the three precursors, syringol generates the largest fraction of higher molecular weight (MW) products. For the same precursor, the SOA formed via reaction with 3C* is less oxidized than that formed via reaction with OH. In addition, oxidation by 3C* enhances the formation of higher MW species, including phenolic dimers, higher oligomers and hydroxylated products, compared to reactions initiated by OH, which appear to favor the formation of organic acids. However, our results indicate that the yields of small organic acids (e.g., formate, acetate, oxalate, and malate) are low for both reaction pathways, together accounting for less than 5% of total SOA mass.

  15. Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

    Science.gov (United States)

    Liechty, Derek S.; Lewis, Mark J.

    2010-01-01

    Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

  16. Artificial chemical reaction optimization of neural networks for efficient prediction of stock market indices

    Directory of Open Access Journals (Sweden)

    S.C. Nayak

    2017-09-01

    Full Text Available The underlying system models of time series prediction are complex and not known a priori, hence, accurate and unbiased estimation cannot be always achieved using well known linear techniques. The estimation process requires more advanced prediction algorithms, such as multilayer perceptrons (MLPs. This paper presents an artificial chemical reaction neural network (ACRNN, which uses artificial chemical reaction optimization (ACRO to train the MLP models for forecasting the stock market indices. The underlying motivation for using ACRO is the ability to overcome the issues of convergence, parameter setting and overfitting and to accurately forecast financial time series data even when the underlying system processes are typically nonlinear. Historical data of seven different stock indices have been collected for 15 years to test the performance of the ACRNN approach. After extensive experimentation, it is observed that the ACRNN technique demonstrates significant improvements in prediction accuracy over the MLP approach.

  17. Topology vs. thermodynamics in chemical reactions: the instability of PH5.

    Science.gov (United States)

    Tantardini, Christian; Benassi, Enrico

    2017-10-18

    The topological approach, based on Bader theory, is compared to the common thermodynamical methodology to study chemical reactivity. It is shown how the former indeed has numerous advantages and provides a more detailed description with respect to the latter about the course of the reaction. The comparison between the two approaches is performed by considering a classical reaction, i.e. the decomposition of PX5 (X = H, F). The topological investigation was supported by using different state-of-the-art topological tools, such as the source function, Espinosa indexes, delocalisation indexes, and domain-averaged Fermi hole analysis. Furthermore, in this work a new topological descriptor, the Bader energy density, PBADER, is introduced and applied to the study case. For the first time since Bader theory was introduced, the distribution of atomic energies in the atomic basins was analysed in detail and used to explain the chemical reactivity a priori.

  18. Expansion of chemical space for natural products by uncommon P450 reactions.

    Science.gov (United States)

    Zhang, Xingwang; Li, Shengying

    2017-08-30

    Covering: 2000 to 2017Cytochrome P450 enzymes (P450s) are the most versatile biocatalysts in nature. The catalytic competence of these extraordinary hemoproteins is broadly harnessed by numerous chemical defenders such as bacteria, fungi, and plants for the generation of diverse and complex natural products. Rather than the common tailoring reactions (e.g. hydroxylation and epoxidation) mediated by the majority of biosynthetic P450s, in this review, we will focus on the unusual P450 enzymes in relation to new chemistry, skeleton construction, and structure re-shaping via their own unique catalytic power or the intriguing protein-protein interactions between P450s and other proteins. These uncommon P450 reactions lead to a higher level of chemical space expansion for natural products, through which a broader spectrum of bioactivities can be gained by the host organisms.

  19. Free convection in MHD micropolar fluid with radiation and chemical reaction effects

    Directory of Open Access Journals (Sweden)

    Srinivasacharya D.

    2014-01-01

    Full Text Available In this paper, the effects of radiation and first order chemical reaction on free convection heat and mass transfer in a micropolar fluid is considered. A uniform magnetic field is applied normal to the plate. The plate is maintained with variable surface heat and mass fluxes. The governing nonlinear partial differential equations are transformed into a system of coupled nonlinear ordinary differential equations using similarity transformations and then solved numerically using the Keller-box method. The numerical results are compared and found to be in good agreement with previously published results as special cases of the present investigation. The dimensionless velocity, microrotation, temperature, concentration and heat and mass transfer rates are presented graphically for various values of coupling number, magnetic parameter, radiation parameter, chemical reaction parameter. The numerical values of the skin friction and wall couple stress for different values of governing parameters are also tabulated.

  20. Radiation and chemical reaction effects on isothermal vertical oscillating plate with variable mass diffusion

    Directory of Open Access Journals (Sweden)

    Manivannan Kaliappan

    2009-01-01

    Full Text Available The unsteady flow of a viscous incompressible flow past an infinite isothermal vertical oscillating plate, in the presence of thermal radiation and homogeneous chemical reaction of first order has been studied. The fluid considered here is a gray, absorbing-emitting radiation but a non-scattering medium. The plate temperature is raised to Tw and the concentration level near the plate is raised linearly with respect to time. An exact solution to the dimensionless governing equations has been obtained by the Laplace transform method, when the plate is oscillating harmonically in its own plane. The effects of velocity, temperature, and concentration are studied for different physical parameters like phase angle, radiation parameter, chemical reaction parameter, Schmidt number, thermal Grashof number, mass Grashof number, and time are studied graphically. It is observed that the velocity increases with decreasing phase angle wt.

  1. MASS TRANSFER EFFECTS ON ACCELERATED VERTICAL PLATE IN A ROTATING FLUID WITH FIRST ORDER CHEMICAL REACTION

    Directory of Open Access Journals (Sweden)

    R. Muthucumaraswamy

    2012-12-01

    Full Text Available The precise analysis of the rotation effects on the unsteady flow of an incompressible fluid past a uniformly accelerated infinite vertical plate with variable temperature and mass diffusion has been undertaken, in the presence of a homogeneous first order chemical reaction. The dimensionless governing equations are solved using the Laplace-transform technique. The plate temperature as well as the concentration near the plate increase linearly with time. The velocity profiles, temperature and concentration are studied for different physical parameters, like the chemical reaction parameter, thermal Grashof number, mass Grashof number, Schmidt number, Prandtl number and time. It is observed that the velocity increases with increasing values of thermal Grashof number or mass Grashof number. It is also observed that the velocity increases with decreasing rotation parameter Ω.

  2. A Gibbs Energy Minimization Approach for Modeling of Chemical Reactions in a Basic Oxygen Furnace

    Science.gov (United States)

    Kruskopf, Ari; Visuri, Ville-Valtteri

    2017-12-01

    In modern steelmaking, the decarburization of hot metal is converted into steel primarily in converter processes, such as the basic oxygen furnace. The objective of this work was to develop a new mathematical model for top blown steel converter, which accounts for the complex reaction equilibria in the impact zone, also known as the hot spot, as well as the associated mass and heat transport. An in-house computer code of the model has been developed in Matlab. The main assumption of the model is that all reactions take place in a specified reaction zone. The mass transfer between the reaction volume, bulk slag, and metal determine the reaction rates for the species. The thermodynamic equilibrium is calculated using the partitioning of Gibbs energy (PGE) method. The activity model for the liquid metal is the unified interaction parameter model and for the liquid slag the modified quasichemical model (MQM). The MQM was validated by calculating iso-activity lines for the liquid slag components. The PGE method together with the MQM was validated by calculating liquidus lines for solid components. The results were compared with measurements from literature. The full chemical reaction model was validated by comparing the metal and slag compositions to measurements from industrial scale converter. The predictions were found to be in good agreement with the measured values. Furthermore, the accuracy of the model was found to compare favorably with the models proposed in the literature. The real-time capability of the proposed model was confirmed in test calculations.

  3. Modeling of Sheath Ion-Molecule Reactions in Plasma Enhanced Chemical Vapor Deposition of Carbon Nanotubes

    Science.gov (United States)

    Hash, David B.; Govindan, T. R.; Meyyappan, M.

    2004-01-01

    In many plasma simulations, ion-molecule reactions are modeled using ion energy independent reaction rate coefficients that are taken from low temperature selected-ion flow tube experiments. Only exothermic or nearly thermoneutral reactions are considered. This is appropriate for plasma applications such as high-density plasma sources in which sheaths are collisionless and ion temperatures 111 the bulk p!asma do not deviate significantly from the gas temperature. However, for applications at high pressure and large sheath voltages, this assumption does not hold as the sheaths are collisional and ions gain significant energy in the sheaths from Joule heating. Ion temperatures and thus reaction rates vary significantly across the discharge, and endothermic reactions become important in the sheaths. One such application is plasma enhanced chemical vapor deposition of carbon nanotubes in which dc discharges are struck at pressures between 1-20 Torr with applied voltages in the range of 500-700 V. The present work investigates The importance of the inclusion of ion energy dependent ion-molecule reaction rates and the role of collision induced dissociation in generating radicals from the feedstock used in carbon nanotube growth.

  4. A Gibbs Energy Minimization Approach for Modeling of Chemical Reactions in a Basic Oxygen Furnace

    Science.gov (United States)

    Kruskopf, Ari; Visuri, Ville-Valtteri

    2017-08-01

    In modern steelmaking, the decarburization of hot metal is converted into steel primarily in converter processes, such as the basic oxygen furnace. The objective of this work was to develop a new mathematical model for top blown steel converter, which accounts for the complex reaction equilibria in the impact zone, also known as the hot spot, as well as the associated mass and heat transport. An in-house computer code of the model has been developed in Matlab. The main assumption of the model is that all reactions take place in a specified reaction zone. The mass transfer between the reaction volume, bulk slag, and metal determine the reaction rates for the species. The thermodynamic equilibrium is calculated using the partitioning of Gibbs energy (PGE) method. The activity model for the liquid metal is the unified interaction parameter model and for the liquid slag the modified quasichemical model (MQM). The MQM was validated by calculating iso-activity lines for the liquid slag components. The PGE method together with the MQM was validated by calculating liquidus lines for solid components. The results were compared with measurements from literature. The full chemical reaction model was validated by comparing the metal and slag compositions to measurements from industrial scale converter. The predictions were found to be in good agreement with the measured values. Furthermore, the accuracy of the model was found to compare favorably with the models proposed in the literature. The real-time capability of the proposed model was confirmed in test calculations.

  5. Studying Equilibrium in the Chemical Reaction between Ferric and Iodide Ions in Solution Using a Simple and Inexpensive Approach

    Science.gov (United States)

    Nikolaychuk, Pavel Anatolyevich; Kuvaeva, Alyona Olegovna

    2016-01-01

    A laboratory experiment on the study of the chemical equilibrium based on the reaction between ferric and iodide ions in solution with the formation of ferrous ions, free iodine, and triiodide ions is developed. The total concentration of iodide and triiodide ions in the reaction mixture during the reaction is determined by the argentometric…

  6. A Microscale Approach to Chemical Kinetics in the General Chemistry Laboratory: The Potassium Iodide Hydrogen Peroxide Iodine-Clock Reaction

    Science.gov (United States)

    Sattsangi, Prem D.

    2011-01-01

    A microscale laboratory for teaching chemical kinetics utilizing the iodine clock reaction is described. Plastic pipets, 3 mL volume, are used to store and deliver precise drops of reagents and the reaction is run in a 24 well plastic tray using a total 60 drops of reagents. With this procedure, students determine the rate of reaction and the…

  7. A stronger necessary condition for the multistationarity of chemical reaction networks

    OpenAIRE

    Soliman, Sylvain

    2013-01-01

    International audience; Biochemical reaction networks grow bigger and bigger, fed by the high-throughput data provided by biologists and bred in open repositories of models allowing merging and evolution. Nevertheless, since the available data is still very far from permitting the identification of the increasing number of kinetic parameters of such models, the necessity of structural analyses for describing the dynamics of chemical networks appears stronger every day. Using the structural in...

  8. Unraveling the Reaction Mechanism of Industrial Processes in Zeolite Catalysis: a Quantum Chemical Approach

    OpenAIRE

    Lesthaeghe, David

    2007-01-01

    Even though acidic zeolites form a crucial catalyst for many petrochemical processes, much of their fundamental reactive behavior is only superficially understood. Most often, catalysts are proposed on an 'ad hoc' basis, without a detailed understanding of their functioning on an atomic scale. It can indeed be difficult to identify the elementary steps of complex reaction networks from a purely experimental basis. For these issues, quantum chemical molecular modeling techniques provide an exc...

  9. Supramolecular Systems and Chemical Reactions in Single-Molecule Break Junctions.

    Science.gov (United States)

    Li, Xiaohui; Hu, Duan; Tan, Zhibing; Bai, Jie; Xiao, Zongyuan; Yang, Yang; Shi, Jia; Hong, Wenjing

    2017-04-01

    The major challenges of molecular electronics are the understanding and manipulation of the electron transport through the single-molecule junction. With the single-molecule break junction techniques, including scanning tunneling microscope break junction technique and mechanically controllable break junction technique, the charge transport through various single-molecule and supramolecular junctions has been studied during the dynamic fabrication and continuous characterization of molecular junctions. This review starts from the charge transport characterization of supramolecular junctions through a variety of noncovalent interactions, such as hydrogen bond, π-π interaction, and electrostatic force. We further review the recent progress in constructing highly conductive molecular junctions via chemical reactions, the response of molecular junctions to external stimuli, as well as the application of break junction techniques in controlling and monitoring chemical reactions in situ. We suggest that beyond the measurement of single molecular conductance, the single-molecule break junction techniques provide a promising access to study molecular assembly and chemical reactions at the single-molecule scale.

  10. Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction.

    Science.gov (United States)

    Zhu, Hongying; Huang, Guangming

    2015-03-31

    In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m(-3), ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. A computational approach to extinction events in chemical reaction networks with discrete state spaces.

    Science.gov (United States)

    Johnston, Matthew D

    2017-12-01

    Recent work of Johnston et al. has produced sufficient conditions on the structure of a chemical reaction network which guarantee that the corresponding discrete state space system exhibits an extinction event. The conditions consist of a series of systems of equalities and inequalities on the edges of a modified reaction network called a domination-expanded reaction network. In this paper, we present a computational implementation of these conditions written in Python and apply the program on examples drawn from the biochemical literature. We also run the program on 458 models from the European Bioinformatics Institute's BioModels Database and report our results. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. General method and thermodynamic tables for computation of equilibrium composition and temperature of chemical reactions

    Science.gov (United States)

    Huff, Vearl N; Gordon, Sanford; Morrell, Virginia E

    1951-01-01

    A rapidly convergent successive approximation process is described that simultaneously determines both composition and temperature resulting from a chemical reaction. This method is suitable for use with any set of reactants over the complete range of mixture ratios as long as the products of reaction are ideal gases. An approximate treatment of limited amounts of liquids and solids is also included. This method is particularly suited to problems having a large number of products of reaction and to problems that require determination of such properties as specific heat or velocity of sound of a dissociating mixture. The method presented is applicable to a wide variety of problems that include (1) combustion at constant pressure or volume; and (2) isentropic expansion to an assigned pressure, temperature, or Mach number. Tables of thermodynamic functions needed with this method are included for 42 substances for convenience in numerical computations.

  13. Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Hongying; Huang, Guangming, E-mail: gmhuang@ustc.edu.cn

    2015-03-31

    Graphical abstract: Direct and humidity independent mass spectrometry analysis of gas phase chemicals could be achieved via ambient proton transfer ionization, ion intensity was found to be stable with humidity ranged from ∼10% to ∼100%. - Highlights: • A humidity independent mass spectrometric method for gas phase samples analysis. • A universal and good sensitivity method. • The method can real time identify plant released raw chemicals. - Abstract: In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m{sup −3}, ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages.

  14. A DAG Scheduling Scheme on Heterogeneous Computing Systems Using Tuple-Based Chemical Reaction Optimization

    Science.gov (United States)

    Jiang, Yuyi; Shao, Zhiqing; Guo, Yi

    2014-01-01

    A complex computing problem can be solved efficiently on a system with multiple computing nodes by dividing its implementation code into several parallel processing modules or tasks that can be formulated as directed acyclic graph (DAG) problems. The DAG jobs may be mapped to and scheduled on the computing nodes to minimize the total execution time. Searching an optimal DAG scheduling solution is considered to be NP-complete. This paper proposed a tuple molecular structure-based chemical reaction optimization (TMSCRO) method for DAG scheduling on heterogeneous computing systems, based on a very recently proposed metaheuristic method, chemical reaction optimization (CRO). Comparing with other CRO-based algorithms for DAG scheduling, the design of tuple reaction molecular structure and four elementary reaction operators of TMSCRO is more reasonable. TMSCRO also applies the concept of constrained critical paths (CCPs), constrained-critical-path directed acyclic graph (CCPDAG) and super molecule for accelerating convergence. In this paper, we have also conducted simulation experiments to verify the effectiveness and efficiency of TMSCRO upon a large set of randomly generated graphs and the graphs for real world problems. PMID:25143977

  15. Probing the bioactivity-relevant chemical space of robust reactions and common molecular building blocks.

    Science.gov (United States)

    Hartenfeller, Markus; Eberle, Martin; Meier, Peter; Nieto-Oberhuber, Cristina; Altmann, Karl-Heinz; Schneider, Gisbert; Jacoby, Edgar; Renner, Steffen

    2012-05-25

    In the search for new bioactive compounds, there is a trend toward increasingly complex compound libraries aiming to target the demanding targets of the future. In contrast, medicinal chemistry and traditional library design rely mainly on a small set of highly established and robust reactions. Here, we probe a set of 58 such reactions for their ability to sample the chemical space of known bioactive molecules, and the potential to create new scaffolds. Combined with ~26,000 common available building blocks, the reactions retrieve around 9% of a scaffold-diverse set of compounds active on human target proteins covering all major pharmaceutical target classes. Almost 80% of generated scaffolds from virtual one-step synthesis products are not present in a large set of known bioactive molecules for human targets, indicating potential for new discoveries. The results suggest that established synthesis resources are well suited to cover the known bioactivity-relevant chemical space and that there are plenty of unexplored regions accessible by these reactions, possibly providing valuable "low-hanging fruit" for hit discovery.

  16. Spatial Heterogeneity and Imperfect Mixing in Chemical Reactions: Visualization of Density-Driven Pattern Formation

    Directory of Open Access Journals (Sweden)

    Sabrina G. Sobel

    2009-01-01

    Full Text Available Imperfect mixing is a concern in industrial processes, everyday processes (mixing paint, bread machines, and in understanding salt water-fresh water mixing in ecosystems. The effects of imperfect mixing become evident in the unstirred ferroin-catalyzed Belousov-Zhabotinsky reaction, the prototype for chemical pattern formation. Over time, waves of oxidation (high ferriin concentration, blue propagate into a background of low ferriin concentration (red; their structure reflects in part the history of mixing in the reaction vessel. However, it may be difficult to separate mixing effects from reaction effects. We describe a simpler model system for visualizing density-driven pattern formation in an essentially unmixed chemical system: the reaction of pale yellow Fe3+ with colorless SCN− to form the blood-red Fe(SCN2+ complex ion in aqueous solution. Careful addition of one drop of Fe(NO33 to KSCN yields striped patterns after several minutes. The patterns appear reminiscent of Rayleigh-Taylor instabilities and convection rolls, arguing that pattern formation is caused by density-driven mixing.

  17. Flow-field development during finger splitting at an exothermic chemical reaction front.

    Science.gov (United States)

    Sebestíková, L; D'Hernoncourt, J; Hauser, M J B; Müller, S C; De Wit, A

    2007-02-01

    Fingertip splitting may be observed at chemical reaction fronts subject to buoyancy-induced Rayleigh-Taylor fingering, as investigated in ascending fronts of the iodate-arsenous acid reaction in vertical Hele-Shaw cells. We study the properties of the flow-field evolution during a tip-splitting event both experimentally and theoretically. Experimental particle-image velocimetry techniques show that the flow field associated to a finger displays a quadrupole of vortices. The evolution of the flow field and the reorganization of the vortices after a tip-splitting event are followed experimentally in detail. Numerical integration of a model reaction-diffusion-convection system for an exothermic reaction taking into account possible heat losses through the walls of the reactor shows that the nonlinear properties of the flow field are different whether the walls are insulating or conducting. In insulating systems, the flow field inside one finger features only one pair of vortices. A quadrupole of flow vortices arranged around a saddle-node structure similar to the one observed experimentally is obtained in the presence of heat losses suggesting that heat effects, even if of very small amplitude, are important in understanding the nonlinear properties of fingering of exothermic chemical fronts.

  18. Computed Potential Energy Surfaces and Minimum Energy Pathways for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. For some dynamics methods, global potential energy surfaces are required. In this case, it is necessary to obtain the energy at a complete sampling of all the possible arrangements of the nuclei, which are energetically accessible, and then a fitting function must be obtained to interpolate between the computed points. In other cases, characterization of the stationary points and the reaction pathway connecting them is sufficient. These properties may be readily obtained using analytical derivative methods. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives usefull results for a number of chemically important systems. The talk will focus on a number of applications including global potential energy surfaces, H + O2, H + N2, O(3p) + H2, and reaction pathways for complex reactions, including reactions leading to NO and soot formation in hydrocarbon combustion.

  19. Recovery of work from exothermic chemical reaction systems by means of turbine expansion

    Energy Technology Data Exchange (ETDEWEB)

    Greeff, I.L.

    2003-12-08

    It is evident that a unique design approach or methodology is needed to develop flow sheet configurations for chemical reaction systems that use turbine expanders to recover reaction heat. It is the aim of this work to address this need by finding a methodology that will lend structure to the development and analysis of the flow sheets for the mentioned systems. Many factors have to be taken into consideration, both relating to the requirements of the chemical process and the requirements of the power cycle created using the process gas. For example, a reasonable pressure ratio is required over compression equipment in the case of a power cycle to produce power efficiently. The physical properties of the process gas, which becomes a working fluid, are also important. Furthermore, a thorough understanding of the role and behaviour of the expander within the chemical process is needed. Consequently, in this work the parameters that impact on the integrated systems will be identified and their roles investigated. Suitable criteria of performance for the integrated systems in question are also needed. In this regard the exergy method is particularly suited since it enables designs that will use energy resources more efficiently. The application of exergy analysis is illustrated and the strengths and limitations are discussed. The purpose of this research is achieved by conducting a number of case studies on different chemical reaction processes. These processes all comprise exothermic, high-pressure reactions, but otherwise differ significantly in terms of aspects such as reactor operation, separation techniques, reactant conversion, etc. The chemicals are also produced on a global scale using well-known processes. This makes realistic modelling of the processes possible. Process data are generated using simulations. The level of modelling and simulation is of a conceptual nature to investigate and illustrate fundamental principles, relations and trends. In Chapter 2

  20. Precision synthesis of functional materials via RAFT polymerization and click-type chemical reactions

    Science.gov (United States)

    Flores, Joel Diez

    2011-12-01

    The need to tailor polymeric architectures with specific physico-chemical properties via the simplest, cleanest, and most efficient synthetic route possible has become the ultimate goal in polymer synthesis. Recent progress in macromolecular science, such as the discoveries of controlled/"living" free radical polymerization (CRP) methods, has brought about synthetic capabilities to prepare (co)polymers with advanced topologies, predetermined molecular weights, narrow molecular weight distributions, and precisely located functional groups. In addition, the establishment of click chemistry has redefined the selected few highly efficient chemical reactions that become highly useful in post-polymerization modification strategies. Hence, the ability to make well-defined topologies afforded by controlled polymerization techniques and the facile incorporation of functionalities along the chain via click-type reactions have yielded complex architectures, allowing the investigation of physical phenomena which otherwise could not be studied with systems prepared via conventional methods. The overarching theme of the research work described in this dissertation is the fusion of the excellent attributes of reversible addition-fragmentation chain transfer (RAFT) polymerization method, which is one of the CRP techniques, and click-type chemical reactions in the precision of synthesis of advanced functional materials. Chapter IV is divided into three sections. In Section I, the direct RAFT homopolymerization of 2-(acryloyloxy)ethyl isocyanate (AOI) and subsequent post-polymerization modifications are described. The polymerization conditions were optimized in terms of the choice of RAFT chain transfer agent (CTA), polymerization temperature and the reaction medium. Direct RAFT polymerization of AOI requires a neutral CTA, and relatively low reaction temperature to yield AOI homopolymers with low polydispersities. Efficient side-chain functionalization of PAOI homopolymers was

  1. Programmable chemical reaction networks: emulating regulatory functions in living cells using a bottom-up approach.

    Science.gov (United States)

    van Roekel, Hendrik W H; Rosier, Bas J H M; Meijer, Lenny H H; Hilbers, Peter A J; Markvoort, Albert J; Huck, Wilhelm T S; de Greef, Tom F A

    2015-11-07

    Living cells are able to produce a wide variety of biological responses when subjected to biochemical stimuli. It has become apparent that these biological responses are regulated by complex chemical reaction networks (CRNs). Unravelling the function of these circuits is a key topic of both systems biology and synthetic biology. Recent progress at the interface of chemistry and biology together with the realisation that current experimental tools are insufficient to quantitatively understand the molecular logic of pathways inside living cells has triggered renewed interest in the bottom-up development of CRNs. This builds upon earlier work of physical chemists who extensively studied inorganic CRNs and showed how a system of chemical reactions can give rise to complex spatiotemporal responses such as oscillations and pattern formation. Using purified biochemical components, in vitro synthetic biologists have started to engineer simplified model systems with the goal of mimicking biological responses of intracellular circuits. Emulation and reconstruction of system-level properties of intracellular networks using simplified circuits are able to reveal key design principles and molecular programs that underlie the biological function of interest. In this Tutorial Review, we present an accessible overview of this emerging field starting with key studies on inorganic CRNs followed by a discussion of recent work involving purified biochemical components. Finally, we review recent work showing the versatility of programmable biochemical reaction networks (BRNs) in analytical and diagnostic applications.

  2. Advancing the molecular movie: Femtosecond X-ray scattering of an electrocyclic chemical reaction

    Science.gov (United States)

    Minitti, Michael

    Since it began operation in 2009, SLAC's Linac Coherent Light Source (LCLS) has allowed scientists to make new types of X-ray measurements that were once thought unattainable by delivering one trillion X-ray photons in incredibly short bursts of less than a few femtoseconds. It was promised that this astonishing quantity of photons, delivered in such a small slice of time, could capture the motions of atoms in chemical reactions. Now we have used this capability to make a ``molecular movie'' of a molecule undergoing a chemical reaction from start to finish, with frames just a few femtoseconds long. We assembled the movie by taking individual X-ray snapshots of the molecules that show the positions of their atoms at each moment in time. Comparing these results to computer simulations of the reaction, we determined the routes the individual molecules followed as it's structure rearranged. This is the first step in developing robust methods for visualizing molecular motions in chemistry, biology, and materials science at the atomic scale. Please enjoy the movie! SLAC National Accelerator Laboratory U.S. DOE, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515.

  3. The removal of dinitrochlorobenzene from industrial residuals by liquid-liquid extraction with chemical reaction

    Directory of Open Access Journals (Sweden)

    G. C. M. Ferreira

    2007-09-01

    Full Text Available Nitrochlorobenzenes (NCBs are very important in the chemical industry since they have been used as raw material for the manufacture of crop protection products, as active ingredients in the pharmaceutical industry, as pigments and as antioxidants as well as for other uses. In industrial processes, NCBs are produced by monochlorobenzene (MCB nitration reactions and one of the main residuals formed is dinitrochlorobenzene (DNCB, which is mainly composed of the isomer 2,4DNCB. This subproduct, although of commercial interest when in its pure state, is generally incinerated due to the high costs of recovery treatment and purification. The objective of this study is to present an alternative to the treatment of industrial residuals containing DNCB. The technique consists of converting DNCB into sodium dinitrophenolate, which is very soluble in water and is also easy to reuse. For this purpose, liquid-liquid extraction with chemical reaction (alkaline hydrolysis with a rotating disc contactor (RDC is used. Experimental data on MCB nitration reactions as well as alkaline hydrolysis using a rotating disc contactor are presented.

  4. Chemical mechanism and specificity of the C5-mannuronan epimerase reaction.

    Science.gov (United States)

    Jerga, Agoston; Stanley, Matthew D; Tipton, Peter A

    2006-08-01

    C5-mannuronan epimerase catalyzes the formation of alpha-L-guluronate residues from beta-D-mannuronate residues in the synthesis of the linear polysaccharide alginate. The reaction requires the abstraction of a proton from C5 of the residue undergoing epimerization followed by re-protonation on the opposite face. Rapid-mixing chemical quench experiments were conducted to determine the nature of the intermediate formed upon proton abstraction in the reaction catalyzed by the enzyme from Pseudomonas aeruginosa. Colorimetric and HPLC analysis of quenched samples indicated that shortened oligosaccharides containing an unsaturated sugar residue form as transient intermediates in the epimerization reaction. This suggests that the carbanion is stabilized by glycal formation, concomitant with cleavage of the glycosidic bond between the residue undergoing epimerization and the adjacent residue. The time dependence of glycal formation suggested that slow steps flank the chemical steps in the catalytic cycle. Solvent isotope effects on V and V/K were unity, consistent with a catalytic cycle in which chemistry is not rate-limiting. The specificity of the epimerase with regard to neighboring residues was examined, and it was determined that the enzyme showed no bias for mannuronate residues adjacent to guluronates versus those adjacent to mannuronates. Proton abstraction and sugar epimerization were irreversible. Existing guluronate residues already present in the polysaccharide were not converted to mannuronates, nor was incorporation of solvent deuterium into existing mannuronates observed.

  5. Systematic Search for Chemical Reactions in Gas Phase Contributing to Methanol Formation in Interstellar Space.

    Science.gov (United States)

    Gamez-Garcia, Victoria G; Galano, Annia

    2017-10-05

    A massive search for chemical routes leading to methanol formation in gas phase has been conducted using computational chemistry, at the CBS-QB3 level of theory. The calculations were performed at five different temperatures (100, 80, 50, 20, and 10 K) and at three pressures (0.1, 0.01, and 0.001 atm) for each temperature. The search was focused on identifying reactions with the necessary features to be viable in the interstellar medium (ISM). A searching strategy was applied to that purpose, which allowed to reduce an initial set of 678 possible reactions to a subset of 11 chemical routes that are recommended, for the first time, as potential candidates for contributing to methanol formation in the gas phase of the ISM. They are all barrier-less, and thus they are expected to take place at collision rates. Hopefully, including these reactions in the currently available models, for the gas-phase methanol formation in the ISM, would help improving the predicted fractional abundance of this molecule in dark clouds. Further investigations, especially those dealing with grain chemistry and electronic excited states, would be crucial to get a complete picture of the methanol formation in the ISM.

  6. Open-source Framework for Storing and Manipulation of Plasma Chemical Reaction Data

    Science.gov (United States)

    Jenkins, T. G.; Averkin, S. N.; Cary, J. R.; Kruger, S. E.

    2017-10-01

    We present a new open-source framework for storage and manipulation of plasma chemical reaction data that has emerged from our in-house project MUNCHKIN. This framework consists of python scripts and C + + programs. It stores data in an SQL data base for fast retrieval and manipulation. For example, it is possible to fit cross-section data into most widely used analytical expressions, calculate reaction rates for Maxwellian distribution functions of colliding particles, and fit them into different analytical expressions. Another important feature of this framework is the ability to calculate transport properties based on the cross-section data and supplied distribution functions. In addition, this framework allows the export of chemical reaction descriptions in LaTeX format for ease of inclusion in scientific papers. With the help of this framework it is possible to generate corresponding VSim (Particle-In-Cell simulation code) and USim (unstructured multi-fluid code) input blocks with appropriate cross-sections.

  7. Reentry blackout prediction for atmospheric reentry demonstrator mission considering uncertainty in chemical reaction rate model

    Science.gov (United States)

    Jung, Minseok; Kihara, Hisashi; Abe, Ken-ichi; Takahashi, Yusuke

    2018-01-01

    A numerical simulation model of plasma flows and electromagnetic waves around a vehicle was developed to predict a radio frequency blackout. Plasma flows in the shock layer and the wake region were calculated using a computational fluid dynamics technique with a three-dimensional model. A finite-catalytic wall condition known to affect plasma properties, such as the number density of electrons, was considered for accurate prediction. A parametric study was performed to investigate the effect of uncertainty in the chemical reaction rate model on evaluating a radio frequency blackout. The behavior of electromagnetic waves in plasma was investigated using a frequency-dependent finite-difference time-domain method. Numerical simulations of reentry blackout were performed for the Atmospheric Reentry Demonstrator mission at various altitudes. The plasma flows and the complex movement of electromagnetic waves around the Atmospheric Reentry Demonstrator vehicle were clarified. The predicted signal loss profile was then directly compared with the experimental flight data to validate the present models. The numerical results generally reproduced the trends over altitudes of the measured data. It is suggested that the present simulation model can be used to investigate the radio frequency blackout and signal loss of electromagnetic waves in the communication of a reentry vehicle. It was confirmed that high associative ionization reaction rates contribute to reducing the electron density in the wake region and radio frequency blackout. It is suggested that the accuracy of predicting the signal loss improved when considering the uncertainty in the chemical reaction model for associative ionizations.

  8. Theoretical research program to study chemical reactions in AOTV bow shock tubes

    Science.gov (United States)

    Taylor, Peter R.

    1993-01-01

    The main focus was the development, implementation, and calibration of methods for performing molecular electronic structure calculations to high accuracy. These various methods were then applied to a number of chemical reactions and species of interest to NASA, notably in the area of combustion chemistry. Among the development work undertaken was a collaborative effort to develop a program to efficiently predict molecular structures and vibrational frequencies using energy derivatives. Another major development effort involved the design of new atomic basis sets for use in chemical studies: these sets were considerably more accurate than those previously in use. Much effort was also devoted to calibrating methods for computing accurate molecular wave functions, including the first reliable calibrations for realistic molecules using full CI results. A wide variety of application calculations were undertaken. One area of interest was the spectroscopy and thermochemistry of small molecules, including establishing small molecule binding energies to an accuracy rivaling, or even on occasion surpassing, the experiment. Such binding energies are essential input to modeling chemical reaction processes, such as combustion. Studies of large molecules and processes important in both hydrogen and hydrocarbon combustion chemistry were also carried out. Finally, some effort was devoted to the structure and spectroscopy of small metal clusters, with applications to materials science problems.

  9. Numerical study of chemical reactions in a surface microdischarge tube with mist flow based on experiment

    Science.gov (United States)

    Shibata, T.; Nishiyama, H.

    2014-03-01

    Recently, a water treatment method of spraying solution into a discharge region has been developed and shows high energy efficiency. In this study, a simulation model of a water treatment method using a surface microdischarge (SMD) tube with mist flow is proposed for further understanding the detailed chemical reactions. Our model has three phases (plasma, gas and liquid) and three simulation steps. The carrier gas is humid air including 2% or 3% water vapour. The chemical species diffusion characteristics in the SMD tube and the concentrations in a droplet are clarified in a wide pH interval. The simulation results show that the chemical species generated on the SMD tube inner wall are diffused to the central axis and dissolved into fine droplets. Especially, OH radicals dissolve into droplets a few mm away from the SMD tube wall because of acidification of the droplets. Furthermore, the hydrogen peroxide density, which is the most important indicator of a radical reaction in water, is influenced by the initial solution pH. This pH dependence results from ozone self-decomposition in water.

  10. A Non-Isothermal Chemical Lattice Boltzmann Model Incorporating Thermal Reaction Kinetics and Enthalpy Changes

    Directory of Open Access Journals (Sweden)

    Stuart Bartlett

    2017-08-01

    Full Text Available The lattice Boltzmann method is an efficient computational fluid dynamics technique that can accurately model a broad range of complex systems. As well as single-phase fluids, it can simulate thermohydrodynamic systems and passive scalar advection. In recent years, it also gained attention as a means of simulating chemical phenomena, as interest in self-organization processes increased. This paper will present a widely-used and versatile lattice Boltzmann model that can simultaneously incorporate fluid dynamics, heat transfer, buoyancy-driven convection, passive scalar advection, chemical reactions and enthalpy changes. All of these effects interact in a physically accurate framework that is simple to code and readily parallelizable. As well as a complete description of the model equations, several example systems will be presented in order to demonstrate the accuracy and versatility of the method. New simulations, which analyzed the effect of a reversible reaction on the transport properties of a convecting fluid, will also be described in detail. This extra chemical degree of freedom was utilized by the system to augment its net heat flux. The numerical method outlined in this paper can be readily deployed for a vast range of complex flow problems, spanning a variety of scientific disciplines.

  11. Prise en compte de l'environnement dans le transfert de technologie ...

    African Journals Online (AJOL)

    A l'aide du modèle STOU, il est montré que le système dans lequel évolue le produit sec doit être pris en compte pour éviter les échecs de transfert des technologies. La méthode de conception distribuée permet de prendre en compte l'environnement. Son application a permis la conception d'un séchoir de mangues; ...

  12. Studying Chemical Reactions, One Bond at a Time, with Single Molecule AFM Techniques

    Science.gov (United States)

    Fernandez, Julio M.

    2008-03-01

    The mechanisms by which mechanical forces regulate the kinetics of a chemical reaction are unknown. In my lecture I will demonstrate how we use single molecule force-clamp spectroscopy and protein engineering to study the effect of force on the kinetics of thiol/disulfide exchange. Reduction of disulfide bond via the thiol/disulfide exchange chemical reaction is crucial in regulating protein function and is of common occurrence in mechanically stressed proteins. While reduction is thought to proceed through a substitution nucleophilic bimolecular (SN2) reaction, the role of a mechanical force in modulating this chemical reaction is unknown. We apply a constant stretching force to single engineered disulfide bonds and measure their rate of reduction by dithiothreitol (DTT). We find that while the reduction rate is linearly dependent on the concentration of DTT, it is exponentially dependent on the applied force, increasing 10-fold over a 300 pN range. This result predicts that the disulfide bond lengthens by 0.34 å at the transition state of the thiol/disulfide exchange reaction. In addition to DTT, we also study the reduction of the engineered disulfide bond by the E. coli enzyme thioredoxin (Trx). Thioredoxins are enzymes that catalyze disulfide bond reduction in all organisms. As before, we apply a mechanical force in the range of 25-450 pN to the engineered disulfide bond substrate and monitor the reduction of these bonds by individual enzymes. In sharp contrast with the data obtained with DTT, we now observe two alternative forms of the catalytic reaction, the first requiring a reorientation of the substrate disulfide bond, causing a shortening of the substrate polypeptide by 0.76±0.07 å, and the second elongating the substrate disulfide bond by 0.21±0.01 å. These results support the view that the Trx active site regulates the geometry of the participating sulfur atoms, with sub-ångström precision, in order to achieve efficient catalysis. Single molecule

  13. Effect of fuel particle size on reaction rate in chemical looping combustion

    Energy Technology Data Exchange (ETDEWEB)

    Iggland, M.; Leion, H.; Mattisson, T.; Lyngfelt, A. [ETH, Zurich (Switzerland). Inst. of Process Engineering

    2010-11-15

    Chemical looping combustion (CLC) uses an oxygen carrier circulating between an air and a fuel reactor to replace direct burning of fuels in air. The very low energy penalty for CO{sub 2} separation in CLC gives it the potential to become an important technology on the way to a CO{sub 2} neutral energy supply. In this work, the influence of the particle size of coal on the rate of reaction of the coal was investigated in a bed of oxygen carrier. In order to do this, a method to quench the reaction of coal with oxygen carriers at a specified time and measure the particle size distribution of the remaining coal was developed. Three size fractions of coal were used in the experiments: 90-125, 180-212 and 250-355 mu m. Particle size distributions of the fuel show a decrease in particle size with time. The influence of devolatilisation of the coal on the coal particle size was measured, showing that coal particles do not break in the fluidized bed reactor used for the experiments. Reaction rates based on measurements of gas phase concentrations of CO{sub 2}, CO and CH{sub 4} showed that the reaction rate is independent of the particle size. These results are in line with literature findings, as studies have shown that carbon gasification is size-independent at conditions similar to those in the performed CLC experiments.

  14. Reaction parameter study for the chemical synthesis of adsorbent silica gel

    Directory of Open Access Journals (Sweden)

    María Carolina Sáenz

    2010-07-01

    Full Text Available This article presents an appropriate set of reaction parameters (reaction temperature, sulphuric acid and sodium silicate reagent concentration for obtaining adsorbent silica gel (ASG using Colombian-produced raw materials. The core of ASG synthesis lies in sulphuric acid’s neutralisation reaction with sodium silicate. Their effect on final ASG moisture adsorption capacity was measured after changing such synthesis’ above–mentioned reaction parameters. Within the range of conditions studied, it was found that the highest adsorption capacity occurred by combining both low sodium silicate concentration with high temperatures or high sulphuric acid concentration and temperature. Synthesised ASG was also compared to a commercial product (Gel de sílice granulare con indicatore. Montedison group. Batch number 1684G100. Code number 453301 using adsorption capacity plots, BET areas, X–ray di-ffraction, mass and infrared spectrometry and mechanical strength measurements. Synthesised ASG presented larger specific surface areas but weaker mechanical strength than the commercial one. Likewise, all evaluated samples exhibited a low degree of molecular arrangement and conventional ASG chemical structure.

  15. Solid-state Chemical Reaction Synthesis and Characterization of Lanthanum Tartrate Nanocrystallites Under Ultrasonication Spectra

    Science.gov (United States)

    Li, Dao-hua; He, Shao-fen; Chen, Jie; Jiang, Cheng-yan; Yang, Cheng

    2017-09-01

    Under near room temperature, by using sodium tartrate, lanthanum trichloride, lanthanum acetate, and lanthanum nitrate as reactants, we synthesize the lanthanum tartrate nanocrystals in one step under the condition that the infrared lamp is irradiated and the polyethylene glycol 400 is used as the surfactant, where the synthesis method of nanoparticles by solid phase chemical reaction is used. Deionized water after washing with ethanol washes. Tartaric acid lanthanum crystalline powder is gotten, respectively. Analyze solid products phase using X-ray diffraction (XRD) and electron diffraction; characterize the functional groups structure with infrared spectra, and analyzethe change of functional groups in drugs before and after reaction; observe the size, shape, and size distribution of particlesby transmission electron microscopy(TEM). Testing 3 types of tartaric acid crystal powder of lanthanum are nano-crystallization, solid products are granular and relatively uniform in size, with an average particle diameter of about 40 nm, and the yield rate is approximately 92.3%. Furthermore, during the synthesis, the solid-state reaction conditions including raw materials, matching proportion of reactants, additions of inert substance, addition of trace solvents, surfactants and porphyrization time, etc, all have some influence on the morphology, particle size and size distribution of the final products. During the synthesis of the lanthanum tartrate nanocrystallites, the solid state reaction conditions such as changing reactant, matching proportion of reactant, adding inert substance, joining a little solvent or surface active solvent and grinding at different times may influence morphology, particle size and the size distribution of final products.

  16. A Macro-Micro-Symbolic Teaching to Promote Relational Understanding of Chemical Reactions

    Science.gov (United States)

    Ziad Jaber, Lama; BouJaoude, Saouma

    2012-05-01

    The purpose of this research is threefold: (1) to identify the difficulties that Grade 10 students in a Lebanese school have that hinder their conceptual understanding at the micro-macro-symbolic interface in chemistry, (2) to investigate the effect of a macro-micro-symbolic teaching approach on students' relational understanding of chemical reactions, and (3) to characterize students' conceptual profiles regarding their understanding of chemical reactions in terms of macro, micro, symbolic levels and the relations among them, at the end of the teaching sequence. Forty six 10th graders from two sections participated in the study. A student-centered approach was followed in both sections based on constructivist pedagogy. Hence the teacher played the role of a facilitator who guided students in a meaning making inductive learning process, through questioning, monitoring, validating, and clarifying ideas. Instruction in the experimental group was characterized by macro-micro-symbolic teaching that focuses on the interplay between the levels, integrates various representations, and engages students in an epistemic discourse about the nature of knowing in chemistry. Data sources for the study included a pre-test and two post-intervention tasks: a post-test and a concept map task, in addition to interviews with selected students from both sections. Findings indicated that macro-micro-symbolic teaching enhanced students' conceptual understanding and relational learning of chemical reactions. Besides, four assertions related to students' conceptual and epistemological thinking in response to the different teaching approaches are presented. Implications for instruction and for teacher education programs, as well as recommendations for further research, are discussed in light of these findings.

  17. Peroxidase chemically attached on polymeric micelle and its reaction with phenolic compounds.

    Science.gov (United States)

    Lee, Moo-Yeal; Bigdelou, Parnian; Hong, Kyung-Jin; Kim, Kyoung-Ae; Shinya, Yoshitsune; Kajiuchi, Toshio

    2018-02-01

    Horseradish peroxidase was chemically modified with comb-shaped polymaleic anhydride-alt-1-tetradecene (PMA-TD) in microemulsion systems to produce surface-active peroxidase that has capability to form micellar structures in aqueous solutions and can be concentrated at liquid/liquid interfaces without unfolding of the enzyme. For chemical modification oil-in-water (O/W) and water-in-oil (W/O) microemulsion systems composed of n-butyl acetate and a buffer solution were prepared because n-butyl acetate turned out to be less detrimental to the activity of peroxidase at high degree of modification compared to other organic solvents. The modification degree of amine groups on the surface of peroxidase by maleic anhydride groups on PMA-TD was reached at equilibrium after 1h reaction at 0°C, and 42% of amine groups were modified with 7-fold amount of PMA-TD to peroxidase (wt/wt). The activity of the PMA-TD-modified peroxidase measured with 2,4-dichlorophenol at pH 7.0 was increased by approximately 2-fold compared to native peroxidase. There was no significant shift in optimum pH after modification, and optimum pH measured with 2,4-dichlorophenol was observed at pH 7.0. For all six phenolic compounds tested, there was a significant increase in the reaction efficiency with the PMA-TD-modified peroxidase. The remarkable enhancement of the reaction efficiency by the modification was presumably because of micellar structures of PMA-TD that could concentrate hydrophobic phenolic oligomers into the core of the micelles. Overall, horseradish peroxidase chemically attached to the surface of PMA-TD micelles was found to be significantly effective for the oxidative polymerization of phenolic compounds. Published by Elsevier Inc.

  18. Density changes of aerosol particles as a result of chemical reaction

    Directory of Open Access Journals (Sweden)

    Y. Katrib

    2005-01-01

    Full Text Available This paper introduces the capability to study simultaneously changes in the density, the chemical composition, the mobility diameter, the aerodynamic diameter, and the layer thickness of multi-layered aerosol particles as they are being altered by heterogeneous chemical reactions. A vaporization-condensation method is used to generate aerosol particles composed of oleic acid outer layers of 2 to 30nm on 101-nm polystyrene latex cores. The layer density is modified by reaction of oleic acid with ozone for variable exposure times. For increasing ozone exposure, the mobility diameter decreases while the vacuum aerodynamic diameter increases, which, for spherical particles, implies that particle density increases. The aerosol particles are confirmed as spherical based upon the small divergence of the particle beam in the aerosol mass spectrometer. The particle and layer densities are calculated by two independent methods, namely one based on the measured aerodynamic and mobility diameters and the other based on the measured mobility diameter and particle mass. The uncertainty estimates for density calculated by the second method are two to three times greater than those of the first method. Both methods indicate that the layer density increases from 0.89 to 1.12g·cm-3 with increasing ozone exposure. Aerosol mass spectrometry shows that, concomitant with the increase in the layer density, the oxygen content of the reacted layer increases. Even after all of the oleic acid has reacted, the layer density and the oxygen content continue to increase slowly with prolonged ozone exposure, a finding which indicates continued chemical reactions of the organic products either with ozone or with themselves. The results of this paper provide new insights into the complex changes occurring for atmospheric particles during the aging processes caused by gas-phase oxidants.

  19. Use of molecular beams for kinetic measurements of chemical reactions on solid surfaces

    Science.gov (United States)

    Zaera, Francisco

    2017-05-01

    In this review we survey the contributions that molecular beam experiments have provided to our understanding of the dynamics and kinetics of chemical interactions of gas molecules with solid surfaces. First, we describe the experimental details of the different instrumental setups and approaches available for the study of these systems under the ultrahigh vacuum conditions and with the model planar surfaces often used in modern surface-science experiments. Next, a discussion is provided of the most important fundamental aspects of the dynamics of chemical adsorption that have been elucidated with the help of molecular beam experiments, which include the development of potential energy surfaces, the determination of the different channels for energy exchange between the incoming molecules and the surface, the identification of adsorption precursor states, the understanding of dissociative chemisorption, the determination of the contributions of corrugation, steps, and other structural details of the surface to the adsorption process, the effect to molecular steering, the identification of avenues for assisting adsorption, and the molecular details associated with the kinetics of the uptake of adsorbates as a function of coverage. We follow with a summary of the work directed at the determination of kinetic parameters and mechanistic details of surface reactions associated with catalysis, mostly those promoted by late transition metals. This discussion we initiate with an overview of what has been learned about simple bimolecular reactions such as the oxidation of CO and H2 with O2 and the reaction of CO with NO, and continue with the review of the studies of more complex systems such as the oxidation of alcohols, the conversion of organic acids, the hydrogenation and isomerization of olefins, and the oxidative activation of alkanes under conditions of short contact times. Sections 6 and 7 of this review deal with the advances made in the use of molecular beams with

  20. Double stratification effects on boundary layer over a stretching cylinder with chemical reaction and heat generation

    Science.gov (United States)

    Sohut, Noor Farizza Haniem Mohd; Aziz, Ahmad Sukri Abd; Ali, Zaileha Md

    2017-09-01

    An analysis of double stratification effects on boundary layer flow along a stretching cylinder with chemical reaction and heat generation is presented in this study. The governing non-linear partial differential equations are transformed into a system of non-linear ordinary differential equations using similarity transformations and solved by Runge-Kutta forth-fifth order (RKF45) with shooting technique. The effects of various parameters on the velocity, temperature and concentration distributions are analyzed graphically. The present analysis is validated by comparing with previously published work and found to be in good agreement.

  1. Unsteady flow of a Maxwell fluid over a stretching surface in presence of chemical reaction

    Directory of Open Access Journals (Sweden)

    Swati Mukhopadhyay

    2012-10-01

    Full Text Available An analysis is presented for unsteady two-dimensional flow of a Maxwell fluid over a stretching surface in presence of a first order constructive/destructive chemical reaction. Using suitable transformations, the governing partial differential equations are converted to ordinary one and are then solved numerically by shooting method. The flow fields and mass transfer are significantly influenced by the governing parameters. Fluid velocity initially decreases with increasing unsteadiness parameter and concentration decreases significantly due to unsteadiness. The effect of increasing values of the Maxwell parameter is to suppress the velocity field. But the concentration is enhanced with increasing Maxwell parameter.

  2. Chemical Vapor Synthesis of Titanium Aluminides by Reaction of Aluminum Subchloride and Titanium Tetrachloride

    Science.gov (United States)

    Zakirov, Roman A.; Parfenov, Oleg G.; Solovyov, Leonid A.

    2017-11-01

    A new process for developing titanium aluminides (TiAls) using chemical vapor synthesis was investigated in a laboratory experiment. Aluminum subchloride (AlCl) was used as the reducing agent in the reaction with TiCl4 and the source of aluminum for Ti-Al alloy. Two types of products, with large crystals and fine particles, were fabricated. The large crystals were determined to be TiAl, with small amounts of Ti and Ti3Al phases. The composition of fine particles, on the other hand, varied in wide range.

  3. Effects of mass transfer on MHD flow of casson fluid with chemical reaction and suction

    Directory of Open Access Journals (Sweden)

    S. A. Shehzad

    2013-03-01

    Full Text Available Effect of mass transfer in the magnetohydrodynamic flow of a Casson fluid over a porous stretching sheet is addressed in the presence of a chemical reaction. A series solution for the resulting nonlinear flow is computed. The skin friction coefficient and local Sherwood number are analyzed through numerical values for various parameters of interest. The velocity and concentration fields are illustrated for several pertinent flow parameters. We observed that the Casson parameter and Hartman number have similar effects on the velocity in a qualitative sense. We further analyzed that the concentration profile decreases rapidly in comparison to the fluid velocity when we increased the values of the suction parameter.

  4. Development of an apparatus to study chemical reactions at high temperature - a progress report

    Energy Technology Data Exchange (ETDEWEB)

    Sturzenegger, M.; Schelling, Th.; Steiner, E.; Wuillemin, D. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    TREMPER is an apparatus that was devised to study kinetic and thermodynamic aspects of high-temperature reactions under concentrated solar irradiation. The design allows investigations on solid or liquid samples under inert or reactive atmospheres. The working temperature is adjustable; the upper limit that has yet been reached is about 1900 K. TREMPER will facilitate chemical reactivity studies on a temperature level that is difficult to access by other means. First experiments were conducted to study the decomposition of manganese oxide MnO{sub 2}. Chemical analysis of exposed samples confirmed that the parent MnO{sub 2} was decomposed to mixtures of Mn O and Mn{sub 3}O{sub 4}. The amount of Mn O ranged from 60 mol-% in air to 86 mol-% under inert atmosphere. (author) 1 fig., 1 tab., 2 refs.

  5. Tabulation of thermodynamic data for chemical reactions involving 58 elements common to radioactive waste package systems

    Energy Technology Data Exchange (ETDEWEB)

    Benson, L.V.; Teague, L.S.

    1980-08-01

    The rate of release and migration of radionuclides from a nuclear waste repository to the biosphere is dependent on chemical interactions between groundwater, the geologic host rock, and the radioactive waste package. For the purpose of this report, the waste package includes the wasteform, canister, overpack, and repository backfill. Chemical processes of interest include sorption (ion exchange), dissolution, complexation, and precipitation. Thermochemical data for complexation and precipitation calculations for 58 elements common to the radioactive waste package are presented. Standard free energies of formation of free ions, complexes, and solids are listed. Common logarithms of equilibrium constants (log K's) for speciation and precipitation reactions are listed. Unless noted otherwise, all data are for 298.15/sup 0/K and one atmosphere.

  6. Classification of chemical substances, reactions, and interactions: The effect of expertise

    Science.gov (United States)

    Stains, Marilyne Nicole Olivia

    2007-12-01

    This project explored the strategies that undergraduate and graduate chemistry students engaged in when solving classification tasks involving microscopic (particulate) representations of chemical substances and microscopic and symbolic representations of different chemical reactions. We were specifically interested in characterizing the basic features to which students pay attention while classifying, identifying the patterns of reasoning that they follow, and comparing the performance of students with different levels of preparation in the discipline. In general, our results suggest that advanced levels of expertise in chemical classification do not necessarily evolve in a linear and continuous way with academic training. Novice students had a tendency to reduce the cognitive demand of the task and rely on common-sense reasoning; they had difficulties differentiating concepts (conceptual undifferentiation) and based their classification decisions on only one variable (reduction). These ways of thinking lead them to consider extraneous features, pay more attention to explicit or surface features than implicit features and to overlook important and relevant features. However, unfamiliar levels of representations (microscopic level) seemed to trigger deeper and more meaningful thinking processes. On the other hand, expert students classified entities using a specific set of rules that they applied throughout the classification tasks. They considered a larger variety of implicit features and the unfamiliarity with the microscopic level of representation did not affect their reasoning processes. Consequently, novices created numerous small groups, few of them being chemically meaningful, while experts created few but large chemically meaningful groups. Novices also had difficulties correctly classifying entities in chemically meaningful groups. Finally, expert chemists in our study used classification schemes that are not necessarily traditionally taught in classroom

  7. A detailed pathway analysis of the chemical reaction system generating the Martian vertical ozone profile

    Science.gov (United States)

    Stock, Joachim W.; Blaszczak-Boxe, Christopher S.; Lehmann, Ralph; Grenfell, J. Lee; Patzer, A. Beate C.; Rauer, Heike; Yung, Yuk L.

    2017-07-01

    Atmospheric chemical composition is crucial in determining a planet's atmospheric structure, stability, and evolution. Attaining a quantitative understanding of the essential chemical mechanisms governing atmospheric composition is nontrivial due to complex interactions between chemical species. Trace species, for example, can participate in catalytic cycles - affecting the abundance of major and other trace gas species. Specifically, for Mars, such cycles dictate the abundance of its primary atmospheric constituent, carbon dioxide (CO2), but also for one of its trace gases, ozone (O3). The identification of chemical pathways/cycles by hand is extremely demanding; hence, the application of numerical methods, such as the Pathway Analysis Program (PAP), is crucial to analyze and quantitatively exemplify chemical reaction networks. Here, we carry out the first automated quantitative chemical pathway analysis of Mars' atmosphere with respect to O3. PAP was applied to JPL/Caltech's 1-D updated photochemical Mars model's output data. We determine all significant chemical pathways and their contribution to O3 production and consumption (up to 80 km) in order to investigate the mechanisms causing the characteristic shape of the O3 volume mixing ratio profile, i.e. a ground layer maximum and an ozone layer at ∼50 km. These pathways explain why an O3 layer is present, why it is located at that particular altitude and what the different processes forming the near-surface and middle atmosphere O3 maxima are. Furthermore, we show that the Martian atmosphere can be divided into two chemically distinct regions according to the O(3P):O3 ratio. In the lower region (below approximately 24 km altitude) O3 is the most abundant Ox (= O3 + O(3P)) species. In the upper region (above approximately 24 km altitude), where the O3 layer is located, O(3P) is the most abundant Ox species. Earlier results concerning the formation of O3 on Mars can now be explained with the help of chemical

  8. Using magnetic levitation to distinguish atomic-level differences in chemical composition of polymers, and to monitor chemical reactions on solid supports.

    Science.gov (United States)

    Mirica, Katherine A; Phillips, Scott T; Shevkoplyas, Sergey S; Whitesides, George M

    2008-12-31

    This communication describes a density-based method that uses magnetic levitation for monitoring solid-supported reactions and for distinguishing differences in chemical composition of polymers. The method is simple, rapid, and inexpensive and is similar to thin-layer chromatography (TLC; for solution-phase chemistry) in its potential for monitoring reactions in solid-phase chemistry. The technique involves levitating a sample of beads (taken from a reaction mixture) in a cuvette containing a paramagnetic solution (e.g., GdCl(3) dissolved in H(2)O) positioned between two NdFeB magnets. The vertical position at which the beads levitate corresponds to the density of the beads and correlates with the progress of a chemical reaction on a solid support. The method is particularly useful for monitoring the kinetics of reactions occurring on polymer beads.

  9. A numerical modelling of gas exchange mechanisms between air and turbulent water with an aquarium chemical reaction

    Science.gov (United States)

    Nagaosa, Ryuichi S.

    2014-01-01

    This paper proposes a new numerical modelling to examine environmental chemodynamics of a gaseous material exchanged between the air and turbulent water phases across a gas-liquid interface, followed by an aquarium chemical reaction. This study uses an extended concept of a two-compartment model, and assumes two physicochemical substeps to approximate the gas exchange processes. The first substep is the gas-liquid equilibrium between the air and water phases, A(g)⇌A(aq), with Henry's law constant H. The second is a first-order irreversible chemical reaction in turbulent water, A(aq)+H2O→B(aq)+H+ with a chemical reaction rate κA. A direct numerical simulation (DNS) technique has been employed to obtain details of the gas exchange mechanisms and the chemical reaction in the water compartment, while zero velocity and uniform concentration of A is considered in the air compartment. The study uses the different Schmidt numbers between 1 and 8, and six nondimensional chemical reaction rates between 10(≈0) to 101 at a fixed Reynolds number. It focuses on the effects of the Schmidt number and the chemical reaction rate on fundamental mechanisms of the gas exchange processes across the interface.

  10. Reprint of: A numerical modelling of gas exchange mechanisms between air and turbulent water with an aquarium chemical reaction

    Science.gov (United States)

    Nagaosa, Ryuichi S.

    2014-08-01

    This paper proposes a new numerical modelling to examine environmental chemodynamics of a gaseous material exchanged between the air and turbulent water phases across a gas-liquid interface, followed by an aquarium chemical reaction. This study uses an extended concept of a two-compartment model, and assumes two physicochemical substeps to approximate the gas exchange processes. The first substep is the gas-liquid equilibrium between the air and water phases, A(g)⇌A(aq), with Henry's law constant H. The second is a first-order irreversible chemical reaction in turbulent water, A(aq)+H2O→B(aq)+H+ with a chemical reaction rate κA. A direct numerical simulation (DNS) technique has been employed to obtain details of the gas exchange mechanisms and the chemical reaction in the water compartment, while zero velocity and uniform concentration of A is considered in the air compartment. The study uses the different Schmidt numbers between 1 and 8, and six nondimensional chemical reaction rates between 10(≈0) to 101 at a fixed Reynolds number. It focuses on the effects of the Schmidt number and the chemical reaction rate on fundamental mechanisms of the gas exchange processes across the interface.

  11. Characterization of atmospheric air pollutants at two sites in northern Kyushu, Japan - chemical form, and chemical reaction

    Science.gov (United States)

    Shimohara, Takaaki; Oishi, Okihiro; Utsunomiya, Akira; Mukai, Hitoshi; Hatakeyama, Shiro; Eun-Suk, Jang; Uno, Itsushi; Murano, Kentaro

    Airborne gaseous and particulate matter in winter was measured over for 37 days in January and December 1997 at 2 sampling sites in northern Kyushu, Japan. One sampling site, Goto Island (an isolated island in the East China Sea), was about 200 km southwest of the other sampling site, Dazaifu city. In winter, acidic sulfates generated over the East Asian continent were transported to northwest Kyushu, to places such as Goto Island and the inland Kyushu area, and high sulfate concentrations were observed at the 2 sampling sites when strong NW winds blew. Acidity around Goto was mainly influenced by particulate NH 4HSO 4. The concentrations of NH 3 at Goto Island were lower than at Dazaifu city. The difference in NH 3 levels at the 2 sampling sites plays an important role in the chemical forms and sizes of the particulate matter. Nitrates at Goto Island were mostly present as NaNO 3 and Ca(NO 3) 2 in coarse-size particles. During the process of long-range transport of air pollutants from the Asian continent to Goto, gaseous HNO 3 was produced by a photochemical reactions of nitrogen oxides in the atmosphere, and particulate NaNO 3 and gaseous HCl were formed by a chlorine-loss reaction between NaCl and gaseous HNO 3. When strong NW winds blew, acidic sulfates together with some of the NaNO 3 and/or Ca(NO 3) 2 and some of gaseous HCl and HNO 3, which exist in the sea to the west of Kyushu and Goto Island, were transported to inland Kyushu such as Dazaifu city. During the process of transport, most of the acidic sulfates and acidic gases were mixed with regional air pollutants such as chlorides and nitrates existing around Dazaifu city, and neutralized forming (NH 4) 2SO 4, NH 4Cl and NH 4NO 3 in an environment of excess NH 3. Therefore, the main chemical forms of NO 3- at Dazaifu city varied day-by-day from fine-sized NH 4NO 3 to coarse-sized NaNO 3 and/or Ca(NO 3) 2. The appearance of NO 3- in coarse-size particles at Dazaifu city was due to the transport of NO 3

  12. Evaluating free energies in different scale systems: Chemical reactions and nanopatterns

    Science.gov (United States)

    Asciutto, Eliana K.

    All the thermodynamical properties of a given system can be obtained from the knowledge of the free energy of such system and its derivatives. Thus, a study of different methods to evaluate free energies is of considerable importance for physical, chemical and biological systems. However, free energy calculations are not straightforward in practice. For chemical systems for example, the complication is mainly due to the difficulty of calculating the entropy of the system. In order to overcome this difficulty, special methodologies have been introduced to provide some tools in the estimation of relative free energies for molecular systems via computer simulations. Another example where free energy calculations are challenging is the physics of phase transitions, i.e. the boiling of a liquid, the transition from paramagnetic to ferromagnetic behavior of a metal, etc. This thesis is divided in two parts. In the first part, the evaluation of free energy differences in chemical reactions is investigated through a novel method developed by Laio et al called Metadynamics (1). This method not only allows for the evaluation of free energy differences but also accelerates the reactions, driving the system through high free energy barriers and sampling regions of low probability. As an application, two important carboxylic acids, malonic and formic acid, were studied and their structure, energetics, intramolecular reactions and solvent interactions were determined. The deprotonation of the formic acid in presence of water was also fully investigated. In the second part, phase transition phenomena are considered, using the phenomenological Laundau-Ginsburg-Wilson Free Energy Functional. We investigated self-assembled domain patterns of modulated systems. They appear as a result of competing short-range attractive and long-range repulsive interactions found in diverse physical and chemical systems. From an application point of view, there is considerable interest in this domain

  13. Chemical morphogenesis: recent experimental advances in reaction-diffusion system design and control.

    Science.gov (United States)

    Szalai, István; Cuiñas, Daniel; Takács, Nándor; Horváth, Judit; De Kepper, Patrick

    2012-08-06

    In his seminal 1952 paper, Alan Turing predicted that diffusion could spontaneously drive an initially uniform solution of reacting chemicals to develop stable spatially periodic concentration patterns. It took nearly 40 years before the first two unquestionable experimental demonstrations of such reaction-diffusion patterns could be made in isothermal single phase reaction systems. The number of these examples stagnated for nearly 20 years. We recently proposed a design method that made their number increase to six in less than 3 years. In this report, we formally justify our original semi-empirical method and support the approach with numerical simulations based on a simple but realistic kinetic model. To retain a number of basic properties of real spatial reactors but keep calculations to a minimal complexity, we introduce a new way to collapse the confined spatial direction of these reactors. Contrary to similar reduced descriptions, we take into account the effect of the geometric size in the confinement direction and the influence of the differences in the diffusion coefficient on exchange rates of species with their feed environment. We experimentally support the method by the observation of stationary patterns in red-ox reactions not based on oxihalogen chemistry. Emphasis is also brought on how one of these new systems can process different initial conditions and memorize them in the form of localized patterns of different geometries.

  14. Improving Density Functional Tight Binding Predictions of Free Energy Surfaces for Slow Chemical Reactions in Solution

    Science.gov (United States)

    Kroonblawd, Matthew; Goldman, Nir

    2017-06-01

    First principles molecular dynamics using highly accurate density functional theory (DFT) is a common tool for predicting chemistry, but the accessible time and space scales are often orders of magnitude beyond the resolution of experiments. Semi-empirical methods such as density functional tight binding (DFTB) offer up to a thousand-fold reduction in required CPU hours and can approach experimental scales. However, standard DFTB parameter sets lack good transferability and calibration for a particular system is usually necessary. Force matching the pairwise repulsive energy term in DFTB to short DFT trajectories can improve the former's accuracy for reactions that are fast relative to DFT simulation times (reactions and the free energy surface are not well-known. We present a force matching approach to improve the chemical accuracy of DFTB. Accelerated sampling techniques are combined with path collective variables to generate the reference DFT data set and validate fitted DFTB potentials. Accuracy of force-matched DFTB free energy surfaces is assessed for slow peptide-forming reactions by direct comparison to DFT for particular paths. Extensions to model prebiotic chemistry under shock conditions are discussed. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

  15. Chemical reaction and radiation effects on MHD flow past an exponentially stretching sheet with heat sink

    Science.gov (United States)

    Nur Wahida Khalili, Noran; Aziz Samson, Abdul; Aziz, Ahmad Sukri Abdul; Ali, Zaileha Md

    2017-09-01

    In this study, the problem of MHD boundary layer flow past an exponentially stretching sheet with chemical reaction and radiation effects with heat sink is studied. The governing system of PDEs is transformed into a system of ODEs. Then, the system is solved numerically by using Runge-Kutta-Fehlberg fourth fifth order (RKF45) method available in MAPLE 15 software. The numerical results obtained are presented graphically for the velocity, temperature and concentration. The effects of various parameters are studied and analyzed. The numerical values for local Nusselt number, skin friction coefficient and local Sherwood number are tabulated and discussed. The study shows that various parameters give significant effect on the profiles of the fluid flow. It is observed that the reaction rate parameter affected the concentration profiles significantly and the concentration thickness of boundary layer decreases when reaction rate parameter increases. The analysis found is validated by comparing with the results previous work done and it is found to be in good agreement.

  16. Adjusting the Chemical Bonding of SnO2 @CNT Composite for Enhanced Conversion Reaction Kinetics.

    Science.gov (United States)

    Cheng, Yayi; Huang, Jianfeng; Qi, Hui; Cao, Liyun; Yang, Jun; Xi, Qiao; Luo, Xiaomin; Yanagisawa, Kazumichi; Li, Jiayin

    2017-08-01

    Carbon nanotubes (CNTs) with excellent electron conductivity are widely used to improve the electrochemical performance of the SnO2 anode. However, the chemical bonding between SnO2 and CNTs is not clearly elucidated despite it may affect the lithiation/delithiation behavior greatly. In this work, an SnO2 @CNT composite with SnC and SnOC bonds as a linkage bridge is reported and the influence of the SnC and SnOC bonds on the lithium storage properties is revealed. It is found that the SnC bond can act as an ultrafast electron transfer path, facilitating the reversible conversion reaction between Sn and Li2 O to form SnO2 . Therefore, the SnO2 @CNT composite with more SnC bond shows high reversible capacity and nearly half capacity contributes from conversion reaction. It is opposite for the SnO2 @CNT composite with more SnOC bond that the electrons cannot be transferred directly to CNTs, resulting in depressed conversion reaction kinetics. Consequently, this work can provide new insight for exploration and design of metal oxide/carbon composite anode materials in lithium-ion battery. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Kinetically constrained ring-polymer molecular dynamics for non-adiabatic chemical reactions.

    Science.gov (United States)

    Menzeleev, Artur R; Bell, Franziska; Miller, Thomas F

    2014-02-14

    We extend ring-polymer molecular dynamics (RPMD) to allow for the direct simulation of general, electronically non-adiabatic chemical processes. The kinetically constrained (KC) RPMD method uses the imaginary-time path-integral representation in the set of nuclear coordinates and electronic states to provide continuous equations of motion that describe the quantized, electronically non-adiabatic dynamics of the system. KC-RPMD preserves the favorable properties of the usual RPMD formulation in the position representation, including rigorous detailed balance, time-reversal symmetry, and invariance of reaction rate calculations to the choice of dividing surface. However, the new method overcomes significant shortcomings of position-representation RPMD by enabling the description of non-adiabatic transitions between states associated with general, many-electron wavefunctions and by accurately describing deep-tunneling processes across asymmetric barriers. We demonstrate that KC-RPMD yields excellent numerical results for a range of model systems, including a simple avoided-crossing reaction and condensed-phase electron-transfer reactions across multiple regimes for the electronic coupling and thermodynamic driving force.

  18. Fast stochastic simulation of biochemical reaction systems by alternative formulations of the chemical Langevin equation

    KAUST Repository

    Mélykúti, Bence

    2010-01-01

    The Chemical Langevin Equation (CLE), which is a stochastic differential equation driven by a multidimensional Wiener process, acts as a bridge between the discrete stochastic simulation algorithm and the deterministic reaction rate equation when simulating (bio)chemical kinetics. The CLE model is valid in the regime where molecular populations are abundant enough to assume their concentrations change continuously, but stochastic fluctuations still play a major role. The contribution of this work is that we observe and explore that the CLE is not a single equation, but a parametric family of equations, all of which give the same finite-dimensional distribution of the variables. On the theoretical side, we prove that as many Wiener processes are sufficient to formulate the CLE as there are independent variables in the equation, which is just the rank of the stoichiometric matrix. On the practical side, we show that in the case where there are m1 pairs of reversible reactions and m2 irreversible reactions there is another, simple formulation of the CLE with only m1 + m2 Wiener processes, whereas the standard approach uses 2 m1 + m2. We demonstrate that there are considerable computational savings when using this latter formulation. Such transformations of the CLE do not cause a loss of accuracy and are therefore distinct from model reduction techniques. We illustrate our findings by considering alternative formulations of the CLE for a human ether a-go-go related gene ion channel model and the Goldbeter-Koshland switch. © 2010 American Institute of Physics.

  19. Light-induced nitrous acid (HONO) production from NO2 heterogeneous reactions on household chemicals

    Science.gov (United States)

    Gómez Alvarez, Elena; Sörgel, Matthias; Gligorovski, Sasho; Bassil, Sabina; Bartolomei, Vincent; Coulomb, Bruno; Zetzsch, Cornelius; Wortham, Henri

    2014-10-01

    Nitrous acid (HONO) can be generated in various indoor environments directly during combustion processes or indirectly via heterogeneous NO2 reactions with water adsorbed layers on diverse surfaces. Indoors not only the concentrations of NO2 are higher but the surface to volume (S/V) ratios are larger and therefore the potential of HONO production is significantly elevated compared to outdoors. It has been claimed that the UV solar light is largely attenuated indoors. Here, we show that solar light (λ > 340 nm) penetrates indoors and can influence the heterogeneous reactions of gas-phase NO2 with various household surfaces. The NO2 to HONO conversion mediated by light on surfaces covered with domestic chemicals has been determined at atmospherically relevant conditions i.e. 50 ppb NO2 and 50% RH. The formation rates of HONO were enhanced in presence of light for all the studied surfaces and are determined in the following order: 1.3·109 molecules cm-2 s-1 for borosilicate glass, 1.7·109 molecules cm-2 s-1 for bathroom cleaner, 1.0·1010 molecules cm-2 s-1 on alkaline detergent (floor cleaner), 1.3·1010 molecules cm-2 s-1 for white wall paint and 2.7·1010 molecules cm-2 s-1 for lacquer. These results highlight the potential of household chemicals, used for cleaning purposes to generate HONO indoors through light-enhanced NO2 heterogeneous reactions. The results obtained have been applied to predict the timely evolution of HONO in a real indoor environment using a dynamic mass balance model. A steady state mixing ratio of HONO has been estimated at 1.6 ppb assuming a contribution from glass, paint and lacquer and considering the photolysis of HONO as the most important loss process.

  20. Feasibility Study of Venus Surfuce Cooling Using Chemical Reactions with the Atmosphere

    Science.gov (United States)

    Evans, Christopher

    2013-01-01

    A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options

  1. Feasibility Study of Venus Surface Cooling Using Chemical Reactions with the Atmosphere

    Science.gov (United States)

    Evans, Christopher

    2013-01-01

    A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options.

  2. Influence of exothermic chemical reactions on laser-induced shock waves.

    Science.gov (United States)

    Gottfried, Jennifer L

    2014-10-21

    Differences in the excitation of non-energetic and energetic residues with a 900 mJ, 6 ns laser pulse (1064 nm) have been investigated. Emission from the laser-induced plasma of energetic materials (e.g. triaminotrinitrobenzene [TATB], cyclotrimethylene trinitramine [RDX], and hexanitrohexaazaisowurtzitane [CL-20]) is significantly reduced compared to non-energetic materials (e.g. sugar, melamine, and l-glutamine). Expansion of the resulting laser-induced shock wave into the air above the sample surface was imaged on a microsecond timescale with a high-speed camera recording multiple frames from each laser shot; the excitation of energetic materials produces larger heat-affected zones in the surrounding atmosphere (facilitating deflagration of particles ejected from the sample surface), results in the formation of additional shock fronts, and generates faster external shock front velocities (>750 m s(-1)) compared to non-energetic materials (550-600 m s(-1)). Non-explosive materials that undergo exothermic chemical reactions in air at high temperatures such as ammonium nitrate and magnesium sulfate produce shock velocities which exceed those of the inert materials but are less than those generated by the exothermic reactions of explosive materials (650-700 m s(-1)). The most powerful explosives produced the highest shock velocities. A comparison to several existing shock models demonstrated that no single model describes the shock propagation for both non-energetic and energetic materials. The influence of the exothermic chemical reactions initiated by the pulsed laser on the velocity of the laser-induced shock waves has thus been demonstrated for the first time.

  3. In–situ Spatiotemporal Chemical Reactions at Water-Solid Interfacial Processes using Microelectrode Techniques: from Biofilm to Metal Corrosion

    Science.gov (United States)

    Recent developments in microscale sensors allows the non-destructive and in–situ measurement of both the absolute and changes in chemical concentrations in engineered and natural aquatic systems. Microelectrodes represent a unique tool for studying in–situ chemical reactions in b...

  4. "Toward High School Biology": Helping Middle School Students Understand Chemical Reactions and Conservation of Mass in Nonliving and Living Systems

    Science.gov (United States)

    Herrmann-Abell, Cari F.; Koppal, Mary; Roseman, Jo Ellen

    2016-01-01

    Modern biology has become increasingly molecular in nature, requiring students to understand basic chemical concepts. Studies show, however, that many students fail to grasp ideas about atom rearrangement and conservation during chemical reactions or the application of these ideas to biological systems. To help provide students with a better…

  5. A new halogen-free chemical oscillator: the reaction between permanganate ion and ninhydrin in a continuously stirred tank reactor

    Science.gov (United States)

    Treindl, Ľudovít; Nagy, Arpád

    1987-07-01

    The reaction between permanganate ion and ninhydrin in the presence of phosphoric acid in aqueous solution shows sustained oscillations in a continuously stirred tank reactor (CSTR). It exhibits a kinetic bistability between an oscillatory and a stationary state. Our new oscillating system seems to be a second permanganate chemical oscillator, thus broadening the small group of non-halogen-based chemical oscillators.

  6. High-Performance Chemically Regenerative Redox Fuel Cells Using a NO3-/NO Regeneration Reaction.

    Science.gov (United States)

    Han, Sang-Beom; Kwak, Da-Hee; Park, Hyun Suk; Choi, In-Ae; Park, Jin-Young; Kim, Si-Jin; Kim, Min-Cheol; Hong, Seongho; Park, Kyung-Won

    2017-03-06

    In this study, we proposed high-performance chemically regenerative redox fuel cells (CRRFCs) using NO 3 - /NO with a nitrogen-doped carbon-felt electrode and a chemical regeneration reaction of NO to NO 3 - via O 2 . The electrochemical cell using the nitrate reduction to NO at the cathode on the carbon felt and oxidation of H 2 as a fuel at the anode showed a maximal power density of 730 mW cm -2 at 80 °C and twofold higher power density of 512 mW cm -2 at 0.8 V, than the target power density of 250 mW cm -2 at 0.8 V in the H 2 /O 2 proton exchange membrane fuel cells (PEMFCs). During the operation of the CRRFCs with the chemical regeneration reactor for 30 days, the CRRFCs maintained 60 % of the initial performance with a regeneration efficiency of about 92.9 % and immediately returned to the initial value when supplied with fresh HNO 3 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. The Oxford-Diamond In Situ Cell for studying chemical reactions using time-resolved X-ray diffraction.

    Science.gov (United States)

    Moorhouse, Saul J; Vranješ, Nenad; Jupe, Andrew; Drakopoulos, Michael; O'Hare, Dermot

    2012-08-01

    A versatile, infrared-heated, chemical reaction cell has been assembled and commissioned for the in situ study of a range of chemical syntheses using time-resolved energy-dispersive X-ray diffraction (EDXRD) on Beamline I12 at the Diamond Light Source. Specialized reactor configurations have been constructed to enable in situ EDXRD investigation of samples under non-ambient conditions. Chemical reactions can be studied using a range of sample vessels such as alumina crucibles, steel hydrothermal autoclaves, and glassy carbon tubes, at temperatures up to 1200 °C.

  8. The Oxford-Diamond In Situ Cell for studying chemical reactions using time-resolved X-ray diffraction

    Science.gov (United States)

    Moorhouse, Saul J.; Vranješ, Nenad; Jupe, Andrew; Drakopoulos, Michael; O'Hare, Dermot

    2012-08-01

    A versatile, infrared-heated, chemical reaction cell has been assembled and commissioned for the in situ study of a range of chemical syntheses using time-resolved energy-dispersive X-ray diffraction (EDXRD) on Beamline I12 at the Diamond Light Source. Specialized reactor configurations have been constructed to enable in situ EDXRD investigation of samples under non-ambient conditions. Chemical reactions can be studied using a range of sample vessels such as alumina crucibles, steel hydrothermal autoclaves, and glassy carbon tubes, at temperatures up to 1200 °C.

  9. Chemical resolution of Pu+ from U+ and Am+ using a band-pass reaction cell inductively coupled plasma mass spectrometer.

    Science.gov (United States)

    Tanner, Scott D; Li, Chunsheng; Vais, Vladimir; Baranov, Vladimir I; Bandura, Dmitry R

    2004-06-01

    Determination of the concentration and distribution of the Pu and Am isotopes is hindered by the isobaric overlaps between the elements themselves and U, generally requiring time-consuming chemical separation of the elements. A method is described in which chemical resolution of the elemental ions is obtained through ion-molecule reactions in a reaction cell of an ICPMS instrument. The reactions of "natural" U(+), (242)Pu(+), and (243)Am(+) with ethylene, carbon dioxide, and nitric oxide are reported. Since the net sensitivities to the isotopes of an element are similar, chemical resolution is inferred when one isobaric element reacts rapidly with a given gas and the isobar (or in this instance surrogate isotope) is unreactive or slowly reactive. Chemical resolution of the m/z 238 isotopes of U and Pu can be obtained using ethylene as a reaction gas, but little improvement in the resolution of the m/z 239 isobars is obtained. However, high efficiency of reaction of U(+) and UH(+) with CO(2), and nonreaction of Pu(+), allows the sub-ppt determination of (239)Pu, (240)Pu, and (242)Pu (single ppt for (238)Pu) in the presence of 7 orders of magnitude excess U matrix without prior chemical separation. Similarly, oxidation of Pu(+) by NO, and nonreaction of Am(+), permit chemical resolution of the isobars of Pu and Am over 2-3 orders of magnitude relative concentration. The method provides the potential for analysis of the actinides with reduced sample matrix separation.

  10. Programming chemical kinetics: engineering dynamic reaction networks with DNA strand displacement

    Science.gov (United States)

    Srinivas, Niranjan

    Over the last century, the silicon revolution has enabled us to build faster, smaller and more sophisticated computers. Today, these computers control phones, cars, satellites, assembly lines, and other electromechanical devices. Just as electrical wiring controls electromechanical devices, living organisms employ "chemical wiring" to make decisions about their environment and control physical processes. Currently, the big difference between these two substrates is that while we have the abstractions, design principles, verification and fabrication techniques in place for programming with silicon, we have no comparable understanding or expertise for programming chemistry. In this thesis we take a small step towards the goal of learning how to systematically engineer prescribed non-equilibrium dynamical behaviors in chemical systems. We use the formalism of chemical reaction networks (CRNs), combined with mass-action kinetics, as our programming language for specifying dynamical behaviors. Leveraging the tools of nucleic acid nanotechnology (introduced in Chapter 1), we employ synthetic DNA molecules as our molecular architecture and toehold-mediated DNA strand displacement as our reaction primitive. Abstraction, modular design and systematic fabrication can work only with well-understood and quantitatively characterized tools. Therefore, we embark on a detailed study of the "device physics" of DNA strand displacement (Chapter 2). We present a unified view of strand displacement biophysics and kinetics by studying the process at multiple levels of detail, using an intuitive model of a random walk on a 1-dimensional energy landscape, a secondary structure kinetics model with single base-pair steps, and a coarse-grained molecular model that incorporates three-dimensional geometric and steric effects. Further, we experimentally investigate the thermodynamics of three-way branch migration. Our findings are consistent with previously measured or inferred rates for

  11. Ultrafast infrared studies of chemical reaction dynamics in room-temperature liquids

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Haw [Univ. of California, Berkeley, CA (United States)

    1999-11-01

    Femtosecond infrared spectroscopy provides sufficient spectral and temporal resolution to support a detailed investigation of the early events of a photochemical reaction. Previously unreported transient species that arise as intermediates during the course of a reaction may have lifetimes that are too short for conventional characterization. For these species, quantum-mechanical (density functional theoretical and ab initio) electronic structure calculations provide invaluable insight into chemical properties including molecular structure and energetic. With the combination of experimental and theoretical results, it is possible to assemble a comprehensive picture of the reaction dynamics of a system that is intricately influenced by the surrounding solvent molecules. The mechanisms of several important organometallic reactions, such as alkane C– H bond activation by η3-Tp*Rh(CO), silane Si–H bond activation by η5-CpMn(CO)2 and η5-CpRe(CO)2, as well as chlorinated methane C–Cl bond cleavage by the Re(CO)5 radical are elucidated. The results demonstrate the importance of molecular morphology change (C–H and Si–H act ivat ion), solvent rearrangement (Si–H activation), intersystem crossing (Si–H activation), and solvent caging (C–Cl cleavage) in understanding the reactivity of the organometallic species, The nature of the apparent free-energy barrier for C–H, Si–H, and C–Cl bond activation reaction is found to be- cleavage of an alkane C–H bond, rearrangement of a silane molecule HSiR3 (R = alkyl group) from a nonreactive alkyl site to the reactive Si–H bond, and Cl atom transfer from a chlorinated methane molecule to Re(CO)5, respectively. These results support previous d initio calculations for C–H and Si–H bond activation reaction profiles which suggest that cleavage of an alkane C–H bond by a transition metal center, unlike that of a silane

  12. Diversion of the melanin synthetic pathway by dopamine product scavengers: A quantum chemical modeling of the reaction mechanisms

    Directory of Open Access Journals (Sweden)

    T. B. Demissie

    2017-01-01

    Full Text Available We report the stability and reactivity of the oxidation products as well as L-cysteine and N-acetylcysteine adducts of dopamine studied using quantum chemical calculations. The overall reactions studied were subdivided into four reaction channels. The first reaction channel is the oxidation of dopamine to form dopaminoquinone. The second reaction channel leads to melanin formation through subsequent reactions. The third and fourth reaction channels are reactions leading to the formation of dopaminoquinone adducts which are aimed to divert the synthesis of melanin. The results indicate that L-cysteine and N-acetylcysteine undergo chemical reactions mainly at C5 position of dopaminoquinone. The analyses of the thermodynamic energies indicate that L-cysteine and N-acetylcysteine covalently bind to dopaminoquinone by competing with the internal cyclization reaction of dopaminoquinone which leads to the synthesis of melanin. The analysis of the results, based on the reaction free energies, is also supported by the investigation of the natural bond orbitals of the reactants and products.

  13. Influence of chemical structure on skin reactions induced by antiepileptic drugs--the role of the aromatic ring.

    Science.gov (United States)

    Wang, Xiang-Qing; Shi, Xiao-Bing; Au, Ran; Chen, Fu-Shun; Wang, Fang; Lang, Sen-Yang

    2011-05-01

    Here we assessed whether the presence of an aromatic ring as a commonality in chemical structures of AEDs can explain skin reaction. We found that 164 cases of skin reactions associated with the use of AEDs were reported. Aromatic AEDs were suspected in 88.41% (145/164) of patients with skin reactions versus 59.80% (2316/3873) of patients without skin reactions. The presence of an aromatic ring in the chemical structure was associated with a significant increased risk of skin reactions (adjusted ROR 3.50; 95% CI 2.29, 5.35). Among the aromatic AEDs, skin reactions were significantly associated with carbamazepine, lamotrigine, and oxarbazepine. These results confirm that the presence of an aromatic ring as a common feature in chemical structures of AEDs partly explains AED-skin reactions. Skin reactions were reported triple as frequently with aromatic AEDs than with non-aromatic AEDs. Copyright © 2011 Elsevier B.V. All rights reserved.

  14. A kinetic-theory approach for computing chemical-reaction rates in upper-atmosphere hypersonic flows.

    Science.gov (United States)

    Gallis, Michael A; Bond, Ryan B; Torczynski, John R

    2009-09-28

    Recently proposed molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction-rate information) are investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases.

  15. Mixed convection heat and mass transfer in peristaltic flow with chemical reaction and inclined magnetic field

    Science.gov (United States)

    Noreen, S.; Hayat, T.; Alsaedi, A.; Qasim, M.

    2013-09-01

    A mathematical model is constructed to investigate the mixed convective heat and mass transfer effects on peristaltic flow of magnetohydrodynamic pseudoplastic fluid in a symmetric channel. An analysis has been carried out to examine the impact of an inclined magnetic field and chemical reaction in presence of heat sink/source. Mechanics of flow and heat/mass transfer described in terms of continuity, linear momentum, energy and concentration equations are predicted by using long wavelength and low Reynolds number. Expressions for stream function, temperature, concentration and pressure gradient are derived. Numerical simulation is performed for the rise in pressure per wave length. Effects of several physical parameters on the flow quantities are analyzed.

  16. Investigating Arctic Tropospheric Ozone Depletion Through a Flowing Chemical Reaction Method of Halogen Free Radical Measurement

    Science.gov (United States)

    Tackett, P. J.; Shepson, P. B.; Bottenheim, J. W.; Steffen, A.

    2008-12-01

    Arctic tropospheric halogen chemistry has been investigated through the measurement of halogen free radicals, ozone, and gaseous elemental mercury in the lower Arctic troposphere during spring 2008 in a unique sea ice surface environment onboard the research icebreaker CCGS Amundsen. Low-level ozone depletion events were observed beginning in early March, with more extensive events occurring later in the month. Bromine monoxide measurements were conducted using a new, flowing chemical reaction method in addition to established DOAS techniques, and was observed with good agreement at concentrations approaching 40 ppt during periods of significant ozone and mercury depletion. Air mass history was observed for the periods leading to depletion, suggesting a dependence on sea ice contact and ambient temperatures below -22 °C as necessary elements for the onset of halogen-induced tropospheric ozone depletion. Here we discuss our data further with the aim of better understanding how ozone depletion events are triggered.

  17. Modelling chemical reactions in dc plasma inside oxygen bubbles in water

    Science.gov (United States)

    Takeuchi, N.; Ishii, Y.; Yasuoka, K.

    2012-02-01

    Plasmas generated inside oxygen bubbles in water have been developed for water purification. Zero-dimensional numerical simulations were used to investigate the chemical reactions in plasmas driven by dc voltage. The numerical and experimental results of the concentrations of hydrogen peroxide and ozone in the solution were compared with a discharge current between 1 and 7 mA. Upon increasing the water vapour concentration inside bubbles, we saw from the numerical results that the concentration of hydrogen peroxide increased with discharge current, whereas the concentration of ozone decreased. This finding agreed with the experimental results. With an increase in the discharge current, the heat flux from the plasma to the solution increased, and a large amount of water was probably vaporized into the bubbles.

  18. Chemical reaction and heat source effects on MHD oscillatory flow in an irregular channel

    Directory of Open Access Journals (Sweden)

    P.V. Satya Narayana

    2016-12-01

    Full Text Available This paper investigates the effect of heat and mass transfer on MHD oscillatory flow in an asymmetric wavy channel with chemical reaction and heat source. The unsteadiness in the flow is due to an oscillatory pressure gradient across the ends of the channel. A magnetic field of uniform strength is applied in the direction perpendicular to the channel. However, the induced magnetic field is neglected due to the assumption of small magnetic Reynolds number. The temperature difference of the channel is also assumed high enough to induce heat transfer due to radiation. The governing equations are solved analytically by regular perturbation method. The analytical results are evaluated numerically and then are presented graphically to discuss the effects of different parameters entering into the problem. It is observed that the heat transport of a system is more increased in oscillatory flow than in ordinary conduction.

  19. Synthesis of Cu-coated Graphite Powders Using a Chemical Reaction Process

    Energy Technology Data Exchange (ETDEWEB)

    Jang, Jun-Ho; Park, Hyun-Kuk; Oh, Ik-Hyun [Korea Institute of Industrial Technology (KITECH), Gwangju (Korea, Republic of); Lim, Jae-Won [Chonbuk National University, Jeonju (Korea, Republic of)

    2017-05-15

    In this paper, Cu-coated graphite powders for a low thermal expansion coefficient and a high thermal conductivity are fabricated using a chemical reaction process. The Cu particles adhere to the irregular graphite powders and they homogeneously disperse in the graphite matrix. Cu-coated graphite powders are coarser at approximately 3-4 μm than the initial graphite powders; furthermore, their XRD patterns exhibit a low intensity in the oxide peak with low Zn powder content. For the passivation powders, the transposition solvent content has low values, and the XRD pattern of the oxide peaks is almost non-existent, but the high transposition solvent content does not exhibit a difference to the non-passivation treated powders.

  20. Effects of gel properties produced by chemical reactions on viscous fingering

    Science.gov (United States)

    Ujiie, Tomohiro; Nagatsu, Yuichiro; Ban, Mitsumasa; Iwata, Shuichi; Kato, Yoshihito; Tada, Yutaka

    2011-11-01

    We have experimentally investigated viscous fingering with chemical reaction producing gel. Here, two systems were employed. In one system, sodium polyacrylate (SPA) solution and ferric ion solution were used as the more and less viscous liquids, respectively. In another system, xthantan gum (XG) solution and the ferric ion solution were used as the more and less viscous liquids, respectively. For high concentration of ferric ion, viscous fingering pattern was changed into spiral pattern in the former system, whereas into fracture pattern in the latter system. We consider that the difference in the change of the patterns in the two systems will be caused by the difference in the properties of the gels. Therefore, we have measured the rheological properties of the gels by means of a rheometer. We have found that the gel in the former case is more elastic. Furthermore, we have discussed the relationship between the measured rheological properties and the observed spiral or fracturing patterns.

  1. Unsteady MHD flow of an UCM fluid over a stretching surface with higher order chemical reaction

    Directory of Open Access Journals (Sweden)

    Sudhagar Palani

    2016-03-01

    Full Text Available The objective of this paper was to illustrate the frequent and wide occurrence of unsteady two dimensional MHD flow of an UCM fluid over a stretching surface in the presence of higher order chemical reaction in a diverse range of applications, both in nature and in technology. The governing partial differential equations are converted into ordinary differential equations by using similarity transformation. The ordinary differential equations were numerically solved by using shooting technique. The effects of different governing parameters on the flow field and mass transfer are shown in graphs and tables. The governing physical parameters significantly influence the flow field and mass transfer. Also, existing results in the literature are compared with the present study as a special case. In addition to practical applications in foams, suspensions, polymer solutions and melts, the present study also contributed to the existing literature.

  2. Chemical reaction effect on MHD free convective surface over a moving vertical plate through porous medium

    Directory of Open Access Journals (Sweden)

    R.S. Tripathy

    2015-09-01

    Full Text Available An attempt has been made to study the heat and mass transfer effect in a boundary layer flow of an electrically conducting viscous fluid subject to transverse magnetic field past over a moving vertical plate through porous medium in the presence of heat source and chemical reaction. The governing non-linear partial differential equations have been transformed into a two-point boundary value problem using similarity variables and then solved numerically by fourth order Runge–Kutta fourth order method with shooting technique. Graphical results are discussed for non-dimensional velocity, temperature and concentration profiles while numerical values of the skin friction, Nusselt number and Sherwood number are presented in tabular form for various values of parameters controlling the flow system.

  3. Stagnation point flow and mass transfer with chemical reaction past a stretching/shrinking cylinder.

    Science.gov (United States)

    Najib, Najwa; Bachok, Norfifah; Arifin, Norihan Md; Ishak, Anuar

    2014-02-26

    This paper is about the stagnation point flow and mass transfer with chemical reaction past a stretching/shrinking cylinder. The governing partial differential equations in cylindrical form are transformed into ordinary differential equations by a similarity transformation. The transformed equations are solved numerically using a shooting method. Results for the skin friction coefficient, Schmidt number, velocity profiles as well as concentration profiles are presented for different values of the governing parameters. Effects of the curvature parameter, stretching/shrinking parameter and Schmidt number on the flow and mass transfer characteristics are examined. The study indicates that dual solutions exist for the shrinking cylinder but for the stretching cylinder, the solution is unique. It is observed that the surface shear stress and the mass transfer rate at the surface increase as the curvature parameter increases.

  4. Stagnation Point Flow and Mass Transfer with Chemical Reaction past a Stretching/Shrinking Cylinder

    Science.gov (United States)

    Najib, Najwa; Bachok, Norfifah; Arifin, Norihan Md.; Ishak, Anuar

    2014-02-01

    This paper is about the stagnation point flow and mass transfer with chemical reaction past a stretching/shrinking cylinder. The governing partial differential equations in cylindrical form are transformed into ordinary differential equations by a similarity transformation. The transformed equations are solved numerically using a shooting method. Results for the skin friction coefficient, Schmidt number, velocity profiles as well as concentration profiles are presented for different values of the governing parameters. Effects of the curvature parameter, stretching/shrinking parameter and Schmidt number on the flow and mass transfer characteristics are examined. The study indicates that dual solutions exist for the shrinking cylinder but for the stretching cylinder, the solution is unique. It is observed that the surface shear stress and the mass transfer rate at the surface increase as the curvature parameter increases.

  5. Flow of an Erying-Powell fluid over a stretching sheet in presence of chemical reaction

    Directory of Open Access Journals (Sweden)

    Khan Ilyas

    2016-01-01

    Full Text Available In this paper we study the flow of an incompressible Erying-Powell fluid bounded by a linear stretching surface. The mass transfer analysis in the presence of destructive /generative chemical reactions is also analyzed. A similarity transformation is used to transform the governing partial differential equations into ordinary differential equations. Computations for dimensionless velocity and concentration fields are performed by an efficient approach namely the homotopy analysis method (HAM and numerical solution is obtained by shooting technique along with Runge-Kutta-Fehlberg integration scheme. Graphical results are prepared to illustrate the details of flow and mass transfer characteristics and their dependence upon the physical parameters. The values for gradient of mass transfer are also evaluated and analyzed. A comparison of the present solutions with published results in the literature is performed and the results are found to be in excellent agreement.

  6. Group Analysis of Free Convection Flow of a Magnetic Nanofluid with Chemical Reaction

    Directory of Open Access Journals (Sweden)

    Md. Jashim Uddin

    2015-01-01

    Full Text Available A theoretical study of two-dimensional magnetohydrodynamics viscous incompressible free convective boundary layer flow of an electrically conducting, chemically reacting nanofluid from a convectively heated permeable vertical surface is presented. Scaling group of transformations is used in the governing equations and the boundary conditions to determine absolute invariants. A third-order ordinary differential equation which corresponds to momentum conservation and two second-order ordinary differential equations which correspond to energy and nanoparticle volume fraction (species conservation are derived. Our (group analysis indicates that, for the similarity solution, the convective heat transfer coefficient and mass transfer velocity are proportional to x-1/4 whilst the reaction rate is proportional to x-1/2, where x is the axial distance from the leading edge of the plate. The effects of the relevant controlling parameters on the dimensionless velocity, temperature, and nanoparticle volume fraction are examined. The accuracy of the technique we have used was tested by performing comparisons with the results of published work and the results were found to be in good agreement. The present computations indicate that the flow is accelerated and temperature enhanced whereas nanoparticle volume fractions are decreased with increasing order of chemical reaction. Furthermore the flow is strongly decelerated, whereas the nanoparticle volume fraction and temperature are enhanced with increasing magnetic field parameter. Increasing convection-conduction parameter increases velocity and temperatures but has a weak influence on nanoparticle volume fraction distribution. The present study demonstrates the thermal enhancement achieved with nanofluids and also magnetic fields and is of relevance to nanomaterials processing.

  7. Implicit coupling of turbulent diffusion with chemical reaction mechanisms for prognostic atmospheric dispersion models

    Energy Technology Data Exchange (ETDEWEB)

    Berlowitz, D.R.

    1996-11-01

    In the last few decades the negative impact by humans on the thin atmospheric layer enveloping the earth, the basis for life on this planet, has increased steadily. In order to halt, or at least slow down this development, the knowledge and study of these anthropogenic influence has to be increased and possible remedies have to be suggested. An important tool for these studies are computer models. With their help the atmospheric system can be approximated and the various processes, which have led to the current situation can be quantified. They also serve as an instrument to assess short or medium term strategies to reduce this human impact. However, to assure efficiency as well as accuracy, a careful analysis of the numerous processes involved in the dispersion of pollutants in the atmosphere is called for. This should help to concentrate on the essentials and also prevent excessive usage of sometimes scarce computing resources. The basis of the presented work is the EUMAC Zooming Model (ETM), and particularly the component calculating the dispersion of pollutants in the atmosphere, the model MARS. The model has two main parts: an explicit solver, where the advection and the horizontal diffusion of pollutants are calculated, and an implicit solution mechanism, allowing the joint computation of the change of concentration due to chemical reactions, coupled with the respective influence of the vertical diffusion of the species. The aim of this thesis is to determine particularly the influence of the horizontal components of the turbulent diffusion on the existing implicit solver of the model. Suggestions for a more comprehensive inclusion of the full three dimensional diffusion operator in the implicit solver are made. This is achieved by an appropriate operator splitting. A selection of numerical approaches to tighten the coupling of the diffusion processes with the calculation of the applied chemical reaction mechanisms are examined. (author) figs., tabs., refs.

  8. Noble metal-free hydrazine fuel cell catalysts: EPOC effect in competing chemical and electrochemical reaction pathways.

    Science.gov (United States)

    Sanabria-Chinchilla, Jean; Asazawa, Koichiro; Sakamoto, Tomokazu; Yamada, Koji; Tanaka, Hirohisa; Strasser, Peter

    2011-04-13

    We report the discovery of a highly active Ni-Co alloy electrocatalyst for the oxidation of hydrazine (N(2)H(4)) and provide evidence for competing electrochemical (faradaic) and chemical (nonfaradaic) reaction pathways. The electrochemical conversion of hydrazine on catalytic surfaces in fuel cells is of great scientific and technological interest, because it offers multiple redox states, complex reaction pathways, and significantly more favorable energy and power densities compared to hydrogen fuel. Structure-reactivity relations of a Ni(60)Co(40) alloy electrocatalyst are presented with a 6-fold increase in catalytic N(2)H(4) oxidation activity over today's benchmark catalysts. We further study the mechanistic pathways of the catalytic N(2)H(4) conversion as function of the applied electrode potential using differentially pumped electrochemical mass spectrometry (DEMS). At positive overpotentials, N(2)H(4) is electrooxidized into nitrogen consuming hydroxide ions, which is the fuel cell-relevant faradaic reaction pathway. In parallel, N(2)H(4) decomposes chemically into molecular nitrogen and hydrogen over a broad range of electrode potentials. The electroless chemical decomposition rate was controlled by the electrode potential, suggesting a rare example of a liquid-phase electrochemical promotion effect of a chemical catalytic reaction ("EPOC"). The coexisting electrocatalytic (faradaic) and heterogeneous catalytic (electroless, nonfaradaic) reaction pathways have important implications for the efficiency of hydrazine fuel cells. © 2011 American Chemical Society

  9. Chemical Reactions Catalyzed by Metalloporphyrin-Based Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Kelly Aparecida Dias de Freitas Castro

    2013-06-01

    Full Text Available The synthetic versatility and the potential application of metalloporphyrins (MP in different fields have aroused researchers’ interest in studying these complexes, in an attempt to mimic biological systems such as cytochrome P-450. Over the last 40 years, synthetic MPs have been mainly used as catalysts for homogeneous or heterogeneous chemical reactions. To employ them in heterogeneous catalysis, chemists have prepared new MP-based solids by immobilizing MP onto rigid inorganic supports, a strategy that affords hybrid inorganic-organic materials. More recently, materials obtained by supramolecular assembly processes and containing MPs as building blocks have been applied in a variety of areas, like gas storage, photonic devices, separation, molecular sensing, magnets, and heterogeneous catalysis, among others. These coordination polymers, known as metal-organic frameworks (MOFs, contain organic ligands or complexes connected by metal ions or clusters, which give rise to a 1-, 2- or 3-D network. These kinds of materials presents large surface areas, Brønsted or redox sites, and high porosity, all of which are desirable features in catalysts with potential use in heterogeneous phases. Building MOFs based on MP is a good way to obtain solid catalysts that offer the advantages of bioinspired systems and zeolitic materials. In this mini review, we will adopt a historical approach to present the most relevant MP-based MOFs applicable to catalytic reactions such as oxidation, reduction, insertion of functional groups, and exchange of organic functions.

  10. Flame Atmospheric Pressure Chemical Ionization Coupled with Negative Electrospray Ionization Mass Spectrometry for Ion Molecule Reactions

    Science.gov (United States)

    Cheng, Sy-Chyi; Bhat, Suhail Muzaffar; Shiea, Jentaie

    2017-07-01

    Flame atmospheric pressure chemical ionization (FAPCI) combined with negative electrospray ionization (ESI) mass spectrometry was developed to detect the ion/molecule reactions (IMRs) products between nitric acid (HNO3) and negatively charged amino acid, angiotensin I (AI) and angiotensin II (AII), and insulin ions. Nitrate and HNO3-nitrate ions were detected in the oxyacetylene flame, suggesting that a large quantity of nitric acid (HNO3) was produced in the flame. The HNO3 and negatively charged analyte ions produced by a negative ESI source were delivered into each arm of a Y-shaped stainless steel tube where they merged and reacted. The products were subsequently characterized with an ion trap mass analyzer attached to the exit of the Y-tube. HNO3 showed the strongest affinity to histidine and formed (Mhistidine-H+HNO3)- complex ions, whereas some amino acids did not react with HNO3 at all. Reactions between HNO3 and histidine residues in AI and AII resulted in the formation of dominant [MAI-H+(HNO3)]- and [MAII-H+(HNO3)]- ions. Results from analyses of AAs and insulin indicated that HNO3 could not only react with basic amino acid residues, but also with disulfide bonds to form [M-3H+(HNO3)n]3- complex ions. This approach is useful for obtaining information about the number of basic amino acid residues and disulfide bonds in peptides and proteins.

  11. Amoeba-Inspired Heuristic Search Dynamics for Exploring Chemical Reaction Paths.

    Science.gov (United States)

    Aono, Masashi; Wakabayashi, Masamitsu

    2015-09-01

    We propose a nature-inspired model for simulating chemical reactions in a computationally resource-saving manner. The model was developed by extending our previously proposed heuristic search algorithm, called "AmoebaSAT [Aono et al. 2013]," which was inspired by the spatiotemporal dynamics of a single-celled amoeboid organism that exhibits sophisticated computing capabilities in adapting to its environment efficiently [Zhu et al. 2013]. AmoebaSAT is used for solving an NP-complete combinatorial optimization problem [Garey and Johnson 1979], "the satisfiability problem," and finds a constraint-satisfying solution at a speed that is dramatically faster than one of the conventionally known fastest stochastic local search methods [Iwama and Tamaki 2004] for a class of randomly generated problem instances [ http://www.cs.ubc.ca/~hoos/5/benchm.html ]. In cases where the problem has more than one solution, AmoebaSAT exhibits dynamic transition behavior among a variety of the solutions. Inheriting these features of AmoebaSAT, we formulate "AmoebaChem," which explores a variety of metastable molecules in which several constraints determined by input atoms are satisfied and generates dynamic transition processes among the metastable molecules. AmoebaChem and its developed forms will be applied to the study of the origins of life, to discover reaction paths for which expected or unexpected organic compounds may be formed via unknown unstable intermediates and to estimate the likelihood of each of the discovered paths.

  12. Sensitivity of polar stratospheric ozone loss to uncertainties in chemical reaction kinetics

    Directory of Open Access Journals (Sweden)

    M. L. Santee

    2009-11-01

    Full Text Available The impact and significance of uncertainties in model calculations of stratospheric ozone loss resulting from known uncertainty in chemical kinetics parameters is evaluated in trajectory chemistry simulations for the Antarctic and Arctic polar vortices. The uncertainty in modeled ozone loss is derived from Monte Carlo scenario simulations varying the kinetic (reaction and photolysis rate parameters within their estimated uncertainty bounds. Simulations of a typical winter/spring Antarctic vortex scenario and Match scenarios in the Arctic produce large uncertainty in ozone loss rates and integrated seasonal loss. The simulations clearly indicate that the dominant source of model uncertainty in polar ozone loss is uncertainty in the Cl2O2 photolysis reaction, which arises from uncertainty in laboratory-measured molecular cross sections at atmospherically important wavelengths. This estimated uncertainty in JCl2O2 from laboratory measurements seriously hinders our ability to model polar ozone loss within useful quantitative error limits. Atmospheric observations, however, suggest that the Cl2O2 photolysis uncertainty may be less than that derived from the lab data. Comparisons to Match, South Pole ozonesonde, and Aura Microwave Limb Sounder (MLS data all show that the nominal recommended rate simulations agree with data within uncertainties when the Cl2O2 photolysis error is reduced by a factor of two, in line with previous in situ ClOx measurements. Comparisons to simulations using recent cross sections from Pope et al. (2007 are outside the constrained error bounds in each case. Other reactions producing significant sensitivity in polar ozone loss include BrO + ClO and its branching ratios. These uncertainties challenge our confidence in modeling polar ozone depletion and projecting future changes in response to changing halogen

  13. In situ laser measurement of oxygen concentration and flue gas temperature utilizing chemical reaction kinetics.

    Science.gov (United States)

    Viljanen, J; Sorvajärvi, T; Toivonen, J

    2017-12-01

    Combustion research requires detailed localized information on the dynamic combustion conditions to improve the accuracy of the simulations and, hence, improve the performance of the combustion processes. We have applied chemical reaction kinetics of potassium to measure the local temperature and O 2 concentration in flue gas. An excess of free atomic potassium is created in the measurement volume by a photofragmenting precursor molecule such as potassium chloride or KOH which are widely released from solid fuels. The decay of the induced potassium concentration is followed with an absorption measurement using a narrow-linewidth diode laser. The temperature and O 2 concentration are solved from the decay curve features using equations obtained from calibration measurements in a temperature range of 800°C-1000°C and in O 2 concentrations of 0.1%-21%. The local flue gas temperature and O 2 concentration were recorded in real time during devolatilization, char burning, and ash cooking phases of combustion in a single-particle reactor with a 5 Hz repetition rate. The method can be further extended to other target species and applications where the chemical dynamics can be disturbed with photofragmentation.

  14. Chemical mechanisms and reaction rates for the initiation of hot corrosion of IN-738

    Science.gov (United States)

    Fryburg, G. C.; Kohl, F. J.; Stearns, C. A.

    1984-01-01

    Sodium-sulfate-induced hot corrosion of preoxidized IN-738 was studied at 975 C with special emphasis placed on the processes occurring during the long induction period. Thermogravimetric tests were run for predetermined periods of time, and then one set of specimens was washed with water. Chemical analysis of the wash solutions yielded information about water soluble metal salts and residual sulfate. A second set of samples was cross sectioned dry and polished in a nonaqueous medium. Element distributions within the oxide scale were obtained from electron microprobe X-ray micrographs. Evolution of SO was monitored throughout the thermogravimetric tests. Kinetic rate studies were performed for several pertinent processes; appropriate rate constants were obtained from the following chemical reactions: Cr2O3 + 2 Na2SO4(1) + 3/2 O2 yields 2 Na2CrO4(1) + 2 SO3(g)n TiO2 + Na2SO4(1) yields Na2O(TiO2)n + SO3(g)n TiO2 + Na2CrO4(1) yields Na2O(TiO2)n + CrO3(g).

  15. Nonequilibrium Thermodynamic Formalism of Nonlinear Chemical Reaction Systems with Waage-Guldberg's Law of Mass Action

    CERN Document Server

    Ge, Hao

    2016-01-01

    Macroscopic entropy production $\\sigma^{(tot)}$ in the general nonlinear isothermal chemical reaction system with mass action kinetics is decomposed into a free energy dissipation and a house-keeping heat: $\\sigma^{(tot)}=\\sigma^{(fd)}+\\sigma^{(hk)}$; $\\sigma^{(fd)}=-\\rd A/\\rd t$, where $A$ is a generalized free enegy function. This yields a novel nonequilibrium free energy balance equation $\\rd A/\\rd t=-\\sigma^{(tot)}+\\sigma^{(hk)}$, which is on a par with celebrated entropy balance equation $\\rd S/\\rd t=\\sigma^{(tot)}+\\eta^{(ex)}$ where $\\eta^{(ex)}$ is the rate of entropy exchange with the environment.For kinetic system with complex balance,$\\sigma^{(fd)},\\sigma^{(hk)}\\ge 0$: $\\sigma^{(fd)}$ characterizes the irreversibility of a transient relaxation kinetics; while $\\sigma^{(hk)}$ is positive even in a steady state, representing irreversibility in open,driven chemical systems with a chemostat.For kinetic system withoutcomplex balance, negative $\\sigma^{(fd)}$ is a necessary condition for multistability, w...

  16. Carbon-Heteroatom Bond Formation by an Ultrasonic Chemical Reaction for Energy Storage Systems.

    Science.gov (United States)

    Kim, Hyun-Tak; Shin, HyeonOh; Jeon, In-Yup; Yousaf, Masood; Baik, Jaeyoon; Cheong, Hae-Won; Park, Noejung; Baek, Jong-Beom; Kwon, Tae-Hyuk

    2017-12-01

    The direct formation of CN and CO bonds from inert gases is essential for chemical/biological processes and energy storage systems. However, its application to carbon nanomaterials for improved energy storage remains technologically challenging. A simple and very fast method to form CN and CO bonds in reduced graphene oxide (RGO) and carbon nanotubes (CNTs) by an ultrasonic chemical reaction is described. Electrodes of nitrogen- or oxygen-doped RGO (N-RGO or O-RGO, respectively) are fabricated via the fixation between N2 or O2 carrier gas molecules and ultrasonically activated RGO. The materials exhibit much higher capacitance after doping (133, 284, and 74 F g-1 for O-RGO, N-RGO, and RGO, respectively). Furthermore, the doped 2D RGO and 1D CNT materials are prepared by layer-by-layer deposition using ultrasonic spray to form 3D porous electrodes. These electrodes demonstrate very high specific capacitances (62.8 mF cm-2 and 621 F g-1 at 10 mV s-1 for N-RGO/N-CNT at 1:1, v/v), high cycling stability, and structural flexibility. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Hybrid models for chemical reaction networks: Multiscale theory and application to gene regulatory systems.

    Science.gov (United States)

    Winkelmann, Stefanie; Schütte, Christof

    2017-09-21

    Well-mixed stochastic chemical kinetics are properly modeled by the chemical master equation (CME) and associated Markov jump processes in molecule number space. If the reactants are present in large amounts, however, corresponding simulations of the stochastic dynamics become computationally expensive and model reductions are demanded. The classical model reduction approach uniformly rescales the overall dynamics to obtain deterministic systems characterized by ordinary differential equations, the well-known mass action reaction rate equations. For systems with multiple scales, there exist hybrid approaches that keep parts of the system discrete while another part is approximated either using Langevin dynamics or deterministically. This paper aims at giving a coherent overview of the different hybrid approaches, focusing on their basic concepts and the relation between them. We derive a novel general description of such hybrid models that allows expressing various forms by one type of equation. We also check in how far the approaches apply to model extensions of the CME for dynamics which do not comply with the central well-mixed condition and require some spatial resolution. A simple but meaningful gene expression system with negative self-regulation is analysed to illustrate the different approximation qualities of some of the hybrid approaches discussed. Especially, we reveal the cause of error in the case of small volume approximations.

  18. Theoretical considerations of Flow Injection Analysis in the Absence of Chemical Reactions

    DEFF Research Database (Denmark)

    Andersen, Jens Enevold Thaulov

    2000-01-01

    The fundamental mechanism of flow injection analysis (FIA) is assumed to be simple dissusion and the response of the detector is included in a model description that provide information about the shape of the FIA peak in terms of, basically, five parameters. Two of the five parameters are associa......The fundamental mechanism of flow injection analysis (FIA) is assumed to be simple dissusion and the response of the detector is included in a model description that provide information about the shape of the FIA peak in terms of, basically, five parameters. Two of the five parameters...... are associated with the compound while the rest yield information about the solvent and friction. By introducing a kinetic-diffusion coefficient, it is shown that the shape of the FIA peak is well described by the theory for diffusion of K3(Fe(CN)6), K2CrO4 and Ni(NO3)2 in distilled water. It is suggested...... that any deviation from the features of the present model and the results of a tentative chemical reaction with one of the test compounds, is related to chemical kinetics....

  19. Hybrid models for chemical reaction networks: Multiscale theory and application to gene regulatory systems

    Science.gov (United States)

    Winkelmann, Stefanie; Schütte, Christof

    2017-09-01

    Well-mixed stochastic chemical kinetics are properly modeled by the chemical master equation (CME) and associated Markov jump processes in molecule number space. If the reactants are present in large amounts, however, corresponding simulations of the stochastic dynamics become computationally expensive and model reductions are demanded. The classical model reduction approach uniformly rescales the overall dynamics to obtain deterministic systems characterized by ordinary differential equations, the well-known mass action reaction rate equations. For systems with multiple scales, there exist hybrid approaches that keep parts of the system discrete while another part is approximated either using Langevin dynamics or deterministically. This paper aims at giving a coherent overview of the different hybrid approaches, focusing on their basic concepts and the relation between them. We derive a novel general description of such hybrid models that allows expressing various forms by one type of equation. We also check in how far the approaches apply to model extensions of the CME for dynamics which do not comply with the central well-mixed condition and require some spatial resolution. A simple but meaningful gene expression system with negative self-regulation is analysed to illustrate the different approximation qualities of some of the hybrid approaches discussed. Especially, we reveal the cause of error in the case of small volume approximations.

  20. Le transfert de la direction des activités vers des institutions ...

    International Development Research Centre (IDRC) Digital Library (Canada)

    de l'Afrique et enrichir sa base de connaissances. Le transfert de la direction des activités vers des ... pour les gouvernorats de la côte nord du Maroc, un projet ayant peaufiné un modèle prédictif d'épidémie de ... données météorologiques et du savoir autochtone aux prévisions climatiques saisonnières pour le secteur ...

  1. Transfert du Tendon du Muscle Jambier Postérieur : à propos de 24 ...

    African Journals Online (AJOL)

    De janvier 1981 à mars 2007, 24 patients souffrants de paralysie irréversible du SPE, ont bénéficié d'une chirurgie de transfert du tendon du muscle jambier postérieur. Les résultats fonctionnels de cette étude rétrospective ont été quantifiiés par la méthode d'évaluation fonctionnelle de STANMORE. Il s'agissait de 14 ...

  2. Static diode pumped alkali lasers: Model calculations of the effects of heating, ionization, high electronic excitation and chemical reactions

    Science.gov (United States)

    Barmashenko, B. D.; Rosenwaks, S.; Heaven, M. C.

    2013-04-01

    The effects of heating, ionization, high electronic excitation and chemical reactions on the operation of diode pumped alkali lasers (DPALs) with a static, non-flowing gain medium are calculated using a semi-analytical model. Unlike other models, assuming a three-level scheme of the laser and neglecting influence of the temperature on the lasing power, it takes into account the temperature rise and losses of neutral alkali atoms due to ionization and chemical reactions, resulting in decrease of the pump absorption and slope efficiency. Good agreement with measurements in a static DPAL [B.V. Zhdanov, J. Sell, R.J. Knize, Electron. Lett. 44 (2008) 582] is obtained. It is found that the ionization processes have a small effect on the laser operation, whereas the chemical reactions of alkali atoms with hydrocarbons strongly affect the lasing power.

  3. Chemical Reaction CO+OH(•) → CO2+H(•) Autocatalyzed by Carbon Dioxide: Quantum Chemical Study of the Potential Energy Surfaces.

    Science.gov (United States)

    Masunov, Artëm E; Wait, Elizabeth; Vasu, Subith S

    2016-08-04

    The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO2 to OH radical and CO molecule, hydrogen transfer from oxygen to carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO2 medium. It may open a new venue for controlling reaction rates for chemical manufacturing.

  4. Soret and dufour effects on free convection flow of a couple stress fluid in a vertical channel with chemical reaction

    Directory of Open Access Journals (Sweden)

    Srinivasacharya D.

    2013-01-01

    Full Text Available The Soret and Dufour effects in the presence of chemical reaction on natural convection heat and mass transfer of a couple stress fluid in a vertical channel formed by two vertical parallel plates is presented. The governing non-linear partial differential equations are transformed into a system of ordinary differential equations using similarity transformations. The resulting equations are then solved using Homotopy Analysis Method (HAM. Profiles of dimensionless velocity, temperature and concentration are shown graphically for various values of Dufour number, Soret number, Couple stress parameter and chemical reaction parameter.

  5. Effects of Chemical Reaction on Dissipative Radiative MHD Flow through a Porous Medium over a Nonisothermal Stretching Sheet

    Directory of Open Access Journals (Sweden)

    S. Mohammed Ibrahim

    2014-01-01

    Full Text Available The steady two-dimensional radiative MHD boundary layer flow of an incompressible, viscous, electrically conducting fluid caused by a nonisothermal linearly stretching sheet placed at the bottom of fluid saturated porous medium in the presence of viscous dissipation and chemical reaction is studied. The governing system of partial differential equations is converted to ordinary differential equations by using the similarity transformations, which are then solved by shooting method. The dimensionless velocity, temperature, and concentration are computed for different thermophysical parameters, namely, the magnetic parameter, permeability parameter, radiation parameter, wall temperature parameter, Prandtl number, Eckert number, Schmidt number, and chemical reaction.

  6. Effect of temperature on a free energy and equilibrium constants during dry flue gas desulphurisation chemical reactions

    Directory of Open Access Journals (Sweden)

    Kuburović Miloš

    2002-01-01

    Full Text Available During dry flue gas desulphurisation (FGD dry particles of reagents are inserted (injected in the stream of flue gas, where they bond SO2. As reagents, the most often are used compounds of calcium (CaCO3, CaO or Ca(OH2. Knowledge of free energy and equilibrium constants of chemical reactions during dry FGD is necessary for understanding of influence of flue gas temperature to course of these chemical reactions as well as to SO2 bonding from flue gases.

  7. LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 3: Illustrative test problems

    Science.gov (United States)

    Bittker, David A.; Radhakrishnan, Krishnan

    1994-01-01

    LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 3 of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part 3 explains the kinetics and kinetics-plus-sensitivity analysis problems supplied with LSENS and presents sample results. These problems illustrate the various capabilities of, and reaction models that can be solved by, the code and may provide a convenient starting point for the user to construct the problem data file required to execute LSENS. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

  8. Adapter ses méthodes de détermination de prix de transfert pour éroder sa base fiscale : le cas Starbucks

    OpenAIRE

    Quévy, Victor

    2017-01-01

    Ce mémoire s’articule en deux parties. La première, théorique, analysera les prix de transfert via les différents rapports fournis par l’OCDE en se concentrant sur les actions de son plan de lutte contre les pratiques d’érosion fiscales (BEPS) qui concernent les prix de transfert. S’en suivra une analyse des méthodes de valorisation des prix de transfert pour pouvoir les utiliser dans la partie pratique et aussi leurs usages abusifs pour voir dans quelle mesure les multinationales peuvent s’e...

  9. Effect of water losses by evaporation and chemical reaction in an industrial slaker reactor

    Directory of Open Access Journals (Sweden)

    Ricardo Andreola

    2007-03-01

    Full Text Available A dynamic model of the slaker reactor was developed and validated for Klabin Paraná Papéis causticizing system, responsable for white liquor generation used by the plant. The model considered water losses by evaporation and chemical reaction. The model showed a good agreement with the industrial plant measures of active alkali, total titratable alkali and temperature, without the need of adjustment of any parameter. The simulated results showed that the water consumption by the slaking reaction and evaporation exerted significant influence on the volumetric flow rate of limed liquor, which imposed a decrease of 4.6% in the amount of water in reactor outlet.Foi desenvolvido e testado um modelo dinâmico do reator de apagamento do sistema de caustificação da Klabin Paraná Papéis, responsável pela geração do licor branco utilizado na planta. O modelo contempla perdas de água por evaporação e por reação química e apresentou boa concordância com dados industriais de álcali ativo, álcali total titulável e temperatura, sem a necessidade de ajuste de nenhum parâmetro. Os resultados obtidos a partir de simulações revelam que o consumo de água pela reação de apagamento, bem como pela evaporação, exercem uma influência significativa sobre a vazão volumétrica na saída do reator, impondo uma diminuição de 4,6% sobre o teor de água na corrente de saída do reator em relação à alimentação.

  10. Kinetic modelling of hydro-treatment reactions by study of different chemical groups; Modelisation cinetique des reactions d`hydrotraitement par regroupement en familles chimiques

    Energy Technology Data Exchange (ETDEWEB)

    Bonnardot, J.

    1998-11-19

    Hydro-treatment of petroleum shortcuts permits elimination of unwanted components in order to increase combustion in engine and to decrease atmospheric pollution. Hydro-desulfurization (HDS), Hydro-denitrogenation (HDN) and Hydrogenation of aromatics (HDA) of a LCO (Light Cycle Oil)-Type gas oil have been studied using a new pilot at a fixed temperature with a NiMo/Al{sub 2}O{sub 3} catalyst. A hydrodynamic study showed that reactions occurring in the up-flow fixed bed reactor that has been used during the experiments, were governed exclusively by chemical reaction rates and not by diffusion. Through detailed chemical analysis, height chemical groups have been considered: three aromatics groups, one sulfided group, one nitrogenized and NH{sub 3}, H{sub 2}S, H{sub 2}. Two Langmuir-Hinshelwood-type kinetic models with either one or two types of sites have been established. The model with two types of site - one site of hydrogenation and one site of hydrogenolysis - showed a better fit in the modeling of the experimental results. This model enables to forecast the influence of partial pressure of H{sub 2}S and partial pressure of H{sub 2} on hydro-treatment reactions of a LCO-type gas oil. (author) 119 refs.

  11. Study of the N=28 shell closure by one neutron transfer reaction: astrophysical application and {beta}-{gamma} spectroscopy of neutron rich nuclei around N=32/34 and N=40; Etude de la fermeture de couche N=28 autour du noyau {sub 18}{sup 46}Ar{sub 28} par reaction de transfert d'un neutron: application a l'astrophysique et Spectroscopie {beta}-{gamma} de noyaux riches en neutrons de N=32/34 et N=40

    Energy Technology Data Exchange (ETDEWEB)

    Gaudefroy, L

    2005-09-15

    The study of the N=28 shell closure has been presented as well as its astrophysical implications. Moreover the structure of neutron rich nuclei around N=32/34 and 40 was studied. The N=28 shell closure has been studied trough the one neutron transfer reaction on {sup 44,46}Ar nuclei. Excitation energies of states in {sup 45,47}Ar nuclei have been obtained, as well as their angular momenta and spectroscopic factors. These results were used to show that N=28 is still a good magic number in the argon isotopic chain. We interpreted the evolution of the spin-orbit partner gaps in terms of the tensor monopolar proton-neutron interaction. Thanks to this latter, we showed it is not necessary to summon up a reduction of the intensity of the spin-orbit force in order to explain this evolution in N=29 isotopes from calcium to argon chains. The neutron capture rates on {sup 44,46}Ar have been determined thanks to the results of the transfer reaction. Their influence on the nucleosynthesis of {sup 46,48}Ca was studied. We proposed stellar conditions to account for the abnormal isotopic ratio observed in the Allende meteorite concerning {sup 46,48}Ca isotopes. The beta decay and gamma spectroscopy of neutron rich nuclei in the scandium to cobalt region has been studied. We showed that beta decay process is dominated by the {nu}f{sub 5/2} {yields} {pi}f{sub 7/2} Gamow-Teller transition. Moreover, we demonstrated that the {nu}g{sub 9/2} hinders this process in the studied nuclei, and influences their structure, by implying the existence of isomers. Our results show that N=34 is not a magic number in the titanium chain and the superior ones. (author)

  12. Kinetics of the benzyl + O(3P) reaction: a quantum chemical/statistical reaction rate theory study.

    Science.gov (United States)

    da Silva, Gabriel; Bozzelli, Joseph W

    2012-12-14

    The resonance stabilized benzyl radical is an important intermediate in the combustion of aromatic hydrocarbons and in polycyclic aromatic hydrocarbon (PAH) formation in flames. Despite being a free radical, benzyl is relatively stable in thermal, oxidizing environments, and is predominantly removed through bimolecular reactions with open-shell species other than O(2). In this study the reaction of benzyl with ground-state atomic oxygen, O((3)P), is examined using quantum chemistry and statistical reaction rate theory. C(7)H(7)O energy surfaces are generated at the G3SX level, and include several novel pathways. Transition state theory is used to describe elementary reaction kinetics, with canonical variational transition state theory applied for barrierless O atom association with benzyl. Apparent rate constants and branching ratios to different product sets are obtained as a function of temperature and pressure from solving the time-dependent master equation, with RRKM theory for microcanonical k(E). These simulations indicate that the benzyl + O reaction predominantly forms the phenyl radical (C(6)H(5)) plus formaldehyde (HCHO), with lesser quantities of the C(7)H(6)O products benzaldehyde, ortho-quinone methide, and para-quinone methide (+H), along with minor amounts of the formyl radical (HCO) + benzene. Addition of O((3)P) to the methylene site in benzyl produces a highly vibrationally excited C(7)H(7)O* adduct, the benzoxyl radical, which can β-scission to benzaldehyde + H and phenyl + HCHO. In order to account for the experimental observation of benzene as the major reaction product, a roaming radical mechanism is proposed that converts the nascent products phenyl and HCHO to benzene + HCO. Oxygen atom addition at the ortho and para ring sites in benzyl, which has not been previously considered, is shown to lead to the quinone methides + H; these species are less-stable isomers of benzaldehyde that are proposed as important combustion intermediates, but

  13. Ozonolysis of mixed oleic-acid/stearic-acid particles: reaction kinetics and chemical morphology.

    Science.gov (United States)

    Katrib, Y; Biskos, G; Buseck, P R; Davidovits, P; Jayne, J T; Mochida, M; Wise, M E; Worsnop, D R; Martin, S T

    2005-12-08

    The ozonolysis of mixed oleic-acid/stearic-acid (OL/SA) aerosol particles from 0/100 to 100/0 wt % composition is studied. The magnitude of the divergence of the particle beam inside an aerosol mass spectrometer shows that, in the concentration range 100/0 to 60/40, the mixed OL/SA particles are liquid prior to reaction. Upon ozonolysis, particles having compositions of 75/25 and 60/40 change shape, indicating that they have solidified during reaction. Transmission electron micrographs show that SA(s) forms needles. For particles having compositions of 75/25, 60/40, and greater SA content, the reaction kinetics exhibit an initial fast decay of OL for low O(3) exposure with no further loss of OL at higher O(3) exposures. For compositions from 50/50 to 10/90, the residual OL concentration remains at 28 +/- 2% of its initial value. The initial reactive uptake coefficient for O(3), as determined by OL loss, decreases linearly from 1.25 (+/-0.2) x 10(-3) to 0.60 (+/-0.15) x 10(-3) for composition changes of 100/0 to 60/40. At 50/50 composition, the uptake coefficient drops abruptly to 0.15 (+/-0.1) x 10(-3), and there are no further changes with increased SA content. These observations can be explained with a combination of three postulates: (1) Unreacted mixed particles remain as supersaturated liquids up to 60/40 composition, and the OL in this form rapidly reacts with O(3). (2) SA, as it solidifies, locks into its crystal structure a significant amount of OL, and this OL is completely inaccessible to O(3). (3) Accompanying crystallization, some stearic acid molecules connect as a filamentous network to form a semipermeable gel containing liquid OL but with a reduced uptake coefficient because of the decrease in molecular diffusivity in the gel. An individual particle of 50/50 to 90/10 is hypothesized as a combination of SA crystals having OL impurities (postulate 2) that are partially enveloped by an SA/OL gel (postulate 3) to explain (a) the abrupt drop in the

  14. Transfers in heterogeneous environments; Transferts en milieux heterogenes

    Energy Technology Data Exchange (ETDEWEB)

    Flesselles, J.M. [Saint-Gobain Recherche, 93 - Aubervilliers (France); Gouesbet, G.; Mees, L.; Roze, C.; Girasole, Th.; Grehan, G. [Laboratoire d' Electromagnetisme et Systemes Particulaires (LESP), UMR CNRS 6614, CORIA. Universite de Rouen et INSA de Rouen, 76 - Saint-Etienne du Rouvray (France); Goyheneche, J.M.; Vignoles, G.; Coindreau, O. [Laboratoire des Composites Thermostructuraux (LCTS), UMR 5801, 33 - Pessac (France); Moyne, Ch. [LEMTA (UMR 7563) CNRS-INPL-UHP, 54 - Vandoeuvre les Nancy (France); Coussy, O. [Institut Navier - ENPC, 77 - Marne-la-Vallee (France); Lassabatere, Th. [Electricite de France Les Renardieres, Dept. Materiaux Mecanique des Composants, 77 - Moret sur Loing (France); Tadrist, L. [IUSTI - UMR 6595, 13 - Marseille (France)

    2004-07-01

    This document gathers the articles and transparencies of the invited talks given at the 2004 French congress of thermal engineering about transfers in heterogeneous environment. Content: transfer phenomena in industrial glass furnaces; simple and multiple scattering diagnosis by femto-second pulsed laser: application to particulate diagnoses; thermal modeling of thermo-structural composites; hybrid mixtures theory, average volumic measurement, periodical or stochastic homogenization: advance in scale change processes; thermo-hydro-chemical-mechanical coupling in porous medium: application to young concrete structures and to clay barriers of disposal facilities; transfers and flows in fluidization: recent advances and future challenges. (J.S.)

  15. Chemical modification of a bitumen and its non-fuel uses. [Reactions of tar sand asphaltenes in synthesis of non-fuel products

    Energy Technology Data Exchange (ETDEWEB)

    Moschopedis, S.E.; Speight, J.G.

    1974-01-01

    Simple reactions are described whereby tar sand bitumen can be converted to a whole range of materials. Examples are given to illustrate the non-fuel uses of the products. The following reactions of Athabasca asphaltenes are considered: oxidation, halogenation, sulfonation and sulfomethylation, phosphorylation, hydrogenation, reactions with S and O, reactions with metal salts, and miscellaneous chemical conversions. (JGB)

  16. Energetic efficiency of mass transfer accompanied by chemical reactions in liquid-liquid systems

    Directory of Open Access Journals (Sweden)

    Jasińska Magdalena

    2017-09-01

    Full Text Available Energetic efficiency depicting the fraction of energy dissipation rate used to perform processes of drop breakup and mass transfer in two-phase, liquid-liquid systems is considered. Results of experiments carried out earlier in two types of high-shear mixers: an in-line rotor-stator mixer and a batch rotor-stator mixer, have been applied to identify and compare the efficiency of drop breakage and mass transfer in both types of mixers. The applied method is based on experimental determination of both: the product distribution of chemical test reactions and the drop size distributions. Experimental data are interpreted using a multifractal model of turbulence for drop breakage and the model by Favelukis and Lavrenteva for mass transfer. Results show that the energetic efficiency of the in-line mixer is higher than that of the batch mixer; two stator geometries were considered in the case of the batch mixer and the energetic efficiency of the device equipped with a standard emulsor screen (SES was higher than the efficiency of the mixer equipped with a general purpose disintegrating head (GPDH for drop breakup but smaller for mass transfer.

  17. The effect of inquiry-flipped classroom model toward students' achievement on chemical reaction rate

    Science.gov (United States)

    Paristiowati, Maria; Fitriani, Ella; Aldi, Nurul Hanifah

    2017-08-01

    The aim of this research is to find out the effect of Inquiry-Flipped Classroom Models toward Students' Achievement on Chemical Reaction Rate topic. This study was conducted at SMA Negeri 3 Tangerang in Eleventh Graders. The Quasi Experimental Method with Non-equivalent Control Group design was implemented in this study. 72 students as the sample was selected by purposive sampling. Students in experimental group were learned through inquiry-flipped classroom model. Meanwhile, in control group, students were learned through guided inquiry learning model. Based on the data analysis, it can be seen that there is significant difference in the result of the average achievement of the students. The average achievement of the students in inquiry-flipped classroom model was 83,44 and the average achievement of the students in guided inquiry learning model was 74,06. It can be concluded that the students' achievement with inquiry-flipped classroom better than guided inquiry. The difference of students' achievement were significant through t-test which is tobs 3.056 > ttable 1.994 (α = 0.005).

  18. The physical and chemical properties of polymerization reaction for contact lens irradiated by electron beam

    Energy Technology Data Exchange (ETDEWEB)

    Sin, Junghyeok; Jun, Jin [Dongshin Univ., Naju (Korea, Republic of)

    2010-07-01

    Can EB irradiation be possible the polymerization of HEMA without the cross-linker and initiator? The physical and chemical properties of the polymers are compared between the two polymerization methods Discuss the effects of the EB irradiation on the polymerization for having a good physical properties for the both hard and soft contact lens. EB irradiation can be used to the polymerization reaction and the EB polymerization take place at a very short period of time without any cross-linker and initiator and initiator above 100 kGy of EB dose. The polymer synthesized by EB irradiation can improve the physical properties of contact lens {yields} increase of the OH group on the surface by EB irradiation, resulting in increase o the water content and oxygen permeability of the contact lens The contact lens synthesized by EB irradiation could improve the physical properties of the contact lens, and specially can apply to a disposable soft contact lens with high water content and oxygen permeability.

  19. Transformer fault diagnosis based on chemical reaction optimization algorithm and relevance vector machine

    Directory of Open Access Journals (Sweden)

    Luo Wei

    2017-01-01

    Full Text Available Power transformer is one of the most important equipment in power system. In order to predict the potential fault of power transformer and identify the fault types correctly, we proposed a transformer fault intelligent diagnosis model based on chemical reaction optimization (CRO algorithm and relevance vector machine(RVM. RVM is a powerful machine learning method, which can solve nonlinear, high-dimensional classification problems with a limited number of samples. CRO algorithm has well global optimization and simple calculation, so it is suitable to solve parameter optimization problems. In this paper, firstly, a multi-layer RVM classification model was built by binary tree recognition strategy. Secondly, CRO algorithm was adopted to optimize the kernel function parameters which could enhance the performance of RVM classifiers. Compared with IEC three-ratio method and the RVM model, the CRO-RVM model not only overcomes the coding defect problem of IEC three-ratio method, but also has higher classification accuracy than the RVM model. Finally, the new method was applied to analyze a transformer fault case, Its predicted result accord well with the real situation. The research provides a practical method for transformer fault intelligent diagnosis and prediction.

  20. Chemical reactions in the processing of MoSi[sub 2] + carbon compacts

    Energy Technology Data Exchange (ETDEWEB)

    Jacobson, N.S.; Lee, K.N. (NASA Lewis Research Center, Cleveland, OH (United States)); Maloy, S.A.; Heuer, A.H. (Case Western Reserve Univ., Cleveland, OH (United States). Dept. of Materials Science and Engineering)

    1993-08-01

    Hot-pressing of MoSi[sub 2] powders with carbon at high temperatures reduces the siliceous grain boundary phase in the resultant compact. The chemical reactions in this process were examined using the Knudsen cell technique. A 2.3 wt% oxygen MoSi[sub 2] powder and a 0.59 wt% oxygen MoSi[sub 2] powder, both with additions of 2 wt% carbon, were examined. The reduction of the siliceous grain boundary phase was examined at 1,350 K and the resultant P(SiO)/P(CO) ratios interpreted in terms of the SiO(g) and CO(g) isobars on the Si-C-O predominance diagram. The MoSi[sub 2] + carbon mixtures were then heated at the hot-pressing temperature of 2,100 K. Large weight losses were observed and could be correlated with the formation of a low-melting eutectic and the formation and vaporization of SiC.

  1. Analysis of turbulent free jet hydrogen-air diffusion flames with finite chemical reaction rates

    Science.gov (United States)

    Sislian, J. P.

    1978-01-01

    The nonequilibrium flow field resulting from the turbulent mixing and combustion of a supersonic axisymmetric hydrogen jet in a supersonic parallel coflowing air stream is analyzed. Effective turbulent transport properties are determined using the (K-epsilon) model. The finite-rate chemistry model considers eight reactions between six chemical species, H, O, H2O, OH, O2, and H2. The governing set of nonlinear partial differential equations is solved by an implicit finite-difference procedure. Radial distributions are obtained at two downstream locations of variables such as turbulent kinetic energy, turbulent dissipation rate, turbulent scale length, and viscosity. The results show that these variables attain peak values at the axis of symmetry. Computed distributions of velocity, temperature, and mass fraction are also given. A direct analytical approach to account for the effect of species concentration fluctuations on the mean production rate of species (the phenomenon of unmixedness) is also presented. However, the use of the method does not seem justified in view of the excessive computer time required to solve the resulting system of equations.

  2. Chemical Reaction Network Theory elucidates sources of multistability in interferon signaling.

    Science.gov (United States)

    Otero-Muras, Irene; Yordanov, Pencho; Stelling, Joerg

    2017-04-01

    Bistability has important implications in signaling pathways, since it indicates a potential cell decision between alternative outcomes. We present two approaches developed in the framework of the Chemical Reaction Network Theory for easy and efficient search of multiple steady state behavior in signaling networks (both with and without mass conservation), and apply them to search for sources of bistability at different levels of the interferon signaling pathway. Different type I interferon subtypes and/or doses are known to elicit differential bioactivities (ranging from antiviral, antiproliferative to immunomodulatory activities). How different signaling outcomes can be generated through the same receptor and activating the same JAK/STAT pathway is still an open question. Here, we detect bistability at the level of early STAT signaling, showing how two different cell outcomes are achieved under or above a threshold in ligand dose or ligand-receptor affinity. This finding could contribute to explain the differential signaling (antiviral vs apoptotic) depending on interferon dose and subtype (α vs β) observed in type I interferons.

  3. Modeling of mass transfer and chemical reactions in a bubble column reactor using a discrete bubble model

    NARCIS (Netherlands)

    Darmana, D.; Deen, N.G.; Kuipers, J.A.M.

    2004-01-01

    A 3D discrete bubble model is adopted to investigate complex behavior involving hydrodynamics, mass transfer and chemical reactions in a gas-liquid bubble column reactor. In this model a continuum description is adopted for the liquid phase and additionally each individual bubble is tracked in a

  4. Detailed modeling of hydrodynamics mass transfer and chemical reactions in a bubble column using a discrete bubble model

    NARCIS (Netherlands)

    Darmana, D.; Deen, N.G.; Kuipers, J.A.M.

    2005-01-01

    A 3D discrete bubble model is adopted to investigate complex behavior involving hydrodynamics, mass transfer and chemical reactions in a gas¿liquid bubble column reactor. In this model a continuum description is adopted for the liquid phase and additionally each individual bubble is tracked in a

  5. Influence of chemical structure on hypersensitivity reactions induced by antiepileptic drugs: the role of the aromatic ring.

    NARCIS (Netherlands)

    Handoko, K.B.; Puijenbroek, E.P. van; Bijl, A.H.; Hermens, W.A.; Rijkom, JE Zwart-van; Hekster, Y.A.; Egberts, T.C.G.

    2008-01-01

    OBJECTIVE: Antiepileptic drugs (AEDs) can cause various 'idiosyncratic' hypersensitivity reactions, i.e. the mechanism by which AEDs induce hypersensitivity is unknown. The aim of this study was to assess whether the presence of an aromatic ring as a commonality in chemical structures of AEDs can

  6. Influence of chemical structure on hypersensitivity reactions induced by antiepileptic drugs : the role of the aromatic ring

    NARCIS (Netherlands)

    Handoko, Kim B; van Puijenbroek, Eugène P; Bijl, Annemarie H; Hermens, Walter A J J; Zwart-van Rijkom, Jeannette E F; Hekster, Yechiel A; Egberts, Toine C G

    2008-01-01

    OBJECTIVE: Antiepileptic drugs (AEDs) can cause various 'idiosyncratic' hypersensitivity reactions, i.e. the mechanism by which AEDs induce hypersensitivity is unknown. The aim of this study was to assess whether the presence of an aromatic ring as a commonality in chemical structures of AEDs can

  7. A chemical and pharmacological study on the role of catecholamines in the dispersion reaction of Xenopus laevis

    NARCIS (Netherlands)

    Brouwer, E.

    Chemical analyses have been made of dopamine in the skin of black backgroundapted Xenopus laevis treated with α-methyl-p-tyrosine (α-MPT), an inhibitor of tyrosine hydroxylase, and without such treatment. Based on the assumption that dopamine is involved in the dispersion reaction induced by MSH,

  8. Direct reaction field force field : A consistent way to connect and combine quantum-chemical and classical descriptions of molecules

    NARCIS (Netherlands)

    Duijnen , van Piet Th.; de Vries, A.H.

    1996-01-01

    The direct reaction field (DRF) force field gives a classical description of intermolecular interactions based on ab initio quantum-chemical descriptions of matter. The parameters of the DRF force field model molecular electrostatic and response properties, which are represented by distributed

  9. Influence of reactions heats on variation of radius, temperature, pressure and chemical species amounts within a single acoustic cavitation bubble.

    Science.gov (United States)

    Kerboua, Kaouther; Hamdaoui, Oualid

    2018-03-01

    The scientific interest toward the study of acoustic bubble is mainly explained by its practical benefit in providing a reactional media favorable to the rapid evolution of chemical mechanism. The evolution of this mechanism is related to the simultaneous and dependent variation of the volume, temperature and pressure within the bubble, retrieved by the resolution of a differential equations system, including among others the thermal balance. This last one is subject to different assumptions, some authors deem simply that the temperature varies adiabatically during the collapsing phase, without considering the reactions heat of the studied mechanism. This paper aims to evaluate the pertinence of neglecting reactions heats in the thermal balance, by analyzing their effect on the variation of radius, temperature, pressure and chemical species amounts. The results show that the introduction of reactions heats conducts to a decrease of the temperature, an increase of the pressure and a reduction of the bubble volume. As a consequence, this leads to a drop of the quantities of free radicals produced by the chemical mechanism evolving within the bubble. This paper also proved that the impact of the consideration of reactions heats is dependent of the frequency and the acoustic amplitude of the ultrasonic wave. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid

    Directory of Open Access Journals (Sweden)

    Andri Cahyo Kumoro

    2015-03-01

    Full Text Available Acetylation is one of the common methods of modifying starch properties by introducing acetil (CH3CO groups to starch molecules at low temperatures. While most acetylation is conducted using starch as anhidroglucose source and acetic anhydride or vinyl acetate as nucleophilic agents, this work employ reactants, namely flour and glacial acetic acid. The purpose of this work are to study the effect of pH reaction and GAA/GF mass ratio on the rate of acetylation reaction and to determine its rate constants. The acetylation of gadung flour with glacial acetic acid in the presence of sodium hydroxide as a homogenous catalyst was studied at ambient temperature with pH ranging from 8-10 and different mass ratio of acetic acid : gadung flour (1:3; 1:4; and 1:5. It was found that increasing pH, lead to increase the degree of substitution, while increasing GAA/GF mass ratio caused such decreases in the degree of substitution, due to the hydrolysis of the acetylated starch. The desired starch acetylation reaction is accompanied by undesirable hydrolysis reaction of the acetylated starch after 40-50 minutes reaction time. Investigation of kinetics of the reaction observed that the value of mass transfer rate constant (Kcs is smaller than the surface reaction rate constant (k. Thus, it can be concluded that rate controlling step is mass transfer.  © 2015 BCREC UNDIP. All rights reservedReceived: 7th August 2014; Revised: 8th September 2014; Accepted: 14th September 2014How to Cite: Kumoro, A.C., Amelia, R. (2015. Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 30-37. (doi:10.9767/bcrec.10.1.7181.30-37Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7181.30-37

  11. Analysis of chemical reaction kinetics of depredating organic pollutants from secondary effluent of wastewater treatment plant in constructed wetlands.

    Science.gov (United States)

    Wang, Hao; Jiang, Dengling; Yang, Yong; Cao, Guoping

    2013-01-01

    Four subsurface constructed wetlands were built to treat the secondary effluent of a wastewater treatment plant in Tangshan, China. The chemical pollutant indexes of chemical oxygen demand (COD) were analyzed to evaluate the removal efficiency of organic pollutants from the secondary effluent of the wastewater treatment plant. In all cases, the subsurface constructed wetlands were efficient in treating organic pollutants. Under the same hydraulic loading condition, the horizontal flow wetlands exhibited better efficiency of COD removal than vertical flow wetlands: the removal rates in horizontal flow wetlands could be maintained at 68.4 ± 2.42% to 92.2 ± 1.61%, compared with 63.8 ± 1.19% to 85.0 ± 1.25% in the vertical flow wetlands. Meanwhile, the chemical reaction kinetics of organic pollutants was analyzed, and the results showed that the degradation courses of the four subsurface wetlands all corresponded with the first order reaction kinetics to a large extent.

  12. Control and Automation of Fluid Flow, Mass Transfer and Chemical Reactions in Microscale Segmented Flow

    Science.gov (United States)

    Abolhasani, Milad

    Flowing trains of uniformly sized bubbles/droplets (i.e., segmented flows) and the associated mass transfer enhancement over their single-phase counterparts have been studied extensively during the past fifty years. Although the scaling behaviour of segmented flow formation is increasingly well understood, the predictive adjustment of the desired flow characteristics that influence the mixing and residence times, remains a challenge. Currently, a time consuming, slow and often inconsistent manual manipulation of experimental conditions is required to address this task. In my thesis, I have overcome the above-mentioned challenges and developed an experimental strategy that for the first time provided predictive control over segmented flows in a hands-off manner. A computer-controlled platform that consisted of a real-time image processing module within an integral controller, a silicon-based microreactor and automated fluid delivery technique was designed, implemented and validated. In a first part of my thesis I utilized this approach for the automated screening of physical mass transfer and solubility characteristics of carbon dioxide (CO2) in a physical solvent at a well-defined temperature and pressure and a throughput of 12 conditions per hour. Second, by applying the segmented flow approach to a recently discovered CO2 chemical absorbent, frustrated Lewis pairs (FLPs), I determined the thermodynamic characteristics of the CO2-FLP reaction. Finally, the segmented flow approach was employed for characterization and investigation of CO2-governed liquid-liquid phase separation process. The second part of my thesis utilized the segmented flow platform for the preparation and shape control of high quality colloidal nanomaterials (e.g., CdSe/CdS) via the automated control of residence times up to approximately 5 minutes. By introducing a novel oscillatory segmented flow concept, I was able to further extend the residence time limitation to 24 hours. A case study of a

  13. Reaction from Dimethyl Carbonate to Diphenyl Carbonate. 1. Experimental Determination of the Chemical Equilibria

    NARCIS (Netherlands)

    Haubrock, J.; Raspe, M.; Versteeg, G.F.; Kooijman, H.A.; Taylor, R.; Hogendoorn, J.A.

    2008-01-01

    New experimental equilibrium data of the reaction of dimethyl carbonate (DMC) and phenol to methyl phenyl carbonate (MPC) and the subsequent disproportion and transesterification reaction of MPC to diphenyl carbonate (DPC) are presented and interpreted in terms of the reaction equilibrium

  14. Reaction from dimethyl carbonate to diphenyl carbonate. 1: Experimental determination of the chemical equilibria

    NARCIS (Netherlands)

    Haubrock, J.; Raspe, M.; Versteeg, Geert; Kooijman, H.A.; Taylor, R.; Hogendoorn, Kees

    2008-01-01

    New experimental equilibrium data of the reaction of dimethyl carbonate (DMC) and phenol to methyl phenyl carbonate (MPC) and the subsequent disproportion and transesterification reaction of MPC to diphenyl carbonate (DPC) are presented and interpreted in terms of the reaction equilibrium

  15. Quantum chemical investigation of the reaction of O (3 2) with ...

    Indian Academy of Sciences (India)

    The reaction of ground-state atomic oxygen [O(32)] with methyl, ethyl, -propyl and isopropyl radicals has been studied using the density functional method and the complete basis set model. The energies of the reactants, products, reaction intermediates and various transition states as well as the reaction enthalpies have ...

  16. Transfers in multiphase environment; Transferts en milieu multiphasique

    Energy Technology Data Exchange (ETDEWEB)

    Marinhas, S.; Delahaye, A.; Fournaison, L. [Cemagref - GPAN, 92 - Antony (France); Dalmazzone, D.; Furst, W. [Ecole Nationale Superieure de Techniques Avancees (ENSTA), 75 - Paris (France); Petitet, J.P. [Laboratoire d' Ingenierie des Materiaux et des Hautes Pressions (LIMHP), CNRS, 93 - Villetaneuse (France); Trinquet, F.; Royon, L.; Kayossi, H.; Guiffant, G. [Laboratoire Matiere Systeme Complexe, CNRS UMR 7057, 75 - Paris (France); El Omari, L.; Baonga, J.B.; Louahlia-Gualous, H.; Panday, P.K. [Institut FEMTO, Dept. C.R.E.S.T.-UTBM-UFC, UMR CNRS 6174, 90 - Belfort (France); Asbik, M.; Ansari, O. [UFR de Modelisation, Optimisation et Ingenierie des Systemes Energetiques, Faculte des Sciences et Techniques, Errachidia (Morocco); Zeghmati, B. [Perpignan Univ., Laboratoire de Mathematiques et Physique des Systemes, Groupe de Mecanique Energetique (M.E.P.S.-G.M.E.), EA 3086, 66 (France); Jamil, A.; Zeraouli, Y.; Dumas, J.P. [Pau Univ. et des Pays de l' Adour, Lab. de Thermique, Energetique et Procedes (LaTEP), 64 (France); Roux, P.; Fichot, F. [CEA Cadarache, Institut de Radioprotection et de Surete Nucleaire (IRSN), 13 - Saint-Paul-lez-Durance (France); Gobin, D.; Goyeau, B. [Laboratoire FAST, 91 - Orsay (France); Quintard, M. [Institut de Mecanique des Fluides, 31 - Toulouse (France); Barthes, M.; Reynard, Ch.; Santini, R.; Tadrist, L. [Laboratoire IUSTI CNRS UMR 6595, 13 - Marseille (France)

    2005-07-01

    This session about heat and mass transfers in multiphase flows gathers 17 papers dealing with: dynamic study of gas hydrate slurry applied to secondary refrigeration; ice melting inside an agitated reactor: experiment and phenomenological approach; experimental and numerical investigation of the local thickness change of a liquid film dripping around an horizontal tube; evaporation of a liquid film dripping around the external wall of an horizontal tube: laminar-turbulent transition phenomenon; coldness distribution by stabilized ice slurries, study of the behaviour under thermal cycling; study of phases disequilibria of two-phase refrigerating fluids; solidification of binary mixtures, influence of the local chemical non-equilibrium and of the effective transport properties; analysis of heat transfers during the growth of a vapor bubble; forecasting of micro-porosity inside Al-Si alloy smelting parts; estimation of a source term in a 2D transient problem: application to electron beam welding; mesoscopic approach of thermal flows; experimental and numerical study of the impact of a circular jet on a heated disc; inverse conduction method for a jet impacting a rotating cylinder: feasibility study; experimental follow up of a fusion-solidification front with and without transfer promoter; parametric study of a latent heat storage tank during horizontal drainage; stability between two layers of a same supercritical fluid; numerical modeling of the heat transfer inside a stainless steel slab. (J.S.)

  17. Treatment of ammonia in waste air using packed column coupling with chemical reaction

    Directory of Open Access Journals (Sweden)

    Thepchai, R.

    2007-05-01

    Full Text Available Ammonia is a common chemical used in various industries. Emission of air contaminated with ammonia to the atmosphere without any treatment causes several effects on human health and environment.A high efficiency method for ammonia removal from waste air is then necessary. In this research, an absorption coupling with chemical reaction was investigated for ammonia removal from waste air using a packedcolumn. The packed column of 10 cm diameter and 200 cm height was packed with 1.4x1.4 cm Raschig rings. Three liquids including water, NaOCl and H2SO4 solution were used as an absorbent for the investigation.The objectives of this research were to determine a suitable absorbent and the optimum condition for ammonia removal from waste air. The packed column was operated at room temperature and atmosphericpressure. The tested conditions were as follows: the gas to liquid ratio (G:L ratio was 35-90 m3 gas/m3 liquid, the inlet concentration of ammonia was 150-500 ppm and the air flow rate was 18 m3/h. The results showedthat the ammonia removal efficiency depends on type of the absorbent and the operating condition. The efficiencies increased with decreasing of G:L ratio and with increasing absorbent concentration. They were70%, 80-92%, and 95-100% for pure water, sodium hypochlorite solution and sulphuric acid solution, respectively. The efficiency decreased with time when water was used as an absorbent while it was almostconstant when NaOCl and H2SO4 solution were applied. The ammonia removal efficiency when using H2SO4 as the absorbent was not dependent on G:L ratio and inlet ammonia concentration, in the range used in thisinvestigation. Since H2SO4 solution gave the highest removal efficiency and can reduce ammonia concentration in waste air to levels which meet the TLV-TWA standard, it is recommended as an absorbent solution forammonia removal from waste air.

  18. Following a Chemical Reaction on the Millisecond Time Scale by Simultaneous X-ray and UV/Vis Spectroscopy.

    Science.gov (United States)

    Olivo, Giorgio; Barbieri, Alessia; Dantignana, Valeria; Sessa, Francesco; Migliorati, Valentina; Monte, Manuel; Pascarelli, Sakura; Narayanan, Theyencheri; Lanzalunga, Osvaldo; Di Stefano, Stefano; D'Angelo, Paola

    2017-07-06

    An innovative approach aimed at disclosing the mechanism of chemical reactions occurring in solution on the millisecond time scale is presented. Time-resolved energy dispersive X-ray absorption and UV/vis spectroscopies with millisecond resolution are used simultaneously to directly follow the evolution of both the oxidation state and the local structure of the metal center in an iron complex. Two redox reactions are studied, the former involving the transformation of FeII into two subsequent FeIII species and the latter involving the more complex FeII-FeIII-FeIV-FeIII sequence. The structural modifications occurring around the iron center are correlated to the reaction mechanisms. This combined approach has the potential to provide unique insights into reaction mechanisms in the liquid phase and represents a new powerful tool to characterize short-lived intermediates that are silent to common spectroscopic techniques.

  19. Harvesting candidate genes responsible for serious adverse drug reactions from a chemical-protein interactome.

    Directory of Open Access Journals (Sweden)

    Lun Yang

    2009-07-01

    Full Text Available Identifying genetic factors responsible for serious adverse drug reaction (SADR is of critical importance to personalized medicine. However, genome-wide association studies are hampered due to the lack of case-control samples, and the selection of candidate genes is limited by the lack of understanding of the underlying mechanisms of SADRs. We hypothesize that drugs causing the same type of SADR might share a common mechanism by targeting unexpectedly the same SADR-mediating protein. Hence we propose an approach of identifying the common SADR-targets through constructing and mining an in silico chemical-protein interactome (CPI, a matrix of binding strengths among 162 drug molecules known to cause at least one type of SADR and 845 proteins. Drugs sharing the same SADR outcome were also found to possess similarities in their CPI profiles towards this 845 protein set. This methodology identified the candidate gene of sulfonamide-induced toxic epidermal necrolysis (TEN: all nine sulfonamides that cause TEN were found to bind strongly to MHC I (Cw*4, whereas none of the 17 control drugs that do not cause TEN were found to bind to it. Through an insight into the CPI, we found the Y116S substitution of MHC I (B*5703 enhances the unexpected binding of abacavir to its antigen presentation groove, which explains why B*5701, not B*5703, is the risk allele of abacavir-induced hypersensitivity. In conclusion, SADR targets and the patient-specific off-targets could be identified through a systematic investigation of the CPI, generating important hypotheses for prospective experimental validation of the candidate genes.

  20. A Novel Approach for Modeling Chemical Reaction in Generalized Fluid System Simulation Program

    Science.gov (United States)

    Sozen, Mehmet; Majumdar, Alok

    2002-01-01

    The Generalized Fluid System Simulation Program (GFSSP) is a computer code developed at NASA Marshall Space Flight Center for analyzing steady state and transient flow rates, pressures, temperatures, and concentrations in a complex flow network. The code, which performs system level simulation, can handle compressible and incompressible flows as well as phase change and mixture thermodynamics. Thermodynamic and thermophysical property programs, GASP, WASP and GASPAK provide the necessary data for fluids such as helium, methane, neon, nitrogen, carbon monoxide, oxygen, argon, carbon dioxide, fluorine, hydrogen, water, a hydrogen, isobutane, butane, deuterium, ethane, ethylene, hydrogen sulfide, krypton, propane, xenon, several refrigerants, nitrogen trifluoride and ammonia. The program which was developed out of need for an easy to use system level simulation tool for complex flow networks, has been used for the following purposes to name a few: Space Shuttle Main Engine (SSME) High Pressure Oxidizer Turbopump Secondary Flow Circuits, Axial Thrust Balance of the Fastrac Engine Turbopump, Pressurized Propellant Feed System for the Propulsion Test Article at Stennis Space Center, X-34 Main Propulsion System, X-33 Reaction Control System and Thermal Protection System, and International Space Station Environmental Control and Life Support System design. There has been an increasing demand for implementing a combustion simulation capability into GFSSP in order to increase its system level simulation capability of a liquid rocket propulsion system starting from the propellant tanks up to the thruster nozzle for spacecraft as well as launch vehicles. The present work was undertaken for addressing this need. The chemical equilibrium equations derived from the second law of thermodynamics and the energy conservation equation derived from the first law of thermodynamics are solved simultaneously by a Newton-Raphson method. The numerical scheme was implemented as a User

  1. A transformation theory of stochastic evolution in Red Moon methodology to time evolution of chemical reaction process in the full atomistic system.

    Science.gov (United States)

    Suzuki, Yuichi; Nagaoka, Masataka

    2017-05-28

    Atomistic information of a whole chemical reaction system, e.g., instantaneous microscopic molecular structures and orientations, offers important and deeper insight into clearly understanding unknown chemical phenomena. In accordance with the progress of a number of simultaneous chemical reactions, the Red Moon method (a hybrid Monte Carlo/molecular dynamics reaction method) is capable of simulating atomistically the chemical reaction process from an initial state to the final one of complex chemical reaction systems. In the present study, we have proposed a transformation theory to interpret the chemical reaction process of the Red Moon methodology as the time evolution process in harmony with the chemical kinetics. For the demonstration of the theory, we have chosen the gas reaction system in which the reversible second-order reaction H2 + I2 ⇌ 2HI occurs. First, the chemical reaction process was simulated from the initial configurational arrangement containing a number of H2 and I2 molecules, each at 300 K, 500 K, and 700 K. To reproduce the chemical equilibrium for the system, the collision frequencies for the reactions were taken into consideration in the theoretical treatment. As a result, the calculated equilibrium concentrations [H2]eq and equilibrium constants Keq at all the temperatures were in good agreement with their corresponding experimental values. Further, we applied the theoretical treatment for the time transformation to the system and have shown that the calculated half-life τ's of [H2] reproduce very well the analytical ones at all the temperatures. It is, therefore, concluded that the application of the present theoretical treatment with the Red Moon method makes it possible to analyze reasonably the time evolution of complex chemical reaction systems to chemical equilibrium at the atomistic level.

  2. Modeling of multiphase flow with solidification and chemical reaction in materials processing

    Science.gov (United States)

    Wei, Jiuan

    Understanding of multiphase flow and related heat transfer and chemical reactions are the keys to increase the productivity and efficiency in industrial processes. The objective of this thesis is to utilize the computational approaches to investigate the multiphase flow and its application in the materials processes, especially in the following two areas: directional solidification, and pyrolysis and synthesis. In this thesis, numerical simulations will be performed for crystal growth of several III-V and II-VI compounds. The effects of Prandtl and Grashof numbers on the axial temperature profile, the solidification interface shape, and melt flow are investigated. For the material with high Prandtl and Grashof numbers, temperature field and growth interface will be significantly influenced by melt flow, resulting in the complicated temperature distribution and curved interface shape, so it will encounter tremendous difficulty using a traditional Bridgman growth system. A new design is proposed to reduce the melt convection. The geometric configuration of top cold and bottom hot in the melt will dramatically reduce the melt convection. The new design has been employed to simulate the melt flow and heat transfer in crystal growth with large Prandtl and Grashof numbers and the design parameters have been adjusted. Over 90% of commercial solar cells are made from silicon and directional solidification system is the one of the most important method to produce multi-crystalline silicon ingots due to its tolerance to feedstock impurities and lower manufacturing cost. A numerical model is developed to simulate the silicon ingot directional solidification process. Temperature distribution and solidification interface location are presented. Heat transfer and solidification analysis are performed to determine the energy efficiency of the silicon production furnace. Possible improvements are identified. The silicon growth process is controlled by adjusting heating power and

  3. Control of chemical chaos through medium viscosity in a batch ferroin-catalysed Belousov-Zhabotinsky reaction.

    Science.gov (United States)

    Budroni, Marcello A; Calabrese, Ilaria; Miele, Ylenia; Rustici, Mauro; Marchettini, Nadia; Rossi, Federico

    2017-12-13

    In this paper we show that the active interplay of nonlinear kinetics and transport phenomena in a chemical oscillator can be exploited to induce and control chaos. To this aim we use as a model system the ferroin-catalysed Belousov-Zhabotinsky (BZ) oscillating reaction, which is known to evolve to characteristic chaotic transient dynamics when carried out under batch and unstirred conditions. In particular, chemical chaos was found to appear and disappear by following a Ruelle-Takens-Newhouse (RTN) scenario. Here we use medium viscosity as a bifurcation parameter to tune the reaction-diffusion-convection (RDC) interplay and force the reaction in a specific sequence of dynamical regimes: either (i) periodic → quasi-periodic → chaotic or (ii) periodic → quasi-periodic or (iii) only periodic. The medium viscosity can be set by adding different amounts of surfactant (sodium dodecyl sulphate), known to have a little impact on the reaction mechanism, above its critical micelle concentration. Experimental results are supported by means of numerical simulations of a RDC model, which combines self-sustained oscillations to the related chemically-induced buoyancy convection.

  4. CERENA: ChEmical REaction Network Analyzer--A Toolbox for the Simulation and Analysis of Stochastic Chemical Kinetics.

    Science.gov (United States)

    Kazeroonian, Atefeh; Fröhlich, Fabian; Raue, Andreas; Theis, Fabian J; Hasenauer, Jan

    2016-01-01

    Gene expression, signal transduction and many other cellular processes are subject to stochastic fluctuations. The analysis of these stochastic chemical kinetics is important for understanding cell-to-cell variability and its functional implications, but it is also challenging. A multitude of exact and approximate descriptions of stochastic chemical kinetics have been developed, however, tools to automatically generate the descriptions and compare their accuracy and computational efficiency are missing. In this manuscript we introduced CERENA, a toolbox for the analysis of stochastic chemical kinetics using Approximations of the Chemical Master Equation solution statistics. CERENA implements stochastic simulation algorithms and the finite state projection for microscopic descriptions of processes, the system size expansion and moment equations for meso- and macroscopic descriptions, as well as the novel conditional moment equations for a hybrid description. This unique collection of descriptions in a single toolbox facilitates the selection of appropriate modeling approaches. Unlike other software packages, the implementation of CERENA is completely general and allows, e.g., for time-dependent propensities and non-mass action kinetics. By providing SBML import, symbolic model generation and simulation using MEX-files, CERENA is user-friendly and computationally efficient. The availability of forward and adjoint sensitivity analyses allows for further studies such as parameter estimation and uncertainty analysis. The MATLAB code implementing CERENA is freely available from http://cerenadevelopers.github.io/CERENA/.

  5. États-Unis / France. Transferts culturels dans le domaine des soins infirmiers, 1854-1938

    Directory of Open Access Journals (Sweden)

    Annick Foucrier

    2012-02-01

    Full Text Available Cet ouvrage a pour but de montrer que la professionnalisation des infirmières françaises (dont l'histoire a souvent été confondue avec l'histoire des infirmières de l'Assistance publique de Paris a, en fait, connu une histoire longue et conflictuelle (1854-1938 au cours de laquelle les influences anglaise et étatsunienne ont été très prégnantes. C'est ce transfert culturel que les deux auteures – Nicole Fouché (docteure en histoire et Evelyne Diebolt (docteur d'État en Histoire – se sont ...

  6. Following the kinetics of a chemical reaction in ultrathin supported polymer films by reliable mass density determination with X-ray reflectivity.

    Science.gov (United States)

    Kontturi, Eero; Lankinen, Aapo

    2010-03-24

    Numerous modern functionalities with ultrathin polymer films involve chemical reactions within the films. X-ray reflectivity can be used to quantitatively follow these chemical reactions by a reliable determination of mass density, which is feasible within certain thickness constraints (e.g., 5-17 nm thickness for common polymer films).

  7. Modeling of Chemical Reactions in Afterburning for the Reduction of N2O

    DEFF Research Database (Denmark)

    Gustavsson, Lennart; Glarborg, Peter; Leckner, Bo

    1996-01-01

    Full scale tests in a 12 MW fluidized bed combustor on reduction of N2O by secondary fuel injection are analyzed in terms a model that involves a detailed reaction mechanism for the gas phase chemistry as well as a description of gas-solid reactions.......Full scale tests in a 12 MW fluidized bed combustor on reduction of N2O by secondary fuel injection are analyzed in terms a model that involves a detailed reaction mechanism for the gas phase chemistry as well as a description of gas-solid reactions....

  8. Structure-reactivity modeling using mixture-based representation of chemical reactions

    Science.gov (United States)

    Polishchuk, Pavel; Madzhidov, Timur; Gimadiev, Timur; Bodrov, Andrey; Nugmanov, Ramil; Varnek, Alexandre

    2017-09-01

    We describe a novel approach of reaction representation as a combination of two mixtures: a mixture of reactants and a mixture of products. In turn, each mixture can be encoded using an earlier reported approach involving simplex descriptors (SiRMS). The feature vector representing these two mixtures results from either concatenated product and reactant descriptors or the difference between descriptors of products and reactants. This reaction representation doesn't need an explicit labeling of a reaction center. The rigorous "product-out" cross-validation (CV) strategy has been suggested. Unlike the naïve "reaction-out" CV approach based on a random selection of items, the proposed one provides with more realistic estimation of prediction accuracy for reactions resulting in novel products. The new methodology has been applied to model rate constants of E2 reactions. It has been demonstrated that the use of the fragment control domain applicability approach significantly increases prediction accuracy of the models. The models obtained with new "mixture" approach performed better than those required either explicit (Condensed Graph of Reaction) or implicit (reaction fingerprints) reaction center labeling.

  9. Sequence-Fenton Reaction for Decreasing Phenol Formation during Benzene Chemical Conversion in Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    SB Mortazavi, A Sabzali, A Rezaee

    2005-04-01

    Full Text Available Advanced oxidation processes such as Fenton reagent generates highly reactive hydroxyl free radicals to oxidize various compounds in the water and wastewater. The efficiency of different Fenton-related oxidative processes such as Fenton, solar-Fenton, UV-Fenton and Fenton reactions in different batch reactors was examined using benzene as pollutant in aqueous solutions. A batch study was conducted to optimize parameters like pH, hydrogen peroxide concentration, temperature, reaction time and ferrous ion concentration governing the Fenton process. The concentrations of produced phenol were measured at the end of the reactions. The role of sequence reaction was tested for decreasing phenol formation during benzene conversion. At optimum conditions, different Fenton-related processes were compared for the degradation of benzene. Increased degradation efficiency was observed in photo-Fenton processes as compared to conventional Fenton process. The formation of phenol in Fenton reaction depended on reaction time, sequence in reaction, purity of hydrogen peroxide and other compounds such as alcohols that contributed into the reaction. In the Fenton process, carboxylic acids like acetic acid and oxalic acid were formed as the end products during the complete degradation of benzene. With the increase in mono-valence, two-valence ions and hardness, Fenton's efficiency decreased, respectively. Sequence Fenton reaction produced less phenol and its end products had smaller COD as compared to conventional Fenton process.

  10. Magnetohydrodynamic Free Convection Flow with Thermal Radiation and Chemical Reaction Effects in the Presence of Variable Suction

    Directory of Open Access Journals (Sweden)

    Usman Halima

    2016-01-01

    Full Text Available The aim of the present study is to investigate the effect of flow parameters on the free convection and mass transfer of an unsteady magnetohydrodynamic flow of an electrically conducting, viscous and incompressible fluid past an infinite vertical porous plate in the presence of variable suction. The thermal radiation and chemical reaction effects are assumed to exist within the channel. Non dimensional partial differential equations of governing equations of flow are solved numerically using Crank Nicolson finite difference method. The skin friction, heat and mass transfer rates as well as the effects of various parameters on velocity, temperature and concentration profiles are analyzed. The signifiant results from this study are that an increase in the values of radiation parameter and chemical reaction parameter causes a reduction in the velocity, temperature and concentration.

  11. Ionic Diffusion and Kinetic Homogeneous Chemical Reactions in the Pore Solution of Porous Materials with Moisture Transport

    DEFF Research Database (Denmark)

    Johannesson, Björn

    2009-01-01

    Results from a systematic continuum mixture theory will be used to establish the governing equations for ionic diffusion and chemical reactions in the pore solution of a porous material subjected to moisture transport. The theory in use is the hybrid mixture theory (HMT), which in its general form...... near equilibrium results obtained from this analysis (using Lagrange multipliers to identify properties) are obtained by expanding linearly about equilibrium. The approach leads to the development of the explicit expressions for the constitutive equations. In this work the derived generalized Fick......’s law of diffusion and the generalized Darcy’s law will be used together with derived constitutive equations for chemical reactions within phases. The mass balance equations for the constituents and the phases together with the constitutive equations gives the coupled set of non-linear differential...

  12. Balanced biochemical reactions: a new approach to unify chemical and biochemical thermodynamics

    National Research Council Canada - National Science Library

    Sabatini, Antonio; Vacca, Alberto; Iotti, Stefano

    2012-01-01

    A novel procedure is presented which, by balancing elements and electric charge of biochemical reactions which occur at constant pH and pMg, allows assessing the thermodynamics properties of reaction Δ(r)G'⁰, Δ(r)H'⁰, Δ(r)S'⁰...

  13. Soret and dufour effects on free convection flow of a couple stress fluid in a vertical channel with chemical reaction

    OpenAIRE

    Srinivasacharya D.; Kaladhar K.

    2013-01-01

    The Soret and Dufour effects in the presence of chemical reaction on natural convection heat and mass transfer of a couple stress fluid in a vertical channel formed by two vertical parallel plates is presented. The governing non-linear partial differential equations are transformed into a system of ordinary differential equations using similarity transformations. The resulting equations are then solved using Homotopy Analysis Method (HAM). Profiles of dimensionless velocity, temperature...

  14. Influences of chemical reaction and wall properties on MHD Peristaltic transport of a Dusty fluid with Heat and Mass transfer

    Directory of Open Access Journals (Sweden)

    R. Muthuraj

    2016-03-01

    Full Text Available The influence of elasticity of flexible walls on peristaltic transport of a dusty fluid with heat and mass transfer in a horizontal channel in the presence of chemical reaction has been investigated under long wavelength approximation. Expressions have been constructed for stream function, temperature and concentration by using perturbation technique. The effects of various parameters on heat and mass transfer characteristics of the flow are discussed through graphs.

  15. CHEMICAL REACTION AND THERMAL RADIATION EFFECTS ON UNSTEADY MHD FLOW OF AN INCOMPRESSIBLE VISCOUS FLUID PAST A MOVING VERTICAL CYLINDER

    OpenAIRE

    B R Sharma*, Nabajyoti Dutta

    2016-01-01

    In the present study, the effects of chemical reaction and thermal radiation on unsteady MHD flow of a viscous, electrically conducting and incompressible fluid mixture past a moving vertical cylinder is studied. The fluid is a gray, absorbing-emitting but non scattering medium and the Rosseland approximation is used to describe the radiative heat flux in the energy equation. The governing dimensionless coupled non-linear partial differential equations are solved numerically using finite di...

  16. Generation of nitrogen functionalities on activated carbons by amidation reactions and Hofmann rearrangement: Chemical and electrochemical characterization

    OpenAIRE

    Mostazo-López, María José; Ruiz Rosas, Ramiro; Morallón Núñez, Emilia; Cazorla Amorós, Diego

    2015-01-01

    Nitrogen functionalization of a highly microporous activated carbon (BET surface area higher than 3000 m2/g) has been achieved using the following sequence of treatments: (i) chemical oxidation using concentrated nitric acid, (ii) amidation by acyl chloride substitution with NH4NO3 and (iii) amination by Hoffman rearrangement. This reaction pathway yielded amide and amine functional groups, and a total nitrogen content higher than 3 at.%. It is achieved producing only a small decrease (20%) o...

  17. Entropy analysis in electrical magnetohydrodynamic (MHD flow of nanofluid with effects of thermal radiation, viscous dissipation, and chemical reaction

    Directory of Open Access Journals (Sweden)

    Yahaya Shagaiya Daniel

    2017-07-01

    Full Text Available The unsteady mixed convection flow of electrical conducting nanofluid and heat transfer due to a permeable linear stretching sheet with the combined effects of an electric field, magnetic field, thermal radiation, viscous dissipation, and chemical reaction have been investigated. A similarity transformation is used to transform the constitutive equations into a system of nonlinear ordinary differential equations. The resultant system of equations is then solved numerically using implicit finite difference method. The velocity, temperature, concentration, entropy generation, and Bejan number are obtained with the dependence of different emerging parameters examined. It is noticed that the velocity is more sensible with high values of electric field and diminished with a magnetic field. The radiative heat transfer and viscous dissipation enhance the heat conduction in the system. Moreover, the impact of mixed convection parameter and Buoyancy ratio parameter on Bejan number profile has reverse effects. A chemical reaction reduced the nanoparticle concentration for higher values. Keywords: Entropy generation, MHD nanofluid, Thermal radiation, Bejan number, Chemical reaction, Viscous dissipation

  18. Combination of cascade chemical reactions with graphene-DNA interaction to develop new strategy for biosensor fabrication.

    Science.gov (United States)

    Zhu, Xiaoli; Sun, Liya; Chen, Yangyang; Ye, Zonghuang; Shen, Zhongming; Li, Genxi

    2013-09-15

    Graphene, a single atom thick and two dimensional carbon nano-material, has been proven to possess many unique properties, one of which is the recent discovery that it can interact with single-stranded DNA through noncovalent π-π stacking. In this work, we demonstrate that a new strategy to fabricate many kinds of biosensors can be developed by combining this property with cascade chemical reactions. Taking the fabrication of glucose sensor as an example, while the detection target, glucose, may regulate the graphene-DNA interaction through three cascade chemical reactions, electrochemical techniques are employed to detect the target-regulated graphene-DNA interaction. Experimental results show that in a range from 5μM to 20mM, the glucose concentration is in a natural logarithm with the logarithm of the amperometric response, suggesting a best detection limit and detection range. The proposed biosensor also shows favorable selectivity, and it has the advantage of no need for labeling. What is more, by controlling the cascade chemical reactions, detection of a variety of other targets may be achieved, thus the strategy proposed in this work may have a wide application potential in the future. Copyright © 2013 Elsevier B.V. All rights reserved.

  19. A single-molecule perspective on the role of solvent hydrogen bonds in protein folding and chemical reactions.

    Science.gov (United States)

    Dougan, Lorna; Koti, Ainavarapu Sri Rama; Genchev, Georgi; Lu, Hui; Fernandez, Julio M

    2008-12-22

    We present an array of force spectroscopy experiments that aim to identify the role of solvent hydrogen bonds in protein folding and chemical reactions at the single-molecule level. In our experiments we control the strength of hydrogen bonds in the solvent environment by substituting water (H(2)O) with deuterium oxide (D(2)O). Using a combination of force protocols, we demonstrate that protein unfolding, protein collapse, protein folding and a chemical reaction are affected in different ways by substituting H(2)O with D(2)O. We find that D(2)O molecules form an integral part of the unfolding transition structure of the immunoglobulin module of human cardiac titin, I27. Strikingly, we find that D(2)O is a worse solvent than H(2)O for the protein I27, in direct contrast with the behaviour of simple hydrocarbons. We measure the effect of substituting H(2)O with D(2)O on the force dependent rate of reduction of a disulphide bond engineered within a single protein. Altogether, these experiments provide new information on the nature of the underlying interactions in protein folding and chemical reactions and demonstrate the power of single-molecule techniques to identify the changes induced by a small change in hydrogen bond strength.

  20. Quantum chemical study of the reactions of Al, AlO and AlOH with H2O2

    Science.gov (United States)

    Sharipov, Alexander S.; Starik, Alexander M.

    2016-02-01

    Quantum chemical calculations with the use of hybrid density functional with perturbative second-order correlation and dispersion correction are carried out to study the reactions of Al, AlO and AlOH with the H2O2 molecule. The values of energy barriers are estimated by means of extrapolation to the basis set limit. The energetically favorable reaction pathways have been revealed during the examination of the potential energy surfaces. Complex character of the processes under study has been established. It has been found that the initial stages of the considered processes are barrierless. Appropriate rate constants for principal channels of the reactions under study have been estimated by using capture model and canonical variational theory. The Arrhenius approximations for these channels have been proposed for the temperature range T = 300-4000 K.

  1. Quantum chemical investigation of the thermal pyrolysis reactions of the carboxylic group in a brown coal model.

    Science.gov (United States)

    Liu, Shengyu; Zhang, Zhiqiang; Wang, Huifang

    2012-01-01

    Different reaction pathways of the carboxylic group in a brown coal model were investigated by applying density function quantum chemical theory, examining the possible cross-linking and decomposition reactions between the hydrogen bonded carboxylic group-carboxylic group and the carboxylic group-hydroxyl group during the thermal pyrolysis process. The results show that bimolecular dehydration and decarboxylation of hydrogen bonded carboxylic groups have distinctly lower activation barriers and therefore, proceed preferentially at low temperature. The esterification reaction between the hydrogen bonded carboxylic group and hydroxyl group, together with unimolecular decarboxylation of isolated single carboxylic groups were also possible at moderate temperature. Aryl-aryl coupling is thought to occur via radical pyrolysis and recombination at relatively high temperature.

  2. LSENS, a general chemical kinetics and sensitivity analysis code for homogeneous gas-phase reactions. 2: Code description and usage

    Science.gov (United States)

    Radhakrishnan, Krishnan; Bittker, David A.

    1994-01-01

    LSENS, the Lewis General Chemical Kinetics Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 2 of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part 2 describes the code, how to modify it, and its usage, including preparation of the problem data file required to execute LSENS. Code usage is illustrated by several example problems, which further explain preparation of the problem data file and show how to obtain desired accuracy in the computed results. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions. Part 1 (NASA RP-1328) derives the governing equations describes the numerical solution procedures for the types of problems that can be solved by lSENS. Part 3 (NASA RP-1330) explains the kinetics and kinetics-plus-sensitivity-analysis problems supplied with LSENS and presents sample results.

  3. Weak Intermolecular Hydrogen Bonds with Fluorine: Detection and Implications for Enzymatic/Chemical Reactions, Chemical Properties, and Ligand/Protein Fluorine NMR Screening.

    Science.gov (United States)

    Dalvit, Claudio; Vulpetti, Anna

    2016-05-23

    It is known that strong hydrogen-bonding interactions play an important role in many chemical and biological systems. However, weak or very weak hydrogen bonds, which are often difficult to detect and characterize, may also be relevant in many recognition and reaction processes. Fluorine serving as a hydrogen-bond acceptor has been the subject of many controversial discussions and there are different opinions about it. It now appears that there is compelling experimental evidence for the involvement of fluorine in weak intramolecular or intermolecular hydrogen bonds. Using established NMR methods, we have previously characterized and measured the strengths of intermolecular hydrogen-bond complexes involving the fluorine moieties CH2 F, CHF2 , and CF3 , and have compared them with the well-known hydrogen-bond complex formed between acetophenone and the strong hydrogen-bond donor p-fluorophenol. We now report evidence for the formation of hydrogen bonds involving fluorine with significantly weaker donors, namely 5-fluoroindole and water. A simple NMR method is proposed for the simultaneous measurement of the strengths of hydrogen bonds between an acceptor and a donor or water. Important implications of these results for enzymatic/chemical reactions involving fluorine, for chemical and physical properties, and for ligand/protein (19) F NMR screening are analyzed through experiments and theoretical simulations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Efficient production of hyperpolarized bicarbonate by chemical reaction on a DNP precursor to measure pH.

    Science.gov (United States)

    Ghosh, Rajat K; Kadlecek, Stephen J; Pourfathi, Mehrdad; Rizi, Rahim R

    2015-11-01

    To produce hyperpolarized bicarbonate indirectly via chemical reaction from a hyperpolarized precursor and utilize it for the simultaneous regional measurement of metabolism and pH. Alpha keto carboxylic acids are first hyperpolarized by dissolution dynamic nuclear polarization (DNP). These precursor molecules are rapidly reacted with hydrogen peroxide (H2O2) to decarboxylate the species, resulting in new target molecules. Unreacted H2O2 is removed from the system by reaction with sulfite. Interrogation of the ratio of dissolved carbon dioxide (CO2) to bicarbonate can be used to determine pH. Conversion of hyperpolarized alpha keto acids to bicarbonate and CO2 results in a minimal loss of the spin order. The reaction can be conducted to completion within seconds and preserves the nuclear spin polarization. Through a rapid chemical reaction, we can conserve the nuclear spin order of a DNP precursor to generate multiple hyperpolarized bioprobes otherwise unamenable to polarization. This indirect technique for the production of hyperpolarized agents can be applied to different precursor compounds to generate additional novel probes. © 2014 Wiley Periodicals, Inc.

  5. Chemical reaction rates of ozone in water infusions of wheat, beech, oak and pine leaves of different ages

    Science.gov (United States)

    Potier, Elise; Loubet, Benjamin; Durand, Brigitte; Flura, Dominique; Bourdat-Deschamps, Marjolaine; Ciuraru, Raluca; Ogée, Jérôme

    2017-02-01

    In this study we present results from a laboratory experiment designed to evaluate the first-order chemical reaction rate (k) of ozone in water films on plant leaves occurring during dew or rain events. Ozone deposition to wet cuticles is indeed known to be a significant pathway of ozone deposition, but the underlying processes are not yet well understood. Leaf infusions obtained by infusing plant leaves with water at room temperature were introduced into a wet effluent denuder fed with a flux of ozone-rich air. Ozone, water vapour concentrations and temperature were measured in both inlet and outlet airflows in order to compute ozone reaction rates kr using an ozone reaction-diffusion model in the water film. Ascorbate solutions were used to validate the set up and led to kr = 3.6 107 M-1 s-1 consistent with the literature. Ozone reaction rates were determined for wheat, beech, oak and pine leaves infusions at several developmental stages, as well as for rain samples. Leaf infusions reaction rates were between 240 s-1 and 3.4 105 s-1 depending on species and developmental stage, while k for rain water ranged from 130 to 830 s-1. Wheat leaves solutions showed significantly (P wheat, k also increased with increasing yellow leaf fraction. Our results are in the range of previously reported ozone deposition on wet leaves in field or chamber studies. Composition of leaves infusions and previous studies on throughfall and dew composition shows that reaction of ozone with inorganic compounds may only explain the smallest measured k. The largest k observed during senescent are most likely due to reaction with organic material. This is confirmed by LC-MS measurements which showed detection of ascorbate and VOCs as well as the reaction products of ozone with these compounds.

  6. Quantum Chemical Study of CH3 + O2 Combustion Reaction System: Catalytic Effects of Additional CO2 Molecule.

    Science.gov (United States)

    Masunov, Artëm E; Wait, Elizabeth; Vasu, Subith S

    2017-08-03

    The supercritical carbon dioxide diluent is used to control the temperature and to increase the efficiency in oxycombustion fossil fuel energy technology. It may affect the rates of combustion by altering mechanisms of chemical reactions, compared to the ones at low CO2 concentrations. Here, we investigate potential energy surfaces of the four elementary reactions in the CH3 + O2 reactive system in the presence of one CO2 molecule. In the case of reaction CH3 + O2 → CH2O + OH (R1 channel), van der Waals (vdW) complex formation stabilizes the transition state and reduces the activation barrier by ∼2.2 kcal/mol. Alternatively, covalently bonded CO2 may form a six-membered ring transition state and reduce the activation barrier by ∼0.6 kcal/mol. In case of reaction CH3 + O2 → CH3O + O (R2 channel), covalent participation of CO2 lowers the barrier for the rate limiting step by 3.9 kcal/mol. This is expected to accelerate the R2 process, important for the branching step of the radical chain reaction mechanism. For the reaction CH3 + O2 → CHO + H2O (R3 channel) with covalent participation of CO2, the activation barrier is lowered by 0.5 kcal/mol. The reaction CH2O + OH → CHO + H2O (R4 channel) involves hydrogen abstraction from formaldehyde by OH radical. Its barrier is reduced from 7.1 to 0.8 kcal/mol by formation of vdW complex with spectator CO2. These new findings are expected to improve the kinetic reaction mechanism describing combustion processes in supercritical CO2 medium.

  7. Note: Reaction of bacteria associated with fish spoilage to chemical and physical stress

    NARCIS (Netherlands)

    Kirby, R.; Silva, da M.; Capell, C.; Vaz-Pires, P.; Luten, J.B.

    2001-01-01

    A cocktail made up of six bacteria isolated from fish was subjected to various heats (30 °C and 60 °C, 20 s) and chemical preservative stresses, alone and in combination. The chemical preservatives tested were potassium sorbate (PS, 1Œ trisodium phosphate (TSP, 10€and tetrasodium pyrophosphate

  8. Numerical techniques for quantitative evaluation of chemical reaction systems with volatile species and their applications to water radiolysis in BWRs

    Science.gov (United States)

    Ibe, Eishi; Uchida, Shunsuke

    1985-02-01

    A mass transfer model in boiling flow was proposed for computer simulation of chemical reaction systems. The model can be applied to a wide variety of chemical engineering applications including nuclear reactor plants. A statistical treatment for simple estimation formulae of distribution of chemical reagents in any plant from the simulated results of a specific plant was also proposed. These two mathematical techniques were applied to water radiolysis in BWR primary systems (Oskarshamn-2 and Dresden-2) to evaluate distributions of oxidizing reagents in the systems. Simulated results from the computer program agreed within a 20% error with measured hydrogen and oxygen concentrations. Hydrogen and oxygen concentrations in Dresden-2 estimated by means of the simplified formulae agreed within 26% error with those of the direct simulation results.

  9. Coherent chemical kinetics as quantum walks. II. Radical-pair reactions in Arabidopsis thaliana.

    Science.gov (United States)

    Chia, A; Górecka, A; Kurzyński, P; Paterek, T; Kaszlikowski, D

    2016-03-01

    We apply the quantum-walk approach proposed in the preceding paper [A. Chia et al., preceding paper, Phys. Rev. E 93, 032407 (2016)] to a radical-pair reaction where realistic estimates for the intermediate transition rates are available. The well-known average hitting time from quantum walks can be adopted as a measure of how quickly the reaction occurs and we calculate this for varying degrees of dephasing in the radical pair. The time for the radical pair to react to a product is found to be independent of the amount of dephasing introduced, even in the limit of no dephasing where the transient population dynamics exhibits strong coherent oscillations. This can be seen to arise from the existence of a rate-limiting step in the reaction and we argue that in such examples, a purely classical model based on rate equations can be used for estimating the time scale of the reaction but not necessarily its population dynamics.

  10. Effect of temperature oscillation on chemical reaction rates in the atmosphere

    Science.gov (United States)

    Eberstein, I. J.

    1974-01-01

    The effect of temperature fluctuations on atmospheric ozone chemistry is examined by considering the Chapman photochemical theory of ozone transport to calculate globally averaged ozone production rates from mean reaction rates, activation energies, and recombination processes.

  11. Sensitivity of Polar Stratospheric Ozone Loss to Uncertainties in Chemical Reaction Kinetics

    Science.gov (United States)

    Kawa, S. Randolph; Stolarksi, Richard S.; Douglass, Anne R.; Newman, Paul A.

    2008-01-01

    Several recent observational and laboratory studies of processes involved in polar stratospheric ozone loss have prompted a reexamination of aspects of our understanding for this key indicator of global change. To a large extent, our confidence in understanding and projecting changes in polar and global ozone is based on our ability to simulate these processes in numerical models of chemistry and transport. The fidelity of the models is assessed in comparison with a wide range of observations. These models depend on laboratory-measured kinetic reaction rates and photolysis cross sections to simulate molecular interactions. A typical stratospheric chemistry mechanism has on the order of 50- 100 species undergoing over a hundred intermolecular reactions and several tens of photolysis reactions. The rates of all of these reactions are subject to uncertainty, some substantial. Given the complexity of the models, however, it is difficult to quantify uncertainties in many aspects of system. In this study we use a simple box-model scenario for Antarctic ozone to estimate the uncertainty in loss attributable to known reaction kinetic uncertainties. Following the method of earlier work, rates and uncertainties from the latest laboratory evaluations are applied in random combinations. We determine the key reactions and rates contributing the largest potential errors and compare the results to observations to evaluate which combinations are consistent with atmospheric data. Implications for our theoretical and practical understanding of polar ozone loss will be assessed.

  12. Chlorination of N-methylacetamide and amide-containing pharmaceuticals. Quantum-chemical study of the reaction mechanism.

    Science.gov (United States)

    Šakić, Davor; Šonjić, Pavica; Tandarić, Tana; Vrček, Valerije

    2014-03-27

    Chlorination of amides is of utmost importance in biochemistry and environmental chemistry. Despite the huge body of data, the mechanism of reaction between amides and hypochlorous acid in aqueous environment remains unclear. In this work, the three different reaction pathways for chlorination of N-methylacetamide by HOCl have been considered: the one-step N-chlorination of the amide, the chlorination via O-chlorinated intermediate, and the N-chlorination of the iminol intermediate. The high-level quantum chemical G3B3 composite procedure, double-hybrid B2-PLYPD, B2K-PLYP methods, and global hybrid M06-2X and BMK methods have been employed. The calculated energy barriers have been compared to the experimental value of ΔG(#)298 ≈ 87 kJ/mol, which corresponds to reaction rate constant k(r) ≈ 0.0036 M(-1) s(-1). Only the mechanism in which the iminol form of N-methylacetamide reacts with HOCl is consistent (ΔG(#)298 = 87.3 kJ/mol at G3B3 level) with experimental results. The analogous reaction mechanism has been calculated as the most favorable pathway in the chlorination of small-sized amides and amide-containing pharmaceuticals: carbamazepine, acetaminophen, and phenytoin. We conclude that the formation of the iminol intermediate followed by its reaction with HOCl is the general mechanism of N-chlorination for a vast array of amides.

  13. RMPCDMD: Simulations of Colloids with Coarse-grained Hydrodynamics, Chemical Reactions and External Fields

    Directory of Open Access Journals (Sweden)

    Pierre de Buyl

    2017-01-01

    Full Text Available The RMPCDMD software package performs hybrid Molecular Dynamics simulations, coupling Multiparticle Collision Dynamics to model the solvent and Molecular Dynamics to model suspended colloids, including hydrodynamics, thermal fluctuations, and chemically active solvent particles and catalytic colloids. The main usage of RMPCDMD is the simulation of chemically powered nanomotors, but other setups are considered: colloids in the presence of a thermal gradients or forced flows. RMPCDMD is developed in Fortran 2008 with OpenMP for multithreaded operation and uses the HDF5-based H5MD file format for storing data. RMPCDMD comes with documentation and a tutorial for the simulation of chemically powered nanomotors.

  14. A New Method for Determining the Nanocrystallite Size Distribution in Systems Where Chemical Reaction between Solid and a Gas Phase Occurs

    Directory of Open Access Journals (Sweden)

    Rafał Pelka

    2013-01-01

    Full Text Available The proposed method, based on measuring the chemical reaction rate in solid phase, is, therefore, limited to such systems where reaction between nanocrystalline materials and a gas phase occurs. Additionally, assumptions of the model of reaction between nanocrystalline materials and a gas phase, where the surface chemical reaction rate is the rate limiting step, are used. As an example of such a reaction, nitriding (with ammonia of the prereduced industrial iron catalysts for ammonia synthesis of different average crystallite sizes was used. To measure the reaction rate, the differential reactor equipped with systems for thermogravimetric measurements and analysis of the chemical composition of the gas phase was used. The crystallites mass and size distributions for the analyzed samples of catalyst were determined.

  15. Improved ADM1 model for anaerobic digestion process considering physico-chemical reactions.

    Science.gov (United States)

    Zhang, Yang; Piccard, Sarah; Zhou, Wen

    2015-11-01

    The "Anaerobic Digestion Model No. 1" (ADM1) was modified in the study by improving the bio-chemical framework and integrating a more detailed physico-chemical framework. Inorganic carbon and nitrogen balance terms were introduced to resolve the discrepancies in the original bio-chemical framework between the carbon and nitrogen contents in the degraders and substrates. More inorganic components and solids precipitation processes were included in the physico-chemical framework of ADM1. The modified ADM1 was validated with the experimental data and used to investigate the effects of calcium ions, magnesium ions, inorganic phosphorus and inorganic nitrogen on anaerobic digestion in batch reactor. It was found that the entire anaerobic digestion process might exist an optimal initial concentration of inorganic nitrogen for methane gas production in the presence of calcium ions, magnesium ions and inorganic phosphorus. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Spontaneous fine-tuning to environment in many-species chemical reaction networks

    Science.gov (United States)

    Horowitz, Jordan M.; England, Jeremy L.

    2017-07-01

    A chemical mixture that continually absorbs work from its environment may exhibit steady-state chemical concentrations that deviate from their equilibrium values. Such behavior is particularly interesting in a scenario where the environmental work sources are relatively difficult to access, so that only the proper orchestration of many distinct catalytic actors can power the dissipative flux required to maintain a stable, far-from-equilibrium steady state. In this article, we study the dynamics of an in silico chemical network with random connectivity in an environment that makes strong thermodynamic forcing available only to rare combinations of chemical concentrations. We find that the long-time dynamics of such systems are biased toward states that exhibit a fine-tuned extremization of environmental forcing.

  17. Spontaneous fine-tuning to environment in many-species chemical reaction networks.

    Science.gov (United States)

    Horowitz, Jordan M; England, Jeremy L

    2017-07-18

    A chemical mixture that continually absorbs work from its environment may exhibit steady-state chemical concentrations that deviate from their equilibrium values. Such behavior is particularly interesting in a scenario where the environmental work sources are relatively difficult to access, so that only the proper orchestration of many distinct catalytic actors can power the dissipative flux required to maintain a stable, far-from-equilibrium steady state. In this article, we study the dynamics of an in silico chemical network with random connectivity in an environment that makes strong thermodynamic forcing available only to rare combinations of chemical concentrations. We find that the long-time dynamics of such systems are biased toward states that exhibit a fine-tuned extremization of environmental forcing.

  18. Insight into shock-induced chemical reaction from the perspective of ring strain and rotation of chemical bonds.

    Science.gov (United States)

    Tan, Bisheng; Long, Xinping; Li, Jinshan; Nie, Fude; Huang, Jinglun

    2012-12-01

    Density functional theory BLYP/DNP and hyperhomodesmotic equations were employed to calculate ring strain energy, the bond dissociation energy of X-NO(2) (X=C, N) and the charges on the nitro groups of several four-membered and six-membered heterocycle compounds. BLYP/DNP and LST/QST + CG method were also applied to calculate bond rotational energy of X-NO(2) (X=C, N) of above mentioned compounds. It indicated that ring strain energy of four-membered heterocycle nitro compounds is apparently higher than that of six-membered heterocycle nitro compounds. Predictably, ring-opening reactions may preferentially occur for those compounds containing higher ring strain energy under shock. In addition, C-NO(2) bonds in these compounds may rotate easier than N-NO(2) bonds in response to the external shock. As for N-NO(2) bonds in these compounds, they also respond to the external shock by the rotation of N-NO(2) bonds, once to the saddle point of the rotational energy barrier, the whole molecule will become relaxed, N-NO(2) bond becomes weaker and eventually leads to the breakage. When one -C=O, -C=NH or -NH(2) group is introduced to the six-membered heterocycle, the charges on the nitro groups of the new compound decrease drastically, and ring strains increase remarkably. It can be predicted that the new compounds will be more sensitive to shock, and the viewpoint is confirmed by the experimental results of shock sensitivity (small scale gap test) of several explosives.

  19. Primary Ion Depletion Kinetics (PIDK) Studies as a New Tool for Investigating Chemical Ionization Fragmentation Reactions with PTR-MS.

    Science.gov (United States)

    Schuhfried, Erna; Märk, Tilmann D; Biasioli, Franco

    2013-01-01

    We report on a new approach for studying fragmentation channels in Proton Transfer Reaction-Mass Spectrometry (PTR-MS), which we name primary ion depletion kinetics (PIDK). PTR-MS is a chemical ionization mass spectrometric (CIMS) technique deploying hydronium ions for the chemical ionization. Induced by extremely high concentrations of analyte M, depletion of the primary ions in the drift tube occurs. This is observed as quasi zero concentration of the primary ion H3O(+), and constant MH(+). Under these non-standard conditions, we find an overall changed fragmentation. We offer two explanations. Either the changed fragmentation pattern is the result of secondary proton transfer reactions. Or, alternatively, the fast depletion of H3O(+) leads to reduced heating of H3O(+) in the drift field, and consequently changed fragmentation following protonation of the analyte M. In any case, we use the observed changes in fragmentation as a successful new approach to fragmentation studies, and term it primary ion depletion kinetics, PIDK. PIDK easily yields an abundance of continuous data points with little deviation, because they are obtained in one experimental run, even for low abundant fragments. This is an advantage over traditional internal kinetic energy variation studies (electric field per number density (E/N) variation studies). Also, some interpretation on the underlying fragmentation reaction mechanisms can be gleamed. We measure low occurring fragmentation (kinetics allows for the identification of dehydrogenation [MH(+) -H2] and adduct formation (RMH(+)) as low abundant fragmentation channels in monosulfides.

  20. Control of chemical reactions with electron beams; Kontrolle chemischer Reaktionen mit Elektronenstrahlung

    Energy Technology Data Exchange (ETDEWEB)

    Boehler, Esther

    2014-03-18

    Interaction between low-energy electrons and molecules can lead to dissociative electron attachment (DEA) or dissociative ionization (DI). In condensed matter, the resulting reactive fragments can attack adjacent molecules to yield larger products. In this thesis, reactions initiated by DEA to acetonitrile in condensed phase have been compared to the known gas phase fragmentation channels. Also, gas phase DEA experiments have been performed on chlorosilanes to study the effect of a variation of the organic ligands on the energy of their molecular orbitals and reactivity in DEA processes. Furthermore, hydroamination reactions induced by DI for different alkenes and amines have been investigated. A similar reaction of ammonia and carbon monoxide was shown to produce formamide (HCONH2), which is the smallest molecule to contain a peptide bond and thus represents an important building block of biologically relevant substances.

  1. Peculiarities of simple and complex chemical reactions in grains of porous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kol`tsov, N.I.; Andreev, V.V. [Chuvash State Univ., Chuvashia (Russian Federation)

    1995-01-01

    The kinetics of simple and consecutive-parallel reactions proceeding in non-isothermal porous catalyst grains of different configurations is considered. Allowance was made for the resistance to the heat-exchange and mass-transfer between the external grain surface and the reaction mixture flow. The effect of several parameters on the catalytic performance, along with the problem of {open_quotes}dead zone{close_quotes} formation are discussed. The optimization conditions of the efficiency factor and selectivity are determined as well.

  2. Chemical reactions of conformationally selected 3-aminophenol molecules in a beam with Coulomb-crystallized Ca+ ions

    Science.gov (United States)

    Rösch, Daniel; Willitsch, Stefan; Chang, Yuan-Pin; Küpper, Jochen

    2014-03-01

    Many molecules exhibit multiple conformers that often easily interconvert under thermal conditions. Therefore, single conformations are difficult to isolate which renders the study of their distinct chemical reactivities challenging. We have recently reported a new experimental method for the characterization of conformer-specific effects in chemical reactions [Y.-P. Chang, K. Długołęcki, J. Küpper, D. Rösch, D. Wild, and S. Willitsch, "Specific chemical reactivities of spatially separated 3-aminophenol conformers with cold Ca+ ions," Science 342, 98-101 (2013)]. Different conformers are spatially separated using inhomogeneous electric fields and reacted with a Coulomb crystal of cold, spatially localized ions in a trap. As a first application, we studied reactions between the two conformers of 3-aminophenol and Ca+. We observed a twofold larger rate constant for the cis compared to the trans conformer which was rationalized in terms of the differences in the long-range ion-molecule interactions. The present article provides a detailed description of the new method and a full account of the experimental results as well as the accompanying theoretical calculations.

  3. On initial steps of chemical prebiotic evolution: Triggering autocatalytic reaction of oligomerization

    Science.gov (United States)

    Bartsev, S. I.; Mezhevikin, V. V.

    2008-12-01

    Searching for extraterrestrial life attracts more and more attention. However this searching hardly can be effective without sufficiently universal concept of life origin, which incidentally tackles a problem of origin of life on the Earth. A concept of initial stages of life origin is stated in the paper. The concept eliminates key difficulties in the problem of life origin, and allows experimental verification of it. According to the concept the predecessor of living beings has to be sufficiently simple to provide non-zero probability of self-assembling during short (in geological or cosmic scale) time. In addition the predecessor has to be capable of autocatalysis, and further complication (evolution). A possible scenario of initial stage of life origin, which can be realized both on other planets, and inside experimental facility is considered. In the scope of the scenario a theoretical model of multivariate oligomeric autocatalyst is presented. Results of computer simulation of two versions of oligomeric autocatalytic reactions are presented. It is shown that the contribution of monomer activation reaction is essential, and in some cases autocatalysis in polymerizing reaction can be achieved without catalyzing proper monomer binding reaction.

  4. A Simple Experiment for Teaching Process Intensification by Static Mixing in Chemical Reaction Engineering

    Science.gov (United States)

    Baz-Rodríguez, Sergio; Herrera-Soberanis, Natali; Rodríguez-Novelo, Miguel; Guillén-Francisc, Juana; Rocha-Uribe, José

    2016-01-01

    An experiment for teaching mixing intensification in reaction engineering is described. For this, a simple tubular reactor was constructed; helical static mixer elements were fabricated from stainless steel strips and inserted into the reactor. With and without the internals, the equipment operates as a static mixer reactor or a laminar flow…

  5. Methyl Salicylate: A Reactive Chemical Warfare Agent Surrogate to Detect Reaction with Hypochlorite (POSTPRINT)

    Science.gov (United States)

    2011-05-01

    acid (Fisher Scientific, Fair Lawn, NJ) was diluted to 1.0 M in water purified by reverse osmosis . Methods. Reactions were initially examined by...reactivity of hypochlorite neutralizants delivered onto a substrate is strongly diffusion limited, an observation likely to be useful as a

  6. Dynamical Studies of Chemical Reactions Relevant to the Local Atmosphere of the Orbiting Space Shuttle

    National Research Council Canada - National Science Library

    Casavecchia, Piergiorgio

    1998-01-01

    ...: The contractor will measure differential cross sections for reactions of O(3P), 0(1D) and OH(2P) with various radial and molecules present in the local atmosphere of the space shuttle in low earth orbit as described in the original proposal for this work.

  7. Kinetic and chemical analyses of the cytokinin dehydrogenase-catalysed reaction : correlations with the crystal structure

    NARCIS (Netherlands)

    Popelková, Hana; Fraaije, Marco W.; Novák, Ondřej; Frébortová, Jitka; Bilyeu, Kristin D.; Frébort, Ivo

    2006-01-01

    CKX (cytokinin dehydrogenase) is a flavoprotein that cleaves cytokinins to adenine and the corresponding side-chain aldehyde using a quinone-type electron acceptor. In the present study, reactions of maize (Zea mays) CKX with five different substrates (N6-isopentenyladenine, trans-zeatin, kinetin,

  8. A Quantum Chemical Exploration of the Horner-Wadsworth-Emmons Reaction

    DEFF Research Database (Denmark)

    Brandt, Peter; Norrby, Per-Ola; Martin, Ivar

    1998-01-01

    The mechanism of the Horner-Wadsworth-Emmons (HWE) reaction has been investigated using high level quantum mechanical calculations on a realistic model system. The solvation contribution has been evaluated using the PCM/DIR method. In the free, anionic system, the rate determining step was found...

  9. Spatiotemporal Imaging of Chemical Reactions: Making Molecular Movies with Femtosecond X-Ray Scattering

    Science.gov (United States)

    Budarz, J. M.; Minitti, M. P.; Kirrander, A.; Hastings, J. B.; Weber, P. M.

    2015-03-01

    The study of ultrafast reaction dynamics of molecular systems has benefited from the rapid development of spectroscopic and imaging techniques that follow their temporal evolution on a sub-picosecond time scale. More complete understanding of molecular behavior, however, is expected to arise from a full observation of electronic and nuclear motions during reactions. Our recent experiments at the Linac Coherent Light Source (LCLS) have allowed us to develop and implement a method wherein the ultrafast reaction dynamics of molecules in dilute gases (4 Torr) are captured by time-resolved X-ray scattering. Using a pump-probe scheme with 267 nm excitation laser and 8.3 keV X-ray probe pulses, we performed a series of measurements on the interatomic positions at variable delay times to produce a `molecular movie.' In our experiments, 1,3-cyclohexadiene (CHD) is prepared on an excited state surface, causing the molecule to accelerate down several potential energy surfaces coupled by conical intersections, to open into 1,3,5-hexatriene within 80 fs. The resulting `movie' has been supplemented with molecular trajectory calculations to separate the multiple pathways the excited molecule takes toward the open ring. In this talk, the experimental methods and designs that made these experiments possible will be presented together with the first results describing the photochemical reaction dynamics of CHD.

  10. Page 1 THE ROLE OF SOLVENT IN CHEMICAL REACTIONS Part II ...

    Indian Academy of Sciences (India)

    It was felt that the use of methyl halides in the first instance will simplify the situation and serve as a starting point in the analysis of solvent influences. The reaction between aniline and methyl iodide proceeded under homo- geneous conditions in both acetone and ethyl alcohol but in nitrobenzene and carbon tetrachloride ...

  11. Interaction of 2'-deoxyguanosine with cis-2-butene-1,4-dial: Computational approach to analysis of multistep chemical reactions

    Directory of Open Access Journals (Sweden)

    Sviatenko L. K.

    2014-05-01

    Full Text Available cis-2-Butene-1,4-dial represents a microsomal metabolite of furan, an industrially important chemical found in cigarette smoke, air pollution, and also in canned or jarred food. It is expected to be a human carcinogen. Aim. Investigation an effect of cis-2-butene-1,4-dial on the 2'-deoxyguanine which is a model of DNA site. Methods. Optimization of reaction species molecular structures, spectral parameters and Gibbs free energy calculations were performed using Gaussian09 program. Systems of differential equations for kinetics generation were solved using Mathcad15 program. Results. The predicted mechanism of the reaction of cis-2-butene-1,4-dial with 2'-deoxyguanine consists of four-step process formation of four diastereomeric primary adducts and further base-mediated five-step transformation of the primary adducts to the secondary one. The reaction kinetics, which allows defining theconcentration change of any reaction species was calculated. Conclusions. Under physiological conditions the interaction between cis-2-butene-1,4-dial and 2'-deoxyguanine leads to the formation of a stable adduct which could be responsible for the furan genotoxicity.

  12. Hybrid quantum and classical methods for computing kinetic isotope effects of chemical reactions in solutions and in enzymes.

    Science.gov (United States)

    Gao, Jiali; Major, Dan T; Fan, Yao; Lin, Yen-Lin; Ma, Shuhua; Wong, Kin-Yiu

    2008-01-01

    A method for incorporating quantum mechanics into enzyme kinetics modeling is presented. Three aspects are emphasized: 1) combined quantum mechanical and molecular mechanical methods are used to represent the potential energy surface for modeling bond forming and breaking processes, 2) instantaneous normal mode analyses are used to incorporate quantum vibrational free energies to the classical potential of mean force, and 3) multidimensional tunneling methods are used to estimate quantum effects on the reaction coordinate motion. Centroid path integral simulations are described to make quantum corrections to the classical potential of mean force. In this method, the nuclear quantum vibrational and tunneling contributions are not separable. An integrated centroid path integral-free energy perturbation and umbrella sampling (PI-FEP/UM) method along with a bisection sampling procedure was summarized, which provides an accurate, easily convergent method for computing kinetic isotope effects for chemical reactions in solution and in enzymes. In the ensemble-averaged variational transition state theory with multidimensional tunneling (EA-VTST/MT), these three aspects of quantum mechanical effects can be individually treated, providing useful insights into the mechanism of enzymatic reactions. These methods are illustrated by applications to a model process in the gas phase, the decarboxylation reaction of N-methyl picolinate in water, and the proton abstraction and reprotonation process catalyzed by alanine racemase. These examples show that the incorporation of quantum mechanical effects is essential for enzyme kinetics simulations.

  13. Non-steady state mass action dynamics without rate constants: dynamics of coupled reactions using chemical potentials

    Science.gov (United States)

    Cannon, William R.; Baker, Scott E.

    2017-10-01

    Comprehensive and predictive simulation of coupled reaction networks has long been a goal of biology and other fields. Currently, metabolic network models that utilize enzyme mass action kinetics have predictive power but are limited in scope and application by the fact that the determination of enzyme rate constants is laborious and low throughput. We present a statistical thermodynamic formulation of the law of mass action for coupled reactions at both steady states and non-stationary states. The formulation uses chemical potentials instead of rate constants. When used to model deterministic systems, the method corresponds to a rescaling of the time dependent reactions in such a way that steady states can be reached on the same time scale but with significantly fewer computational steps. The relationships between reaction affinities, free energy changes and generalized detailed balance are central to the discussion. The significance for applications in systems biology are discussed as is the concept and assumption of maximum entropy production rate as a biological principle that links thermodynamics to natural selection.

  14. Organometallic Bonding in an Ullmann-Type On-Surface Chemical Reaction Studied by High-Resolution Atomic Force Microscopy.

    Science.gov (United States)

    Kawai, Shigeki; Sadeghi, Ali; Okamoto, Toshihiro; Mitsui, Chikahiko; Pawlak, Rémy; Meier, Tobias; Takeya, Jun; Goedecker, Stefan; Meyer, Ernst

    2016-10-01

    The on-surface Ullmann-type chemical reaction synthesizes polymers by linking carbons of adjacent molecules on solid surfaces. Although an organometallic compound is recently identified as the reaction intermediate, little is known about the detailed structure of the bonded organometallic species and its influence on the molecule and the reaction. Herein atomic force microscopy at low temperature is used to study the reaction with 3,9-diiododinaphtho[2,3-b:2',3'-d]thiophene (I-DNT-VW), which is polymerized on Ag(111) in vacuum. Thermally sublimated I-DNT-VW picks up a Ag surface atom, forming a CAg bond at one end after removing an iodine. The CAg bond is usually short-lived, and a CAgC organometallic bond immediately forms with an adjacent molecule. The existence of the bonded Ag atoms strongly affects the bending angle and adsorption height of the molecular unit. Density functional theory calculations reveal the bending mechanism, which reveals that charge from the terminus of the molecule is transferred via the Ag atom into the organometallic bond and strengths the local adsorption to the substrate. Such deformations vanish when the Ag atoms are removed by annealing and CC bonds are established. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Unveiling the structure and composition of titanium oxide nanotubes through ion exchange chemical reactions and thermal decomposition processes

    Directory of Open Access Journals (Sweden)

    Ferreira Odair P.

    2006-01-01

    Full Text Available In this paper we report the ion exchange reactions and the thermal decomposition of titanium oxide nanotubes, obtained by hydrothermal treatment of TiO2 and NaOH. Based on these results we propose a new composition for the as-prepared nanotubes as Na2Ti3O7.nH2O. Our results also suggest that nanotube walls have structure similar to those observed in the layer of the bulk Na2Ti3O7. Depending on how the washing process is performed on the nanotubes (water or acid solutions the Na+ content can be modified via the exchange reaction of Na+ by H+. Thus, a general chemical formula was also proposed: Na2-xHxTi3O7 .nH2O (0 < x < 2, x being dependent on the washing process.

  16. Free Convection Heat and Mass Transfer MHD Flow in a Vertical Channel in the Presence of Chemical Reaction

    Directory of Open Access Journals (Sweden)

    R. N. Barik

    2013-09-01

    Full Text Available An analysis is made to study the effects of diffusion-thermo and chemical reaction on fully developed laminar MHD flow of electrically conducting viscous incompressible fluid in a vertical channel formed by two vertical parallel plates was taken into consideration with uniform temperature and concentration. The analytical solution by Laplace transform technique of partial differential equations is used to obtain the expressions for the velocity, temperature and concentration. It is interesting to note that during the course of computation, the transient solution at large time coincides with steady state solution derived separately and the diffusion-thermo effect creates an anomalous situation in temperature and velocity profiles for small Prandtl numbers. The study is restricted to only destructive reaction and non-conducting case cannot be derived as a particular case still it is quite interesting and more realistic than the earlier one.

  17. Stagnation-point flow and mass transfer with chemical reaction past a permeable stretching/shrinking sheet

    Science.gov (United States)

    Najib, Najwa; Bachok, Norfifah; Aziz, Siti Fatima Abdul; Arifin, Norihan Md

    2014-07-01

    An analysis is carried out to investigate the steady two-dimensional boundary layer stagnation point flow past a permeable stretching/shrinking sheet with chemical reaction. Using a similarity transformation, the governing equations are transformed into coupled, nonlinear ordinary differential equations which are then solved numerically using a shooting method. Effects of uniform suction and injection on the flow and mass transfer characteristics are thoroughly examined. Different from a stretching sheet, it is found that the solutions for a shrinking sheet are non-unique. The range of parameter b/a where the similarity solution exists for the steady stagnation point flow over a stretching/shrinking sheet with suction effect is larger compared with injection effect. The results indicate that the concentration boundary layer thickness decreases with increasing values of Schmidt number and reaction-rate parameter for both solutions.

  18. Analysis of Chemical Reaction Kinetics Behavior of Nitrogen Oxide During Air-staged Combustion in Pulverized Boiler

    Directory of Open Access Journals (Sweden)

    Jun-Xia Zhang

    2016-03-01

    Full Text Available Because the air-staged combustion technology is one of the key technologies with low investment running costs and high emission reduction efficiency for the pulverized boiler, it is important to reveal the chemical reaction kinetics mechanism for developing various technologies of nitrogen oxide reduction emissions. At the present work, a three-dimensional mesh model of the large-scale four corner tangentially fired boiler furnace is established with the GAMBIT pre-processing of the FLUENT software. The partial turbulent premixed and diffusion flame was simulated for the air-staged combustion processing. Parameters distributions for the air-staged and no the air-staged were obtained, including in-furnace flow field, temperature field and nitrogen oxide concentration field. The results show that the air-staged has more regular velocity field, higher velocity of flue gas, higher turbulence intensity and more uniform temperature of flue gas. In addition, a lower negative pressure zone and lower O2 concentration zone is formed in the main combustion zone, which is conducive to the NO of fuel type reduced to N2, enhanced the effect of NOx reduction. Copyright © 2016 BCREC GROUP. All rights reserved Received: 5th November 2015; Revised: 14th January 2016; Accepted: 16th January 2016  How to Cite: Zhang, J.X., Zhang, J.F. (2016. Analysis of Chemical Reaction Kinetics Behavior of Nitrogen Oxide During Air-staged Combustion in Pulverized Boiler. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 100-108. (doi:10.9767/bcrec.11.1.431.100-108 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.431.100-108

  19. Studies in Photochemical Smog Chemistry: I. Atmospheric Chemistry of Toluene. I. Analysis of Chemical Reaction Mechanisms for Photochemical Smog

    Science.gov (United States)

    Leone, Joseph Anthony

    This study focuses on two related topics in the gas phase organic chemistry of importance in urban air pollution. Part I describes an experimental and modeling effort aimed at developing a new explicit reaction mechanism for the atmospheric photooxidation of toluene. This mechanism is tested using experimental data from both indoor and outdoor smog chamber facilities. The predictions of the new reaction mechanism are found to be in good agreement with both sets of experimental data. Additional simulations performed with the new mechanism are used to investigate various mechanistic paths, and to gain insight into areas where our understanding is not complete. The outdoor experimental facility, which was built to provide the second set of experimental data, consists of a 65 cubic meter teflon smog chamber together with full instrumentation capable of measuring ozone, nitrogen dioxide, nitric oxide, peroxyacetyl nitrate (PAN), carbon monoxide, relative humidity, temperature, aerosol size distributions, and of course toluene and its photooxidation products. In Part II, we present a theoretical analysis of lumped chemical reaction mechanisms for photochemical smog. Included is a description of a new counter species analysis technique which can be used to analyze any complex chemical reaction mechanism. When applied to mechanisms for photochemical smog, this analysis is shown capable of providing answers to previously inaccessible questions such as the relative contributions of individual organics to photochemical ozone formation. The counter species analysis is applied to six existing mechanisms for photochemical smog to determine why they predict substantially different degrees of emission controls to achieve the same desired air quality under identical conditions. For each mechanism critical areas are identified that when altered bring the predictions of the various mechanisms into much closer agreement. Finally, a new lumped mechanism for photochemical smog is

  20. Steepest-entropy-ascent nonequilibrium quantum thermodynamic framework to model chemical reaction rates at an atomistic level.

    Science.gov (United States)

    Beretta, G P; Al-Abbasi, Omar; von Spakovsky, M R

    2017-04-01

    The steepest entropy ascent (SEA) dynamical principle provides a general framework for modeling the dynamics of nonequilibrium (NE) phenomena at any level of description, including the atomistic one. It has recently been shown to provide a precise implementation and meaning to the maximum entropy production principle and to encompass many well-established theories of nonequilibrium thermodynamics into a single unifying geometrical framework. Its original formulation in the framework of quantum thermodynamics (QT) assumes the simplest and most natural Fisher-Rao metric to geometrize from a dynamical standpoint the manifold of density operators, which represent the thermodynamic NE states of the system. This simplest SEAQT formulation is used here to develop a general mathematical framework for modeling the NE time evolution of the quantum state of a chemically reactive mixture at an atomistic level. The method is illustrated for a simple two-reaction kinetic scheme of the overall reaction F+H_{2}⇔HF+F in an isolated tank of fixed volume. However, the general formalism is developed for a reactive system subject to multiple reaction mechanisms. To explicitly implement the SEAQT nonlinear law of evolution for the density operator, both the energy and the particle number eigenvalue problems are set up and solved analytically under the dilute gas approximation. The system-level energy and particle number eigenvalues and eigenstates are used in the SEAQT equation of motion to determine the time evolution of the density operator, thus effectively describing the overall kinetics of the reacting system as it relaxes toward stable chemical equilibrium. The predicted time evolution in the near-equilibrium limit is compared to the reaction rates given by a standard detailed kinetic model so as to extract the single time constant needed by the present SEA model.

  1. Potential Utilization of Fusel Oil: A Kinetic Approach for Production of Fusel Oil Esters Through Chemical Reaction

    OpenAIRE

    Küçük, Zeki; CEYLAN, Kadim

    2014-01-01

    Fusel oil is a by-product of the distillation of ethyl alcohol from the fermentation of molasses and contains mainly C3-C5 alcohols. Acetic acid and butyric acid esters of its major alcohol components have economic value as chemicals for flavor and fragrance manufacturing. This study presents some data regarding the uncatalyzed esterification of fusel oil with acetic acid, propionic acid and butyric acid. The reactions were carried out at two temperatures, i.e., 45\\circC and under the reflux ...

  2. MHD oscillatory channel flow, heat and mass transfer in a physiological fluid in presence of chemical reaction

    Directory of Open Access Journals (Sweden)

    J.C. Misra

    2016-03-01

    Full Text Available In the present paper, the problem of oscillatory MHD flow of blood in a porous arteriole in presence of chemical reaction and an external magnetic field has been investigated. Heat and mass transfer during arterial blood flow are also studied. A mathematical model is developed and analyzed by using appropriate mathematical techniques. Expressions for the velocity profile, volumetric flow rate, wall shear stress and rates of heat and mass transfer have been obtained. Variations of the said quantities with different parameters are computed by using MATHEMATICA software. The quantitative estimates are presented through graphs and table.

  3. Sign conditions for injectivity of generalized polynomial maps with applications to chemical reaction networks and real algebraic geometry

    DEFF Research Database (Denmark)

    Müller, Stefan; Feliu, Elisenda; Regensburger, Georg

    2016-01-01

    We give necessary and sufficient conditions in terms of sign vectors for the injectivity of families of polynomials maps with arbitrary real exponents defined on the positive orthant. Our work relates and extends existing injectivity conditions expressed in terms of Jacobian matrices...... and determinants. In the context of chemical reaction networks with power-law kinetics, our results can be used to preclude as well as to guarantee multiple positive steady states. In the context of real algebraic geometry, our results reveal the first ...

  4. Thermal-diffusion effects on mixed convection flow in a heat absorbing fluid with Newtonian heating and chemical reaction

    Science.gov (United States)

    Hussanan, Abid; Salleh, Mohd Zuki; Tahar, Razman Mat; Khan, Ilyas

    2015-02-01

    Thermal-diffusion and chemical reaction effects on mixed convection heat and mass transfer flow past an infinite oscillating vertical plate with Newtonian heating is investigated. The governing equations are transformed to a system of linear partial differential equations using appropriate non-dimensional variables. Using Laplace transform method the resulting equations are solved analytically and the expression for velocity, temperature and concentration are obtained. They satisfy all imposed initial and boundary conditions. Numerical results for temperature and concentration are shown in various graphs for embedded flow parameters and discussed in details.

  5. [Determination of trace amounts of nitrite and its chemical reaction kinetics].

    Science.gov (United States)

    Luo, Zhi-yong; Zheng, Huai-li

    2014-06-01

    A catalytic kinetic spectrophotometric method for the determination of nitrite, NO2(-)-S2O8(2-)-MR, was developed. It is based on the fading reaction of methyl red (MR) oxidized by potassium persulfate which can be catalyzed by NO2- in the medium of dilute HCl. The optimum experimental conditions were gained by combining single factor experiments with orthogonal experiments. Calibration curve, detection limit, precision, and anti-interference under the optimum experimental conditions were researched. Its kinetics principles and parameters were discussed. Its quantitative principle was investigated. The results show that the optimum experimental conditions of this method should be as follows: 1.0 mL 0.3 mol x L(-1) HCl, 1.0 mL 0.01 mol x L(-1) K2S2O8, 0.6 mL 0.2 g x L(-1) MR, reaction temperature 80 degrees C and reaction time 9 min. The principles for the quantitative determination of trace nitrite is that variation of MR concentration at the maximum absorption wavelength of 518 nm, ln(A0/A), shows a good linear relationship with the concentration of NO2- under the optimum experimental conditions. Its determination range is 0.01-0.80 mg x L(-1) and its detection limit is 0.007 mg x L(-1). The kinetic characteristics are that the reaction order in NO2- is 1 and the fading reaction is a pseudo first order reaction. Its apparent activation energy is 85.04 kJ x mol(-1). Its apparent rate constant is 0.021 4 min(-1), and the half-life is 32.39 min at 80 degrees C. The kinetic principle is that the variation of MR concentration is directly proportional to the concentration of NO2-, ln(A0/A) = kc(NO2-). This new method for the determination of trace nitrite has never previously been reported in the published literature so far. It is highly sensitive and selective. Most of the common ions don't interfere with the determination of nitrite. This method has the advantages of convenient operation and the regents used are cheap and nontoxic. It was applied to the determination

  6. Polyoxometalate (POM) catalyst systems : chemical principles and reactions with lignin and oxygen

    Science.gov (United States)

    I.A. Weinstock; R.H. Atalla; J.S. Bond; E.M.G. Barbuzzi; V.A. Grigoriev; Y. Gueletii; J.J. Cowan; D.M. Sonnen; R.S. Reiner; S.E. Reichel; R.A. Heintz; C.J. Houtman; A.J. Bailey; C.L. Hill

    2000-01-01

    Chemical data pertinent to most-recently developed POM delignification systems will be presented. These data will be used to demonstrate the fundamental basis for the stability, self-buffering properties, versatility and high selectivity of these systems when used in combination with oxygen to convert native or residual lignin in wood or wood-pulp fibers to CO2 and H2O...

  7. On the Use of Interactive Texts in Undergraduate Chemical Reaction Engineering Courses: A Pedagogical Experience

    Science.gov (United States)

    Asensio, Daniela A.; Barassi, Francisca J.; Zambon, Mariana T.; Mazza, Germán D.

    2010-01-01

    This paper describes the results of a pedagogical experience carried out at the University of Comahue, Argentina, with an interactive text (IT) concerning Homogeneous Chemical Reactors Analysis. The IT was built on the frame of the "Mathematica" software with the aim of providing students with a robust computational tool. Students'…

  8. Reactions of. cap alpha. -hydroxy acid chemical exchange in titanium (3) and vanadyl (2) coordination compounds

    Energy Technology Data Exchange (ETDEWEB)

    Glebov, A.N.; Sal' nikov, Yu.I.; Zakharov, A.V.; Saprykova, Z.A.; Gogolashvili, Eh.L. (Kazanskij Gosudarstvennyj Univ. (USSR))

    1983-06-01

    For the first time a study was made on the effect of chemical exchange of oxygen-containing ligands (lactic, mandelic, sulfosalicylic acids) on the relaxation period of solvent water protons. Constants of exchange rates of protonated ligand forms were evaluated. The mechanism of the observed processes are proposed.

  9. Subcritical water - a perspective reaction media for biomass processing to chemicals

    OpenAIRE

    Pavlovič, Irena; Škerget, Mojca; Knez, Željko

    2015-01-01

    Biomass and water are recognized as a key renewable feedstock in sustainable production of chemicals, fuels and energy. Subcritical water (SubCW), or commonly referred as hot compressed water (HCW), is the water above boiling and below critical point (CP

  10. Exploring the native chemical ligation concept for highly stereospecific glycosylation reactions.

    Science.gov (United States)

    Hoang, Kim Le Mai; Bai, Yaguang; Ge, Xin; Liu, Xue-Wei

    2013-06-07

    Various O-alkyl glycosides were obtained in a highly stereospecific manner with retention of configuration at the anomeric center. Our method has customized native chemical ligation concept for glycoconjugates synthesis, utilizing a meticulously controlled activating system. To explain the origin of stereoselective preference, an S(N)i mechanism was proposed and corroborated by computational calculations.

  11. Positronium in a Liquid Phase: Formation, Bubble State and Chemical Reactions

    Directory of Open Access Journals (Sweden)

    Sergey V. Stepanov

    2012-01-01

    Full Text Available The present approach describes the e+ fate since its injection into a liquid until its annihilation. Several stages of the e+ evolution are discussed: (1 energy deposition and track structure of fast positrons: ionization slowing down, number of ion-electron pairs, typical sizes, thermalization, electrostatic interaction between e+ and the constituents of its blob, and effect of local heating; (2 positronium formation in condensed media: the Ore model, quasifree Ps state, intratrack mechanism of Ps formation; (3 fast intratrack diffusion-controlled reactions: Ps oxidation and ortho-paraconversion by radiolytic products, reaction rate constants, and interpretation of the PAL spectra in water at different temperatures; (4 Ps bubble models. Inner structure of positronium (wave function, energy contributions, relationship between the pick-off annihilation rate and the bubble radius.

  12. Constrained reaction volume approach for studying chemical kinetics behind reflected shock waves

    KAUST Repository

    Hanson, Ronald K.

    2013-09-01

    We report a constrained-reaction-volume strategy for conducting kinetics experiments behind reflected shock waves, achieved in the present work by staged filling in a shock tube. Using hydrogen-oxygen ignition experiments as an example, we demonstrate that this strategy eliminates the possibility of non-localized (remote) ignition in shock tubes. Furthermore, we show that this same strategy can also effectively eliminate or minimize pressure changes due to combustion heat release, thereby enabling quantitative modeling of the kinetics throughout the combustion event using a simple assumption of specified pressure and enthalpy. We measure temperature and OH radical time-histories during ethylene-oxygen combustion behind reflected shock waves in a constrained reaction volume and verify that the results can be accurately modeled using a detailed mechanism and a specified pressure and enthalpy constraint. © 2013 The Combustion Institute.

  13. Reaction mechanism of zinc-dependent cytosine deaminase from Escherichia coli: a quantum-chemical study.

    Science.gov (United States)

    Manta, Bianca; Raushel, Frank M; Himo, Fahmi

    2014-05-29

    The reaction mechanism of cytosine deaminase from Escherichia coli is studied using density functional theory. This zinc-dependent enzyme catalyzes the deamination of cytosine to form uracil and ammonia. The calculations give a detailed description of the catalytic mechanism and establish the role of important active-site residues. It is shown that Glu217 is essential for the initial deprotonation of the metal-bound water nucleophile and the subsequent protonation of the substrate. It is also demonstrated that His246 is unlikely to function as a proton shuttle in the nucleophile activation step, as previously proposed. The steps that follow are nucleophilic attack by the metal-bound hydroxide, protonation of the leaving group assisted by Asp313, and C-N bond cleavage. The calculated overall barrier is in good agreement with the experimental findings. Finally, the calculations reproduce the experimentally determined inverse solvent deuterium isotope effect, which further corroborates the suggested reaction mechanism.

  14. Oxidation of a PAH polluted soil using modified Fenton reaction in unsaturated condition affects biological and physico-chemical properties.

    Science.gov (United States)

    Laurent, F; Cébron, A; Schwartz, C; Leyval, C

    2012-02-01

    A batch experiment was conducted to assess the impact of chemical oxidation using modified Fenton reaction on PAH content and on physico-chemical and biological parameters of an industrial PAH contaminated soil in unsaturated condition. Two levels of oxidant (H(2)O(2), 6 and 65 g kg(-1)) and FeSO(4) were applied. Agronomic parameters, bacterial and fungal density, microbial activity, seed germination and ryegrass growth were assessed. Partial removal of PAHs (14% and 22%) was obtained with the addition of oxidant. The impact of chemical oxidation on PAH removal and soil physico-chemical and biological parameters differed depending on the level of reagent. The treatment with the highest concentration of oxidant decreased soil pH, cation exchange capacity and extractable phosphorus content. Bacterial, fungal, and PAH degrading bacteria densities were also lower in oxidized soil. However a rebound of microbial populations and an increased microbial activity in oxidized soil were measured after 5 weeks of incubation. Plant growth on soil treated by the highest level of oxidant was negatively affected. Copyright © 2011 Elsevier Ltd. All rights reserved.

  15. Toward a conceptual model relating chemical reaction fronts to water flow paths in hills

    Science.gov (United States)

    Brantley, Susan L.; Lebedeva, Marina I.; Balashov, Victor N.; Singha, Kamini; Sullivan, Pamela L.; Stinchcomb, Gary

    2017-01-01

    Both vertical and lateral flows of rock and water occur within eroding hills. Specifically, when considered over geological timeframes, rock advects vertically upward under hilltops in landscapes experiencing uplift and erosion. Once rock particles reach the land surface, they move laterally and down the hillslope because of erosion. At much shorter timescales, meteoric water moves vertically downward until it reaches the regional water table and then moves laterally as groundwater flow. Water can also flow laterally in the shallow subsurface as interflow in zones of permeability contrast. Interflow can be perched or can occur during periods of a high regional water table. The depths of these deep and shallow water tables in hills fluctuate over time. The fluctuations drive biogeochemical reactions between water, CO2, O2, and minerals and these in turn drive fracturing. The depth intervals of water table fluctuation for interflow and groundwater flow are thus reaction fronts characterized by changes in composition, fracture density, porosity, and permeability. The shallow and deep reaction zones can separate over meters in felsic rocks. The zones act like valves that reorient downward unsaturated water flow into lateral saturated flow. The valves also reorient the upward advection of rock into lateral flow through solubilization. In particular, groundwater removes highly soluble, and interflow removes moderately soluble minerals. As rock and water moves through the system, hills may evolve toward a condition where the weathering advance rate, W, approaches the erosion rate, E. If W = E, the slopes of the deep and shallow reaction zones and the hillsides must allow removal of the most soluble, moderately soluble, and least soluble minerals respectively. A permeability architecture thus emerges to partition each evolving hill into dissolved and particulate material fluxes as it approaches steady state.

  16. Quantum chemical and conventional TST calculations of rate constants for the OH + alkane reaction

    Energy Technology Data Exchange (ETDEWEB)

    Bravo-Perez, Graciela [Prog. Investig. Medio Ambiente y Seguridad, Instituto Mexicano del Petroleo, Av. Eje Central Lazaro Cardenas 152, 07730, AP 14805 Mexico DF (Mexico)]. E-mail: gbperez@imp.mx; Alvarez-Idaboy, J. Raul [Prog. Investig. Medio Ambiente y Seguridad, Instituto Mexicano del Petroleo, Av. Eje Central Lazaro Cardenas 152, 07730, AP 14805 Mexico DF (Mexico)]. E-mail: jidaboy@imp.mx; Jimenez, Annia Galano [Prog. Investig. Medio Ambiente y Seguridad, Instituto Mexicano del Petroleo, Av. Eje Central Lazaro Cardenas 152, 07730, AP 14805 Mexico DF (Mexico); Cruz-Torres, Armando [Prog. Investig. Medio Ambiente y Seguridad, Instituto Mexicano del Petroleo, Av. Eje Central Lazaro Cardenas 152, 07730, AP 14805 Mexico DF (Mexico)

    2005-04-04

    Reactions of OH with methane, ethane, propane, i-butane, and n-butane have been modeled using ab initio (MP2) and hybrid DFT (BHandHLYP) methods, and the 6-311G(d,p) basis set. Furthermore, single-point calculations at the CCSD(T) level were carried out at the optimized geometries. The rate constants have been calculated using the conventional transition-state theory (CTST). Arrhenius equations are proposed in the temperature range of 250-650 K. Hindered Internal Rotation partition functions calculations were explicitly carried out and included in the total partition functions. These corrections showed to be relevant in the determination of the pre-exponential parameters, although not so important as in the NO{sub 3} + alkane reactions [G. Bravo-Perez, J.R. Alvarez-Idaboy, A. Cruz-Torres, M.E. Ruiz, J. Phys. Chem. A 106 (2002) 4645]. The explicit participation of the tunnel effect has been taken into account. The calculated rate coefficients provide a very good agreement with the experimental data. The best agreement for the overall alkane + OH reactions seemed to occur when the BHandHLYP geometries and partition functions are used. For propane and i-butane, in addition to the respective secondary and tertiary H-abstraction channels, the primary one has been considered. These pathways are confirmed to be significant in spite of the large differences in activation energies between primary and secondary or primary and tertiary channels, respectively of propane and i-butane reactions and should not be disregarded.

  17. Quantifying Chemical and Electrochemical Reactions in Liquids by in situ Electron Microscopy

    DEFF Research Database (Denmark)

    Canepa, Silvia

    of electrochemical deposition of copper (Cu) by electrochemical liquid scanning electron microscopy (EC-SEM) was done in order to direct observe the formation of dendritic structures. Finally the shape evolution from solid to hollow structures through galvanic replacement reactions were observed for different silver...... (Ag) nanotemplates (cube, rod, nanowires) and gold chloride solution. Results demonstrated that by combining in situ LTEM and ECSEM microscopy with quantitative analysis and systematic studies, meaningful information about the controllable synthesis of metal NPs is achievable....

  18. On the nature of the reaction intermediate in the HIV-1 protease: a quantum chemical study

    Science.gov (United States)

    Carnevale, V.; Raugei, S.; Piana, S.; Carloni, P.

    2008-07-01

    Several mechanistic aspects of Aspartic Proteases' enzymatic reaction are currently highly controversial. There is general consensus that the first step of the reaction involves a nucleophilic attack of a water molecule to the substrate carbonyl carbon with subsequent formation of a metastable intermediate (INT). However, the exact nature of this intermediate is subject of debate. While ab initio and QM/MM calculations predict that INT is a neutral gem-diol specie, empirical valence bond calculations suggest that the protein frame can stabilize a charged oxyanion intermediate. Here the relative stability of the gem diol and oxyanion intermediate is calculated by performing density functional and post-Hartree-Fock calculations. The robustness of the results is assessed by increasing the size of the system and of the basis set and by performing QM/MM calculations that explicitly include protein/solvent electrostatic effects. Our results suggest that the neutral gem-diol intermediate is 20-30 kcal/mol more stable than the charged oxyanion. It is therefore concluded that only the neutral specie is populated during the enzymatic reaction.

  19. Mechanochemical synthesis of Co and Ni decorated with chemically deposited Pt as electrocatalysts for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Flores-Rojas, E.; Cabañas-Moreno, J.G. [Programa de Nanociencias y Nanotecnología, Centro de Investigación y de Estudios Avanzados, CINVESTAV-IPN, Av. Instituto Politécnico Nacional 2508, Col. Zacatenco, 07360 Mexico City (Mexico); Pérez-Robles, J.F. [Programa de Nanociencias y Nanotecnología, Centro de Investigación y de Estudios Avanzados, CINVESTAV-IPN, Av. Instituto Politécnico Nacional 2508, Col. Zacatenco, 07360 Mexico City (Mexico); Dpto. Ciencia de los Materiales, CINVESTAV-IPN Unidad Queretaro, Libramiento Norponiente No. 2000 Fracc. Real de Juriquilla, 76230, Queretaro (Mexico); Solorza-Feria, O., E-mail: osolorza@cinvestav.mx [Programa de Nanociencias y Nanotecnología, Centro de Investigación y de Estudios Avanzados, CINVESTAV-IPN, Av. Instituto Politécnico Nacional 2508, Col. Zacatenco, 07360 Mexico City (Mexico); Depto. Química, CINVESTAV-IPN, 07360, México City (Mexico)

    2016-11-01

    High energy milling in combination with galvanic displacement were used for the preparation of bimetallic nanocatalysts. Co and Ni monometallic powders milled for 30 and 20 h, respectively were both produced in air atmosphere and used as precursors for the preparation of M-Pt (M = Co,Ni) compounds. Nanosized monometallic powders were physically supported on Vulcan carbon, and covered with 20 wt%Pt through a Galvanic Displacement Reaction (GDR) to produce Co-20Pt/C and Ni-20Pt/C electrocatalysts. XRD was used for phase identification on milled powders and for demonstrating structural transformations of Co powders during milling. Results on unmilled metallic Co powder show a predominant HCP structure modifying to a FCC structure after milling. Ni powders maintain their same FCC structure. Energy Dispersive X-Ray Spectometry (EDX) was used for chemical composition analysis on milled powders at several milling times. Scanning Transmission Electron Microscopy (STEM) show the formation of heterogeneous particle with ∼10 nm in size for both electrocatalysts. The electrocatalytic activity was evaluated by Cyclic Voltammetry (CV) and steady state Rotating Disk Electrode (RDE) for the Oxygen Reduction Reaction (ORR) in 0.1 M HClO{sub 4}. The kinetic parameters on Co-20Pt/C conducted to the highest mass activity for the cathodic reaction. - Highlights: • Monometallic powders of Co, and Ni were used as precursors for the preparation of M-Pt (M = Co,Ni) electrocatalysts. • Nanosized monometallic powders were decorated with Pt by a Galvanic Displacement Reaction. • The kinetic parameters on Co-20Pt/C conducted to the highest mass activity for the ORR reaction.

  20. Controlling nanomaterial synthesis, chemical reactions and self assembly in dynamic thin films.

    Science.gov (United States)

    Chen, Xianjue; Smith, Nicole M; Iyer, K Swaminathan; Raston, Colin L

    2014-03-07

    Recent advances in continuous-flow processors, which integrate sustainability metrics including scalability, have established their utility in materials and chemical processing. In this review the spinning disc processor (SDP) and the related rotating tube processor (RTP), are highlighted in the use of highly sheared and micro-mixed dynamic thin films in gaining control over such processing for a wide range of applications. Both SDP and RTP have a number of control parameters beyond traditional batch processing which are effective in (i) manipulating the size, shape, defects, agglomeration, and precipitation of nanoparticles, as well as decorating preformed nano-structures, for a variety of inorganic and organic compounds, (ii) controlling chemical reactivity and selectivity including the formation of polymers, and (iii) disassembling self organised nano-structures, as a tool for probing macromolecular structure under shear conditions.