WorldWideScience

Sample records for chemical reactions

  1. Microfluidic chemical reaction circuits

    Science.gov (United States)

    Lee, Chung-cheng; Sui, Guodong; Elizarov, Arkadij; Kolb, Hartmuth C.; Huang, Jiang; Heath, James R.; Phelps, Michael E.; Quake, Stephen R.; Tseng, Hsian-rong; Wyatt, Paul; Daridon, Antoine

    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.

  2. 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

  3. 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

  4. Introduction to chemical reaction engineering

    International Nuclear Information System (INIS)

    This deals with chemical reaction engineering with thirteen chapters. The contents of this book are introduction on reaction engineering, chemical kinetics, thermodynamics and chemical reaction, abnormal reactor, non-isothermal reactor, nonideal reactor, catalysis in nonuniform system, diffusion and reaction in porosity catalyst, design catalyst heterogeneous reactor in solid bed, a high molecule polymerization, bio reaction engineering, reaction engineering in material process, control multi-variable reactor process using digital computer.

  5. Chemical reaction and separation method

    NARCIS (Netherlands)

    Jansen, J.C.; Kapteijn, F.; Strous, S.A.

    2005-01-01

    The invention is directed to process for performing a chemical reaction in a reaction mixture, which reaction produces water as by-product, wherein the reaction mixture is in contact with a hydroxy sodalite membrane, through which water produced during the reaction is removed from the reaction mixtu

  6. Chemical burn or reaction

    Science.gov (United States)

    ... and buy only as much as needed. Many household products are made of toxic chemicals. It is important ... follow label instructions, including any precautions. Never store household products in food or drink containers. Leave them in ...

  7. Speeding chemical reactions by focusing

    Science.gov (United States)

    Lacasta, A. M.; Ramírez-Piscina, L.; Sancho, J. M.; Lindenberg, K.

    2013-04-01

    We present numerical results for a chemical reaction of colloidal particles which are transported by a laminar fluid and are focused by periodic obstacles in such a way that the two components are well mixed and consequently the chemical reaction is speeded up. The roles of the various system parameters (diffusion coefficients, reaction rate, and obstacles sizes) are studied. We show that focusing speeds up the reaction from the diffusion limited rate ˜t-1/2 to very close to the perfect mixing rate, ˜t-1.

  8. Speeding chemical reactions by focusing

    CERN Document Server

    Lacasta, A M; Sancho, J M; Lindenberg, K

    2012-01-01

    We present numerical results for a chemical reaction of colloidal particles which are transported by a laminar fluid and are focused by periodic obstacles in such a way that the two components are well mixed and consequently the chemical reaction is speeded up. The roles of the various system parameters (diffusion coefficients, reaction rate, obstacles sizes) are studied. We show that focusing speeds up the reaction from the diffusion limited rate (t to the power -1/2) to very close to the perfect mixing rate, (t to the power -1).

  9. Fundamentals of chemical reaction engineering

    CERN Document Server

    Davis, Mark E

    2012-01-01

    Appropriate for a one-semester undergraduate or first-year graduate course, this text introduces the quantitative treatment of chemical reaction engineering. It covers both homogeneous and heterogeneous reacting systems and examines chemical reaction engineering as well as chemical reactor engineering. The authors take a chemical approach, helping students develop an intuitive feeling for concepts, rather than an engineering approach, which tends to overlook the inner workings of systems and objects.Each chapter contains numerous worked-out problems and real-world vignettes involving commercia

  10. Reduction of chemical reaction models

    Science.gov (United States)

    Frenklach, Michael

    1991-01-01

    An attempt is made to reconcile the different terminologies pertaining to reduction of chemical reaction models. The approaches considered include global modeling, response modeling, detailed reduction, chemical lumping, and statistical lumping. The advantages and drawbacks of each of these methods are pointed out.

  11. Programmability of Chemical Reaction Networks

    Science.gov (United States)

    Cook, Matthew; Soloveichik, David; Winfree, Erik; Bruck, Jehoshua

    Motivated by the intriguing complexity of biochemical circuitry within individual cells we study Stochastic Chemical Reaction Networks (SCRNs), a formal model that considers a set of chemical reactions acting on a finite number of molecules in a well-stirred solution according to standard chemical kinetics equations. SCRNs have been widely used for describing naturally occurring (bio)chemical systems, and with the advent of synthetic biology they become a promising language for the design of artificial biochemical circuits. Our interest here is the computational power of SCRNs and how they relate to more conventional models of computation. We survey known connections and give new connections between SCRNs and Boolean Logic Circuits, Vector Addition Systems, Petri nets, Gate Implementability, Primitive Recursive Functions, Register Machines, Fractran, and Turing Machines. A theme to these investigations is the thin line between decidable and undecidable questions about SCRN behavior.

  12. 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...

  13. Apparent tunneling in chemical reactions

    DEFF Research Database (Denmark)

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

    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...

  14. 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…

  15. Laser-induced chemical reactions

    International Nuclear Information System (INIS)

    A classical model for the interaction of laser radiation with a molecular system is derived. This model is used to study the enhancement of a chemical reaction via a collision induced absorption. It was found that an infrared laser will in general enhance the rate of a chemical reaction, even if the reactants are infrared inactive. Results for an illustrative analytically solvable model are presented, as well as results from classical trajectory studies on a number of systems. The collision induced absorption spectrum in these systems can be written as the Fourier transform of a particular dipole correlation function. This is used to obtain the collision induced absorption spectrum for a state-selected, mono-energetic reactive collision system. Examples treated are a one-dimensional barrier problem, reactive and nonreactive collisions of H + H2, and a modified H + H2 potential energy surface which leads to a collision intermediate. An extension of the classical model to treat laser-induced electronically nonadiabatic collision processes is constructed. The model treats all degrees of freedom, molecular, electronic and radiation, in a dynamically consistent framework within classical mechanics. Application is made to several systems. Several interesting phenomena are discovered including a Franck-Condon-like effect causing maxima in the reaction probability at energies much below the classical threshold, laser de-enhancement of chemical reactions and an isotope effect. In order to assess the validity of the classical model for electronically nonadiabatic process (without a laser field), a model problem involving energy transfer in a collinear atom-diatom system is studied, and the results compared to the available quantum mechanical calculation. The calculations are in qualitative agreement

  16. Chemical reactions at aqueous interfaces

    Science.gov (United States)

    Vecitis, Chad David

    2009-12-01

    Interfaces or phase boundaries are a unique chemical environment relative to individual gas, liquid, or solid phases. Interfacial reaction mechanisms and kinetics are often at variance with homogeneous chemistry due to mass transfer, molecular orientation, and catalytic effects. Aqueous interfaces are a common subject of environmental science and engineering research, and three environmentally relevant aqueous interfaces are investigated in this thesis: 1) fluorochemical sonochemistry (bubble-water), 2) aqueous aerosol ozonation (gas-water droplet), and 3) electrolytic hydrogen production and simultaneous organic oxidation (water-metal/semiconductor). Direct interfacial analysis under environmentally relevant conditions is difficult, since most surface-specific techniques require relatively `extreme' conditions. Thus, the experimental investigations here focus on the development of chemical reactors and analytical techniques for the completion of time/concentration-dependent measurements of reactants and their products. Kinetic modeling, estimations, and/or correlations were used to extract information on interfacially relevant processes. We found that interfacial chemistry was determined to be the rate-limiting step to a subsequent series of relatively fast homogeneous reactions, for example: 1) Pyrolytic cleavage of the ionic headgroup of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorbed to cavitating bubble-water interfaces during sonolysis was the rate-determining step in transformation to their inorganic constituents carbon monoxide, carbon dioxide, and fluoride; 2) ozone oxidation of aqueous iodide to hypoiodous acid at the aerosol-gas interface is the rate-determining step in the oxidation of bromide and chloride to dihalogens; 3) Electrolytic oxidation of anodic titanol surface groups is rate-limiting for the overall oxidation of organics by the dichloride radical. We also found chemistry unique to the interface, for example: 1

  17. An Experiment on Mining Chemical Reaction Databases

    OpenAIRE

    Berasaluce, Sandra; Laurenço, Claude; Napoli, Amedeo; Niel, Gilles

    2004-01-01

    In this paper, we present an experiment on knowledge discovery in chemical reaction databases. Chemical reactions are the main elements on which relies synthesis in organic chemistry, and this is why chemical reactions databases are of first importance. From a problem-solving process perspective, synthesis in organic chemistry must be considered at several levels of abstraction: mainly a strategic level where general synthesis methods are involved, and a tactic level where actual chemical rea...

  18. 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…

  19. Modelling Chemical Reasoning to Predict Reactions

    CERN Document Server

    Segler, Marwin H S

    2016-01-01

    The ability to reason beyond established knowledge allows Organic Chemists to solve synthetic problems and to invent novel transformations. Here, we propose a model which 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. We show that our 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 ac...

  20. Stochastic thermodynamics of chemical reaction networks

    OpenAIRE

    Schmiedl, Tim; Seifert, Udo

    2006-01-01

    For chemical reaction networks described by a master equation, we define energy and entropy on a stochastic trajectory and develop a consistent nonequilibrium thermodynamic description along a single stochastic trajectory of reaction events. A first-law like energy balance relates internal energy, applied (chemical) work and dissipated heat for every single reaction. Entropy production along a single trajectory involves a sum over changes in the entropy of the network itself and the entropy o...

  1. A Unified Theory of Chemical Reactions

    CERN Document Server

    Aubry, S

    2014-01-01

    We propose a new and general formalism for elementary chemical reactions where quantum electronic variables are used as reaction coordinates. This formalism is in principle applicable to all kinds of chemical reactions ionic or covalent. Our theory reveals the existence of an intermediate situation between ionic and covalent which may be almost barrierless and isoenegetic and which should be of high interest for understanding biochemistry.

  2. 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

  3. 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

  4. 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

  5. Modeling of turbulent chemical reaction

    Science.gov (United States)

    Chen, J.-Y.

    1995-01-01

    Viewgraphs are presented on modeling turbulent reacting flows, regimes of turbulent combustion, regimes of premixed and regimes of non-premixed turbulent combustion, chemical closure models, flamelet model, conditional moment closure (CMC), NO(x) emissions from turbulent H2 jet flames, probability density function (PDF), departures from chemical equilibrium, mixing models for PDF methods, comparison of predicted and measured H2O mass fractions in turbulent nonpremixed jet flames, experimental evidence of preferential diffusion in turbulent jet flames, and computation of turbulent reacting flows.

  6. CHEMICAL REACTIONS AT NANOMETAL PARTICLES

    OpenAIRE

    GALO CÁRDENAS-TRIVIÑO

    2005-01-01

    The concept of nanochemistry and the reactions involved are discussed. The work is focused on nanoparticles obtained from colloidal dispersions. The colloidal particles by transmission electron microscopy of low and high resolution were analyzed. The high resolution electron miscroscopy (HRTEM) allow us to classify the nanostructure of the metal particles in some polyhedral models: cubooctahedron, truncated octahedron, tetracai decahedron and icosahedron. Some HRTEM of Pd-2 propanol and Ge-2-...

  7. 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.

  8. 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.

  9. 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…

  10. Genetic Recombination as a Chemical Reaction Network

    OpenAIRE

    Müller, Stefan; Hofbauer, Josef

    2015-01-01

    The process of genetic recombination can be seen as a chemical reaction network with mass-action kinetics. We review the known results on existence, uniqueness, and global stability of an equilibrium in every compatibility class and for all rate constants, from both the population genetics and the reaction networks point of view.

  11. Potential energy surfaces for chemical reactions

    International Nuclear Information System (INIS)

    Research into potential energy surfaces for chemical reactions at Lawrence Berkeley Laboratory during 1976 is described. Topics covered include: the fuzzy interface between surface chemistry catalysis and organometallic chemistry; potential energy surfaces for elementary fluorine hydrogen reactions; structure, energetics, and reactivity of carbenes; and the theory of self-consistent electron pairs

  12. Molecular dynamics simulation of a chemical reaction

    International Nuclear Information System (INIS)

    Molecular dynamics is used to study the chemical reaction A+A→B+B. It is shown that the reaction rate constant follows the Arrhenius law both for Lennard-Jones and hard sphere interaction potentials between substrate particles. A. For the denser systems the reaction rate is proportional to the value of the radial distribution function at the contact point of two hard spheres. 10 refs, 4 figs

  13. Computed potential energy surfaces for chemical reactions

    Science.gov (United States)

    Walch, Stephen P.

    1994-01-01

    Quantum mechanical methods have been used to compute potential energy surfaces for chemical reactions. The reactions studied were among those believed to be important to the NASP and HSR programs and included the recombination of two H atoms with several different third bodies; the reactions in the thermal Zeldovich mechanism; the reactions of H atom with O2, N2, and NO; reactions involved in the thermal De-NO(x) process; and the reaction of CH(squared Pi) with N2 (leading to 'prompt NO'). These potential energy surfaces have been used to compute reaction rate constants and rates of unimolecular decomposition. An additional application was the calculation of transport properties of gases using a semiclassical approximation (and in the case of interactions involving hydrogen inclusion of quantum mechanical effects).

  14. Aerosol simulation including chemical and nuclear reactions

    Energy Technology Data Exchange (ETDEWEB)

    Marwil, E.S.; Lemmon, E.C.

    1985-01-01

    The numerical simulation of aerosol transport, including the effects of chemical and nuclear reactions presents a challenging dynamic accounting problem. Particles of different sizes agglomerate and settle out due to various mechanisms, such as diffusion, diffusiophoresis, thermophoresis, gravitational settling, turbulent acceleration, and centrifugal acceleration. Particles also change size, due to the condensation and evaporation of materials on the particle. Heterogeneous chemical reactions occur at the interface between a particle and the suspending medium, or a surface and the gas in the aerosol. Homogeneous chemical reactions occur within the aersol suspending medium, within a particle, and on a surface. These reactions may include a phase change. Nuclear reactions occur in all locations. These spontaneous transmutations from one element form to another occur at greatly varying rates and may result in phase or chemical changes which complicate the accounting process. This paper presents an approach for inclusion of these effects on the transport of aerosols. The accounting system is very complex and results in a large set of stiff ordinary differential equations (ODEs). The techniques for numerical solution of these ODEs require special attention to achieve their solution in an efficient and affordable manner. 4 refs.

  15. Theoretical study of chemical reactions in solution

    International Nuclear Information System (INIS)

    Quantum chemical calculations in solution are becoming more and more important in chemistry. Reference interaction site model self-consistent field (RISM-SCF) is one of the powerful approaches to perform quantum chemical calculations in solution. In this work, we developed a new generation of RISM-SCF, where a robust fitting method was newly introduced. We applied the new method to tautomerization reaction of cytosine in aqueous phase. Our calculation reproduced experimentally obtained relative stabilities and relative free energies correctly

  16. Classification of Chemical Reactions: Stages of Expertise

    Science.gov (United States)

    Stains, Marilyne; Talanquer, Vicente

    2008-01-01

    In this study we explore the strategies that undergraduate and graduate chemistry students use when engaged in classification tasks involving symbolic and microscopic (particulate) representations of different chemical reactions. We were specifically interested in characterizing the basic features to which students pay attention when classifying…

  17. Chemical reactions in reverse micelle systems

    Science.gov (United States)

    Matson, Dean W.; Fulton, John L.; Smith, Richard D.; Consani, Keith A.

    1993-08-24

    This invention is directed to conducting chemical reactions in reverse micelle or microemulsion systems comprising a substantially discontinuous phase including a polar fluid, typically an aqueous fluid, and a microemulsion promoter, typically a surfactant, for facilitating the formation of reverse micelles in the system. The system further includes a substantially continuous phase including a non-polar or low-polarity fluid material which is a gas under standard temperature and pressure and has a critical density, and which is generally a water-insoluble fluid in a near critical or supercritical state. Thus, the microemulsion system is maintained at a pressure and temperature such that the density of the non-polar or low-polarity fluid exceeds the critical density thereof. The method of carrying out chemical reactions generally comprises forming a first reverse micelle system including an aqueous fluid including reverse micelles in a water-insoluble fluid in the supercritical state. Then, a first reactant is introduced into the first reverse micelle system, and a chemical reaction is carried out with the first reactant to form a reaction product. In general, the first reactant can be incorporated into, and the product formed in, the reverse micelles. A second reactant can also be incorporated in the first reverse micelle system which is capable of reacting with the first reactant to form a product.

  18. Chemical computing with reaction-diffusion processes.

    Science.gov (United States)

    Gorecki, J; Gizynski, K; Guzowski, J; Gorecka, J N; Garstecki, P; Gruenert, G; Dittrich, P

    2015-07-28

    Chemical reactions are responsible for information processing in living organisms. It is believed that the basic features of biological computing activity are reflected by a reaction-diffusion medium. We illustrate the ideas of chemical information processing considering the Belousov-Zhabotinsky (BZ) reaction and its photosensitive variant. The computational universality of information processing is demonstrated. For different methods of information coding constructions of the simplest signal processing devices are described. The function performed by a particular device is determined by the geometrical structure of oscillatory (or of excitable) and non-excitable regions of the medium. In a living organism, the brain is created as a self-grown structure of interacting nonlinear elements and reaches its functionality as the result of learning. We discuss whether such a strategy can be adopted for generation of chemical information processing devices. Recent studies have shown that lipid-covered droplets containing solution of reagents of BZ reaction can be transported by a flowing oil. Therefore, structures of droplets can be spontaneously formed at specific non-equilibrium conditions, for example forced by flows in a microfluidic reactor. We describe how to introduce information to a droplet structure, track the information flow inside it and optimize medium evolution to achieve the maximum reliability. Applications of droplet structures for classification tasks are discussed. PMID:26078345

  19. Minimum Energy Pathways for Chemical Reactions

    Science.gov (United States)

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

    1995-01-01

    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. 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 useful results for a number of chemically important systems. The talk will focus on a number of applications to reactions leading to NOx and soot formation in hydrocarbon combustion.

  20. 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.

  1. Chemical reaction systems with toric steady states

    CERN Document Server

    Millan, Mercedes Perez; Shiu, Anne; Conradi, Carsten

    2011-01-01

    Mass-action chemical reaction systems are frequently used in Computational Biology. The corresponding polynomial dynamical systems are often large, consisting of tens or even hundreds of ordinary differential equations, and poorly parameterized (due to noisy measurement data and a small number of data points and repetitions). Therefore, it is often difficult to establish the existence of (positive) steady states or to determine whether more complicated phenomena such as multistationarity exist. If, however, the steady state ideal of the system is a binomial ideal, then we show that these questions can be answered easily. The focus of this work is on systems with this property, and we say that such systems have toric steady states. Our main result gives sufficient conditions for a chemical reaction system to have toric steady states. Furthermore, we analyze the capacity of such a system to exhibit positive steady states and multistationarity. Examples of systems with toric steady states include weakly-reversib...

  2. Neural Networks in Chemical Reaction Dynamics

    CERN Document Server

    Raff, Lionel; Hagan, Martin

    2011-01-01

    This monograph presents recent advances in neural network (NN) approaches and applications to chemical reaction dynamics. Topics covered include: (i) the development of ab initio potential-energy surfaces (PES) for complex multichannel systems using modified novelty sampling and feedforward NNs; (ii) methods for sampling the configuration space of critical importance, such as trajectory and novelty sampling methods and gradient fitting methods; (iii) parametrization of interatomic potential functions using a genetic algorithm accelerated with a NN; (iv) parametrization of analytic interatomic

  3. Optimization of a Chemical Reaction Train

    Directory of Open Access Journals (Sweden)

    Bahar Sansar

    2010-01-01

    Full Text Available This project consists of the optimization of a chemical reactor train. The reactor considered here is the continuous stirred tank reactor (CSTR, one of the reactor models used in engineering. Given the design equation for the CSTR and the cost function for a reactor, the following values are determined; the optimum number of reactors in the reaction train, the volume of each reactor and the total cost.

  4. Optimization of a Chemical Reaction Train

    OpenAIRE

    Bahar Sansar

    2010-01-01

    This project consists of the optimization of a chemical reactor train. The reactor considered here is the continuous stirred tank reactor (CSTR), one of the reactor models used in engineering. Given the design equation for the CSTR and the cost function for a reactor, the following values are determined; the optimum number of reactors in the reaction train, the volume of each reactor and the total cost.

  5. Suppression of Ostwald Ripening by Chemical Reactions

    Science.gov (United States)

    Zwicker, David; Hyman, Anthony A.; Jülicher, Frank

    2015-03-01

    Emulsions consisting of droplets immersed in a fluid are typically unstable and coarsen over time. One important coarsening process is Ostwald ripening, which is driven by the surface tension of the droplets. Ostwald ripening must thus be suppressed to stabilize emulsions, e.g. to control the properties of pharmaceuticals, food, or cosmetics. Suppression of Ostwald ripening is also important in biological cells, which contain stable liquid-like compartments, e.g. germ granules, Cajal-bodies, and centrosomes. Such systems are often driven away from equilibrium by chemical reactions and can thus be called active emulsions. Here, we show that non-equilibrium chemical reactions can suppress Ostwald Ripening, leading to stable, monodisperse emulsions. We derive analytical approximations of the typical droplet size, droplet count, and time scale of the dynamics from a coarse-grained description of the droplet dynamics. We also compare these results to numerical simulations of the continuous concentration fields. Generally, we thus show how chemical reactions can be used to stabilize emulsions and to control their properties in technology and nature.

  6. The smallest chemical reaction system with bistability

    Directory of Open Access Journals (Sweden)

    Wilhelm Thomas

    2009-09-01

    Full Text Available Abstract Background Bistability underlies basic biological phenomena, such as cell division, differentiation, cancer onset, and apoptosis. So far biologists identified two necessary conditions for bistability: positive feedback and ultrasensitivity. Results Biological systems are based upon elementary mono- and bimolecular chemical reactions. In order to definitely clarify all necessary conditions for bistability we here present the corresponding minimal system. According to our definition, it contains the minimal number of (i reactants, (ii reactions, and (iii terms in the corresponding ordinary differential equations (decreasing importance from i-iii. The minimal bistable system contains two reactants and four irreversible reactions (three bimolecular, one monomolecular. We discuss the roles of the reactions with respect to the necessary conditions for bistability: two reactions comprise the positive feedback loop, a third reaction filters out small stimuli thus enabling a stable 'off' state, and the fourth reaction prevents explosions. We argue that prevention of explosion is a third general necessary condition for bistability, which is so far lacking discussion in the literature. Moreover, in addition to proving that in two-component systems three steady states are necessary for bistability (five for tristability, etc., we also present a simple general method to design such systems: one just needs one production and three different degradation mechanisms (one production, five degradations for tristability, etc.. This helps modelling multistable systems and it is important for corresponding synthetic biology projects. Conclusion The presented minimal bistable system finally clarifies the often discussed question for the necessary conditions for bistability. The three necessary conditions are: positive feedback, a mechanism to filter out small stimuli and a mechanism to prevent explosions. This is important for modelling bistability with

  7. Chemical reaction due to stronger Ramachandran interaction

    Indian Academy of Sciences (India)

    Andrew Das Arulsamy

    2014-05-01

    The origin of a chemical reaction between two reactant atoms is associated with the activation energy, on the assumption that, high-energy collisions between these atoms, are the ones that overcome the activation energy. Here, we show that a stronger attractive van der Waals (vdW) and electron-ion Coulomb interactions between two polarized atoms are responsible for initiating a chemical reaction, either before or after the collision. We derive this stronger vdW attraction formula exactly using the quasi one-dimensional Drude model within the ionization energy theory and the energy-level spacing renormalization group method. Along the way, we expose the precise physical mechanism responsible for the existence of a stronger vdW interaction for both long and short distances, and also show how to technically avoid the electron-electron Coulomb repulsion between polarized electrons from these two reactant atoms. Finally, we properly and correctly associate the existence of this stronger attraction with Ramachandran’s `normal limits’ (distance shorter than what is allowed by the standard vdW bond) between chemically nonbonded atoms.

  8. 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.

  9. Sonoluminescence air bubbles as chemical reaction chambers

    CERN Document Server

    Lohse, D; Dupont, T F; Hilgenfeldt, S; Johnston, B; Lohse, Detlef; Brenner, Michael P; Dupont, Todd F; Hilgenfeldt, Sascha; Johnston, Blaine

    1996-01-01

    Sound driven gas bubbles can emit light pulses, a phenomenon called sonoluminescence. Air is found to be one of the most friendly gases towards this phenomenon, but only if it contains 1\\% argon. We suggest a chemical mechanism to account for the strong dependence on the gas mixture, based on the dissociation of nitrogen at high temperatures and reactions which form \\rm{NO}_3^- and \\rm{NH}_4^+, among other ions; the reaction products should be investigated experimentally. Inert gases are crucial for stable sonoluminescence because they do not react with the fluid. Our phase diagram in the concentration vs forcing pressure space is applicable to any gas mixture and in good agreement with latest measurements of the UCLA group.

  10. Law of Localization in Chemical Reaction Networks

    Science.gov (United States)

    Okada, Takashi; Mochizuki, Atsushi

    2016-07-01

    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. Nonzero response patterns turn out to exhibit two characteristic features, 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.

  11. Chemical Reaction Dynamics in Nanoscle Environments

    Energy Technology Data Exchange (ETDEWEB)

    Evelyn M. Goldfield

    2006-09-26

    The major focus of the research in this program is the study of the behavior of molecular systems confined in nanoscale environments. The goal is to develop a theoretical framework for predicting how chemical reactions occur in nanoscale environments. To achieve this goal we have employed ab initio quantum chemistry, classical dynamics and quantum dynamics methods. Much of the research has focused on the behavior of molecules confined within single-walled carbon nanotubes (SWCNTs). We have also studied interactions of small molecules with the exterior surface of SWCNTs. Nonequilibrium molecular dynamics of interfaces of sliding surface interfaces have also been performed.

  12. 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.

  13. 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...

  14. 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…

  15. Mass transfer with complex reversible chemical reactions. II: Parallel reversible chemical reactions

    NARCIS (Netherlands)

    Versteeg, G.F.; Kuipers, J.A.M.; Beckum, van F.P.H.; Swaaij, van W.P.M.

    1990-01-01

    An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and co

  16. Thermodynamic performance for a chemical reactions model

    International Nuclear Information System (INIS)

    This paper presents the analysis efficiency of a chemical reaction model of four states, such that their activated states can occur at any point (fixed but arbitrary) of the transition from one state to another. This mechanism operates under a single heat reservoir temperature, unlike the internal combustion engines where there are two thermal sources. Different efficiencies are compared to this model, which operate at different optimum engine regimes. Thus, some analytical methods are used to give an approximate expression, facilitating the comparison between them. Finally, the result is compared with that obtained by other authors considered a general model of an isothermal molecular machine. Taking into account the above, the results seems to follow a similar behaviour for all the optimized engines, which resemble that observed in the case of heat engine efficiencies

  17. Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium chemical reactions

    International Nuclear Information System (INIS)

    Chemical energy transfer mechanisms at finite temperature are explored by a chemical energy transfer theory which is capable of investigating various chemical mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium. Gibbs energy fluxes are obtained as a function of chemical potential, time, and displacement. Diffusion, convection, internal convection, and internal equilibrium chemical energy fluxes are demonstrated. The theory reveals that there are chemical energy flux gaps and broken discrete symmetries at the activation chemical potential, time, and displacement. The statistical, thermodynamic theory is the unification of diffusion and internal convection chemical reactions which reduces to the non-equilibrium generalization beyond the quasi-equilibrium theories of migration and diffusion processes. The relationship between kinetic theories of chemical and electrochemical reactions is also explored. The theory is applied to explore non-equilibrium chemical reactions as an illustration. Three variable separation constants indicate particle number constants and play key roles in describing the distinct chemical reaction mechanisms. The kinetics of chemical energy transfer accounts for the four control mechanisms of chemical reactions such as activation, concentration, transition, and film chemical reactions. - Highlights: • Chemical energy transfer theory is proposed for non-, quasi-, and equilibrium. • Gibbs energy fluxes are expressed by chemical potential, time, and displacement. • Relationship between chemical and electrochemical reactions is discussed. • Theory is applied to explore nonequilibrium energy transfer in chemical reactions. • Kinetics of non-equilibrium chemical reactions shows the four control mechanisms

  18. Deterministic Function Computation with Chemical Reaction Networks

    CERN Document Server

    Chen, Ho-Lin; Soloveichik, David

    2012-01-01

    We study the deterministic computation of functions on tuples of natural numbers by chemical reaction networks (CRNs). CRNs have been shown to be efficiently Turing-universal when allowing for a small probability of error. CRNs that are guaranteed to converge on a correct answer, on the other hand, have been shown to decide only the semilinear predicates. We introduce the notion of function, rather than predicate, computation by representing the output of a function f:N^k --> N^l by a count of some molecular species, i.e., if the CRN starts with n_1,...,n_k molecules of some "input" species X_1,...,X_k, the CRN is guaranteed to converge to having f(n_1,...,n_k) molecules of the "output" species Y_1,...,Y_l. We show that a function f:N^k --> N^l is deterministically computed by a CRN if and only if its graph {(x,y) \\in N^k x N^l | f(x) = y} is a semilinear set. Finally, we show that each semilinear function f can be computed on input x in expected time O(polylog |x|).

  19. Flows and chemical reactions in an electromagnetic field

    CERN Document Server

    Prud'homme, Roger

    2014-01-01

    This book - a sequel of previous publications 'Flows and Chemical Reactions', 'Chemical Reactions Flows in Homogeneous Mixtures' and 'Chemical Reactions and Flows in Heterogeneous Mixtures' - is devoted to flows with chemical reactions in the electromagnetic field. The first part, entitled basic equations, consists of four chapters. The first chapter provides an overview of the equations of electromagnetism in Minkowski spacetime. This presentation is extended to balance equations, first in homogeneous media unpolarized in the second chapter and homogeneous fluid medium polarized in the thir

  20. 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.

  1. Semiclassical methods in chemical reaction dynamics

    International Nuclear Information System (INIS)

    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

  2. Semiclassical methods in chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Keshavamurthy, S.

    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.

  3. 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.

  4. 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.

  5. Stereodynamics: From elementary processes to macroscopic chemical reactions

    International Nuclear Information System (INIS)

    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

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

    OpenAIRE

    Rappoport, Dmitrij; Galvin, Cooper J.; Zubarev, Dmitry; Aspuru-Guzik, Alan

    2014-01-01

    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 reacti...

  7. Thermo effect of chemical reaction in irreversible electrochemical systems

    International Nuclear Information System (INIS)

    From first law of thermodynamics the expressions of statistical calculation of 'Fundamental' and 'Thermo-chemical' thermal effects are obtained. Besides, method of calculation of thermal effect of chemical reactions in non-equilibrium electro-chemical systems is accurately discussed. (author). 7 refs

  8. Acoustic wave propagation in fluids with coupled chemical reactions

    International Nuclear Information System (INIS)

    This investigation presents a hydroacoustic theory which accounts for sound absorption and dispersion in a multicomponent mixture of reacting fluids (assuming a set of first-order acoustic equations without diffusion) such that several coupled reactions can occur simultaneously. General results are obtained in the form of a biquadratic characteristic equation (called the Kirchhoff-Langevin equation) for the complex propagation variable chi = - (α + iω/c) in which α is the attenuation coefficient, c is the phase speed of the progressive wave and ω is the angular frequency. Computer simulations of sound absorption spectra have been made for three different chemical systems, each comprised of two-step chemical reactions using physico-chemical data available in the literature. The chemical systems studied include: (1) water-dioxane, (2) aqueous solutions of glycine and (3) cobalt polyphosphate mixtures. Explicit comparisons are made between the exact biquadratic characteristic solution and the approximate equation (sometimes referred to as a Debye equation) previously applied to interpret the experimental data for the chemical reaction contribution to the absorption versus frequency. The relative chemical reaction and classical viscothermal contributions to the sound absorption are also presented. Several discrepancies that can arise when estimating thermodynamic data (chemical reaction heats or volume changes) for multistep chemical reaction systems when making dilute solution or constant density assumptions are discussed

  9. Non-equilibrium effects in high temperature chemical reactions

    Science.gov (United States)

    Johnson, Richard E.

    1987-01-01

    Reaction rate data were collected for chemical reactions occurring at high temperatures during reentry of space vehicles. The principle of detailed balancing is used in modeling kinetics of chemical reactions at high temperatures. Although this principle does not hold for certain transient or incubation times in the initial phase of the reaction, it does seem to be valid for the rates of internal energy transitions that occur within molecules and atoms. That is, for every rate of transition within the internal energy states of atoms or molecules, there is an inverse rate that is related through an equilibrium expression involving the energy difference of the transition.

  10. Communication: Control of chemical reactions using electric field gradients.

    Science.gov (United States)

    Deshmukh, Shivaraj D; Tsori, Yoav

    2016-05-21

    We examine theoretically a new idea for spatial and temporal control of chemical reactions. When chemical reactions take place in a mixture of solvents, an external electric field can alter the local mixture composition, thereby accelerating or decelerating the rate of reaction. The spatial distribution of electric field strength can be non-trivial and depends on the arrangement of the electrodes producing it. In the absence of electric field, the mixture is homogeneous and the reaction takes place uniformly in the reactor volume. When an electric field is applied, the solvents separate and the reactants are concentrated in the same phase or separate to different phases, depending on their relative miscibility in the solvents, and this can have a large effect on the kinetics of the reaction. This method could provide an alternative way to control runaway reactions and to increase the reaction rate without using catalysts. PMID:27208928

  11. Communication: Control of chemical reactions using electric field gradients

    Science.gov (United States)

    Deshmukh, Shivaraj D.; Tsori, Yoav

    2016-05-01

    We examine theoretically a new idea for spatial and temporal control of chemical reactions. When chemical reactions take place in a mixture of solvents, an external electric field can alter the local mixture composition, thereby accelerating or decelerating the rate of reaction. The spatial distribution of electric field strength can be non-trivial and depends on the arrangement of the electrodes producing it. In the absence of electric field, the mixture is homogeneous and the reaction takes place uniformly in the reactor volume. When an electric field is applied, the solvents separate and the reactants are concentrated in the same phase or separate to different phases, depending on their relative miscibility in the solvents, and this can have a large effect on the kinetics of the reaction. This method could provide an alternative way to control runaway reactions and to increase the reaction rate without using catalysts.

  12. Visualizing chemical reactions confined under graphene.

    Science.gov (United States)

    Mu, Rentao; Fu, Qiang; Jin, Li; Yu, Liang; Fang, Guangzong; Tan, Dali; Bao, Xinhe

    2012-05-14

    An undercover agent: graphene has been used as an imaging agent to visualize interfacial reactions under its cover, and exhibits a strong confinement effect on the chemistry of molecules underneath. In a CO atmosphere, CO penetrates into the graphene/Pt(111) interface and reacts with O(2) therein, whereas intercalated CO desorbs from the Pt surface. PMID:22492473

  13. Charge exchange and chemical reactions with trapped Th3+

    International Nuclear Information System (INIS)

    We have measured the reaction rates of trapped, buffer gas cooled Th3+ 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 Th3+ make them more prone to loss. Our results show that reactions of Th3+ 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 Th3+ with oxygen and methane proceed primarily via charge exchange, while simultaneous charge exchange and chemical reaction occurs between Th3+ and carbon dioxide. Loss rates of Th3+ in helium are consistent with reaction with impurities in the gas. Reaction rates of Th3+ with nitrogen and argon depend on the internal electronic configuration of the Th3+.

  14. 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$^{3+}$.

  15. Inelastic Collisions and Chemical Reactions of Molecules at Ultracold Temperatures

    OpenAIRE

    Quéméner, Goulven; Balakrishnan, Naduvalath; Dalgarno, Alexander

    2010-01-01

    This paper summarizes the recent theoretical works on inelastic collisions and chemical reactions at cold and ultracold temperatures involving neutral or ionic systems of atoms and molecules. Tables of zero-temperature rate constants of various molecules are provided.

  16. Pyrimidine-specific chemical reactions useful for DNA sequencing.

    OpenAIRE

    Rubin, C M; Schmid, C. W.

    1980-01-01

    Potassium permanganate reacts selectively with thymidine residues in DNA (1) while hydroxylamine hydrochloride at pH 6 specifically attacks cytosine (2). We have adopted these reactions for use with the chemical sequencing method developed by Maxam and Gilbert (3).

  17. CHEMICAL REACTIONS SIMULATED BY GROUND-WATER-QUALITY MODELS.

    Science.gov (United States)

    Grove, David B.; Stollenwerk, Kenneth G.

    1987-01-01

    Recent literature concerning the modeling of chemical reactions during transport in ground water is examined with emphasis on sorption reactions. The theory of transport and reactions in porous media has been well documented. Numerous equations have been developed from this theory, to provide both continuous and sequential or multistep models, with the water phase considered for both mobile and immobile phases. Chemical reactions can be either equilibrium or non-equilibrium, and can be quantified in linear or non-linear mathematical forms. Non-equilibrium reactions can be separated into kinetic and diffusional rate-limiting mechanisms. Solutions to the equations are available by either analytical expressions or numerical techniques. Saturated and unsaturated batch, column, and field studies are discussed with one-dimensional, laboratory-column experiments predominating. A summary table is presented that references the various kinds of models studied and their applications in predicting chemical concentrations in ground waters.

  18. 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

  19. Systematic Error Estimation for Chemical Reaction Energies

    CERN Document Server

    Simm, Gregor N

    2016-01-01

    For the theoretical understanding of the reactivity of complex chemical systems accurate relative energies between intermediates and transition states are required. Despite its popularity, density functional theory (DFT) often fails to provide sufficiently accurate data, especially for molecules containing transition metals. Due to the huge number of intermediates that need to be studied for all but the simplest chemical processes, DFT is to date the only method that is computationally feasible. Here, we present a Bayesian framework for DFT that allows for error estimation of calculated properties. Since the optimal choice of parameters in present-day density functionals is strongly system dependent, we advocate for a system-focused re-parameterization. While, at first sight, this approach conflicts with the first-principles character of DFT that should make it in principle system independent, we deliberately introduce system dependence because we can then assign a stochastically meaningful error to the syste...

  20. 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

  1. Reaction path analysis of sodium-water chemical reaction field using laser diagnostics

    International Nuclear Information System (INIS)

    In a sodium-cooled fast reactor (SFR), liquid sodium is used as a heat transfer fluid because of its excellent heat transport capability. On the other hand, it has strong chemical reactivity with water vapor. One of the design basis accidents of the SFR is the water leakage into the liquid sodium flow by a breach of heat transfer tubes. Therefore, the study on sodium-water chemical reactions is of importance for security reasons. This study aims to clarify the gas phase sodium-water reaction path and reaction products. Na, Na2, H2O, and reaction products in the counter-flow sodium-water reaction field were measured using laser diagnostics such as Raman scattering and photo-fragmentation. The main product in the sodium-water reaction was determined to be NaOH and its reaction path was discussed using Na-H2O elementally reaction analysis. (author)

  2. 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.

  3. Chemical reactions driven by concentrated solar energy

    Science.gov (United States)

    Levy, Moshe

    Solar energy can be used for driving endothermic reactions, either photochemically or thermally. The fraction of the solar spectrum that can be photochemically active is quite small. Therefore, it is desirable to be able to combine photochemical and thermal processes in order to increase the overall efficiency. Two thermally driven reactions are being studied: oil shale gasification and methane reforming. In both cases, the major part of the work was done in opaque metal reactors where photochemical reactions cannot take place. We then proceeded working in transparent quartz reactors. The results are preliminary, but they seem to indicate that there may be some photochemical enhancement. The experimental solar facilities used for this work include the 30 kW Schaeffer Solar Furnace and the 3 MW Solar Central Receiver in operation at the Weizmann Institute. The furnace consists of a 96 sq. m flat heliostat, that follows the sun by computer control. It reflects the solar radiation onto a spherical concentrator, 7.3 m in diameter, with a rim angle of 65 degrees. The furnace was characterized by radiometric and calorimetric measurements to show a solar concentration ratio of over 10,000 suns. The central receiver consists of 64 concave heliostats, 54 sq. m each, arranged in a north field and facing a 52 m high tower. The tower has five target levels that can be used simultaneously. The experiments with the shale gasification were carried out at the lowest level, 20 m above ground, which has the lowest solar efficiency and is assigned for low power experiments. We used secondary concentrators to boost the solar flux.

  4. 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…

  5. A network dynamics approach to chemical reaction networks

    NARCIS (Netherlands)

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

    2016-01-01

    A treatment of chemical reaction network theory is given from the perspective of nonlinear network dynamics, in particular of consensus dynamics. By starting from the complex-balanced assumption the reaction dynamics governed by mass action kinetics can be rewritten into a form which allows for a ve

  6. Open complex-balanced mass action chemical reaction networks

    NARCIS (Netherlands)

    Rao, Shodhan; van der Schaft, Arjan; Jayawardhana, Bayu

    2014-01-01

    We consider open chemical reaction networks, i.e. ones with inflows and outflows. We assume that all the inflows to the network are constant and all outflows obey the mass action kinetics rate law. We define a complex-balanced open reaction network as one that admits a complex-balanced steady state.

  7. 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…

  8. On the Complexity of Reconstructing Chemical Reaction Networks

    DEFF Research Database (Denmark)

    Fagerberg, Rolf; Flamm, Christoph; Merkle, Daniel;

    2013-01-01

    The analysis of the structure of chemical reaction networks is crucial for a better understanding of chemical processes. Such networks are well described as hypergraphs. However, due to the available methods, analyses regarding network properties are typically made on standard graphs derived from...... the full hypergraph description, e.g. on the so-called species and reaction graphs. However, a reconstruction of the underlying hypergraph from these graphs is not necessarily unique. In this paper, we address the problem of reconstructing a hypergraph from its species and reaction graph and show NP...

  9. Use of radioactive tracers in chemical reactions

    International Nuclear Information System (INIS)

    A method for the determination of small quantities of nickel using radioactive tracers is presented. An analytical application of the displacement reaction between nickel and zinc ethylenediaminetetraacetate labeled with zinc-65 is pursued. This method is based on the extraction of radioactive zinc displaced by nickel from the zinc chelate into a dithizone-carbon tetracloride solution and the subsequent measurement of the activity of an aliquot of the extract. The method is very sensitive and nickel can be measured in concentrations as small as 0.1μg/ml or even less, depending on the specific activity of the radioreagent used. The precision and the accuracy of the method are determined. The problem of interferences, trying to eliminate them by using masking agents or by means of a previous separation between nickel and other interfering metals, is also investigated

  10. Chemical kinetic reaction mechanism for the combustion of propane

    Science.gov (United States)

    Jachimowski, C. J.

    1984-01-01

    A detailed chemical kinetic reaction mechanism for the combustion of propane is presented and discussed. The mechanism consists of 27 chemical species and 83 elementary chemical reactions. Ignition and combustion data as determined in shock tube studies were used to evaluate the mechanism. Numerical simulation of the shock tube experiments showed that the kinetic behavior predicted by the mechanism for stoichiometric mixtures is in good agrement with the experimental results over the entire temperature range examined (1150-2600K). Sensitivity and theoretical studies carried out using the mechanism revealed that hydrocarbon reactions which are involved in the formation of the HO2 radical and the H2O2 molecule are very important in the mechanism and that the observed nonlinear behavior of ignition delay time with decreasing temperature can be interpreted in terms of the increased importance of the HO2 and H2O2 reactions at the lower temperatures.

  11. Numerical simulation of rising bubble with chemical reaction

    Science.gov (United States)

    Sahu, Kirti; Tripathi, Manoj; Matar, Omar; Karapetsas, George

    2014-11-01

    The dynamics of a rising bubble under the action of gravity and in the presence of an exothermic chemical reaction at the interface is investigated via direct numerical simulation using Volume-of-Fluid (VOF) method. The product of the chemical reaction, and temperature rise due to the exothermic chemical reaction influence the local viscosity and surface tension near the interfacial region, which in turn give rise to many interesting dynamics. The flow is governed by continuity, Navier-Stokes equations along with the convection equation of the volume fraction of the outer fluid and the energy equation. The effects of the Bond, Damkohler, and Reynolds numbers, and of the dimensionless heat of reaction are investigated. The results of this parametric study will be presented at the meeting.

  12. Chemical reaction between single hydrogen atom and graphene

    International Nuclear Information System (INIS)

    We study chemical reaction between a single hydrogen atom and a graphene, which is the elemental reaction between hydrogen and graphitic carbon materials. In the present work, classical molecular dynamics simulation is used with modified Brenner's empirical bond order potential. The three reactions, that is, absorption reaction, reflection reaction and penetration reaction, are observed in our simulation. Reaction rates depend on the incident energy of the hydrogen atom and the graphene temperature. The dependence can be explained by the following mechanisms: (1) The hydrogen atom receives repulsive force by π-electrons in addition to nuclear repulsion. (2) Absorbing the hydrogen atom, the graphene transforms its structure to the 'overhand' configuration such as sp3 state. (3) The hexagonal hole of the graphene is expanded during the penetration of the hydrogen atom. (author)

  13. Isotope effects of sulfur in chemical reactions

    International Nuclear Information System (INIS)

    Sulfur is an important component of organic matter because it forms compounds with many elements. Due to high chemical activity of sulfur, it takes part in biological and geological processes in which isotope effects are occurring. It has been shown during last years research of isotope effects that we have take into account not only mass difference but also many other physical properties of nuclides e.g. even or odd number of neutrons in nuclei, shape and distribution of charge, turn of nuclear spin etc. The factor remains that new theoretical ideas have been formed on the base of data, being obtained in fractionation processes of heavy element isotope, particularly uranium. Now it is being well known that effects unconnected with vibration energy have also caused an effect on fractionation of considerably lighter elements like iron and magnesium. The important question is, if these effects would come to light during the separation of sulfur isotopes. Sulfur have three even isotopes M = (32, 34, 36) and one odd M 33). This problem is still open. (author)

  14. 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.

  15. Matrix isolation as a tool for studying interstellar chemical reactions

    Science.gov (United States)

    Ball, David W.; Ortman, Bryan J.; Hauge, Robert H.; Margrave, John L.

    1989-01-01

    Since the identification of the OH radical as an interstellar species, over 50 molecular species were identified as interstellar denizens. While identification of new species appears straightforward, an explanation for their mechanisms of formation is not. Most astronomers concede that large bodies like interstellar dust grains are necessary for adsorption of molecules and their energies of reactions, but many of the mechanistic steps are unknown and speculative. It is proposed that data from matrix isolation experiments involving the reactions of refractory materials (especially C, Si, and Fe atoms and clusters) with small molecules (mainly H2, H2O, CO, CO2) are particularly applicable to explaining mechanistic details of likely interstellar chemical reactions. In many cases, matrix isolation techniques are the sole method of studying such reactions; also in many cases, complexations and bond rearrangements yield molecules never before observed. The study of these reactions thus provides a logical basis for the mechanisms of interstellar reactions. A list of reactions is presented that would simulate interstellar chemical reactions. These reactions were studied using FTIR-matrix isolation techniques.

  16. The role of van der Waals interactions in chemical reactions

    International Nuclear Information System (INIS)

    We are studying the role of van der Waals interactions in the chemical reactions from the theoretical view point, especially, a case related to the tunnel effect. The fist case that the cumulative reaction probability depends on the tunnel effect was increased by the van der waals force. This case was proved by theoretical calculation of the reaction rate constant of the reaction: Mu + F2 → MuF + F. The second case was that a van der Waals well was so deep that pseudo bound state was observed in the reaction: F + H2 → HF + H. A van der Waals complex such as AB(v=j=0)...C was excited to the resonance state of AB(vij)...C and A...BC(v,j) by laser, than the resonance state proceeded to AB + C (predissociation) or A + BC(pre-reaction). We succeeded for the first time to calculate theoretically the pre-reaction by the real three dimentional potential curve. The pre-reaction can be observed only the case that the tunnel probability is larger than the non-adiabatic transition probability. The chemical reactions in solid were explained, too. (S.Y.)

  17. 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. PMID:25373137

  18. Mathematical model on surface reaction diffusion in the presence of front chemical reaction

    OpenAIRE

    Permikin, D. V.; Zverev, V. S.

    2013-01-01

    The article discusses a mathematical model of solid-phase diffusion over substance surface accompanied a frontal chemical reaction. The purpose of our article is to describe the concentration distribution and surface reacted layer growth. The model is a system parabolic equations, complicated with the presence of mobile front. It takes account of diffusive fluxes redistribution, sublimation from the surface, chemical reaction reversibility. The asymptotic approximation of the obtained nonline...

  19. Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms

    Science.gov (United States)

    Gao, Connie W.; Allen, Joshua W.; Green, William H.; West, Richard H.

    2016-06-01

    Reaction Mechanism Generator (RMG) constructs kinetic models composed of elementary chemical reaction steps using a general understanding of how molecules react. Species thermochemistry is estimated through Benson group additivity and reaction rate coefficients are estimated using a database of known rate rules and reaction templates. At its core, RMG relies on two fundamental data structures: graphs and trees. Graphs are used to represent chemical structures, and trees are used to represent thermodynamic and kinetic data. Models are generated using a rate-based algorithm which excludes species from the model based on reaction fluxes. RMG can generate reaction mechanisms for species involving carbon, hydrogen, oxygen, sulfur, and nitrogen. It also has capabilities for estimating transport and solvation properties, and it automatically computes pressure-dependent rate coefficients and identifies chemically-activated reaction paths. RMG is an object-oriented program written in Python, which provides a stable, robust programming architecture for developing an extensible and modular code base with a large suite of unit tests. Computationally intensive functions are cythonized for speed improvements.

  20. The Electronic Flux in Chemical Reactions. Insights on the Mechanism of the Maillard Reaction

    Science.gov (United States)

    Flores, Patricio; Gutiérrez-Oliva, Soledad; Herrera, Bárbara; Silva, Eduardo; Toro-Labbé, Alejandro

    2007-11-01

    The electronic transfer that occurs during a chemical process is analysed in term of a new concept, the electronic flux, that allows characterizing the regions along the reaction coordinate where electron transfer is actually taking place. The electron flux is quantified through the variation of the electronic chemical potential with respect to the reaction coordinate and is used, together with the reaction force, to shed light on reaction mechanism of the Schiff base formation in the Maillard reaction. By partitioning the reaction coordinate in regions in which different process might be taking place, electronic reordering associated to polarization and transfer has been identified and found to be localized at specific transition state regions where most bond forming and breaking occur.

  1. Clarification of sodium-water chemical reaction using laser diagnostics

    International Nuclear Information System (INIS)

    In a sodium-cooled fast reactor (SFR), liquid sodium is used as a heat transfer fluid because of its excellent heat transport capability. One of the design basis accidents of the SFR is the water leakage into the liquid sodium flow by a breach of heat transfer tubes in a steam generator. Therefore the study on sodium-water chemical reactions is of paramount importance for safety reasons. This study aims to clarify the sodium-water reaction mechanisms using laser diagnostics. The sodium-water, sodium-oxygen and sodium-hydrogen counter-flow reactions were measured using laser diagnostics such as Raman, absorption and photo-fragmentation spectroscopies. The measurement results show that the main product of the sodium-water reaction is NaOH. The sodium-water reaction rate is slower than that of the sodium-oxygen reaction and hydrogen does not react noticeably with sodium. (author)

  2. Is There a Minimum Electrophilicity Principle in Chemical Reactions?

    Institute of Scientific and Technical Information of China (English)

    NOORIZADEH,Siamak

    2007-01-01

    For 25 simple reactions, the changes of the hardness (△η), polarizability (△α) and electrophilicity index (△ω)and their cube-roots (△η1/3, △α1/3, △ω1/3) were calculated. It is shown that although the Maximum Hardness and Minimum Polarizability Principles are not valid for all reactions, but in most cases △ω1/3<0, whereas we always find △ω<0. Our observation impliesto this fact that for those chemical reactions in which the number of moles decreases or at least remains constant, the most stable species (reactants or products) have the lowest sum of electrophilicities. In other words "the natural direction of a chemical reaction is toward a state of minimum electrophilicity". This fact may be called Minimum Electrophilicity Principle (MEP).

  3. Chemical selforganization of composite catalysts during catalytic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Imbihl, Ronald, E-mail: imbihl@pci.uni-hannover.de [Institut fuer Physikalische Chemie und Elektrochemie, Leibniz-Universitaet Hannover, Callinstrasse 3-3a, D-30167 Hannover (Germany)

    2012-10-15

    Highlights: Black-Right-Pointing-Pointer Selforganization of composite catalysts under reaction conditions. Black-Right-Pointing-Pointer Reactive phase separation causes demixing of catalysts. Black-Right-Pointing-Pointer Condensation patterns in supported oxide catalysts. -- Abstract: Recent progress in the study of selforganization phenomena in catalytic reactions on multi-component surfaces is reviewed. As chemically more complex systems a Rh(1 1 1) surface with ultra-thin vanadium oxide layers ({theta}{sub V} < 0.5 MLE) and a bimetallic Rh(1 1 1)/Ni surface, both subjected to the H{sub 2} + O{sub 2} reaction, were chosen. Applying spatially resolving methods in situ, it is shown that under reaction conditions a reversible redistribution of the components of the catalyst occurs. The redistribution processes are essentially driven by the different chemical affinities of the components to reacting species.

  4. Model Reduction of Chemical Reaction Systems using Elimination

    OpenAIRE

    Boulier, François; Lefranc, Marc; Lemaire, François; Morant, Pierre-Emmanuel

    2007-01-01

    There exist different schemes of model reduction for parametric ordinary differential systems arising from chemical reaction systems. In this paper, we focus on some schemes which rely on quasi-steady states approximations. We show that these schemes can be formulated by means of differential and algebraic elimination. Our formulation is simpler than the classical ones. It permitted us to obtain an approximation of the basic enzymatic reaction system which is different from those of Henri-Mic...

  5. A network dynamics approach to chemical reaction networks

    Science.gov (United States)

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

    2016-04-01

    A treatment of a chemical reaction network theory is given from the perspective of nonlinear network dynamics, in particular of consensus dynamics. By starting from the complex-balanced assumption, the reaction dynamics governed by mass action kinetics can be rewritten into a form which allows for a very simple derivation of a number of key results in the chemical reaction network theory, and which directly relates to the thermodynamics and port-Hamiltonian formulation of the system. Central in this formulation is the definition of a balanced Laplacian matrix on the graph of chemical complexes together with a resulting fundamental inequality. This immediately leads to the characterisation of the set of equilibria and their stability. Furthermore, the assumption of complex balancedness is revisited from the point of view of Kirchhoff's matrix tree theorem. Both the form of the dynamics and the deduced behaviour are very similar to consensus dynamics, and provide additional perspectives to the latter. Finally, using the classical idea of extending the graph of chemical complexes by a 'zero' complex, a complete steady-state stability analysis of mass action kinetics reaction networks with constant inflows and mass action kinetics outflows is given, and a unified framework is provided for structure-preserving model reduction of this important class of open reaction networks.

  6. Waste dissolution with chemical reaction, diffusion and advection

    International Nuclear Information System (INIS)

    This paper extends the mass-transfer analysis to include the effect of advective transport in predicting the steady-state dissolution rate, with a chemical-reaction-rate boundary condition at the surface of a waste form of arbitrary shape. This new theory provides an analytic means of predicting the ground-water velocities at which dissolution rate in a geologic environment will be governed entirely to the chemical reaction rate. As an illustration, we consider the steady-state potential flow of ground water in porous rock surrounding a spherical waste solid. 3 refs., 2 figs

  7. Simulation of chemical reaction dynamics on an NMR quantum computer

    CERN Document Server

    Lu, Dawei; Xu, Ruixue; Chen, Hongwei; Gong, Jiangbin; Peng, Xinhua; Du, Jiangfeng

    2011-01-01

    Quantum simulation can beat current classical computers with minimally a few tens of qubits and will likely become the first practical use of a quantum computer. One promising application of quantum simulation is to attack challenging quantum chemistry problems. Here we report an experimental demonstration that a small nuclear-magnetic-resonance (NMR) quantum computer is already able to simulate the dynamics of a prototype chemical reaction. The experimental results agree well with classical simulations. We conclude that the quantum simulation of chemical reaction dynamics not computable on current classical computers is feasible in the near future.

  8. The Heck reaction in the production of fine chemicals

    OpenAIRE

    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 3,3,3-trifluoropropene. The sunscreen agent 2-ethylhexyl p-methoxy-cinnamate has been produced on pilot scale using Pd/C as catalyst. Naproxen™ is produced via the Heck reaction of 2-bromo-6-methoxy-naphthalene...

  9. Program Helps To Determine Chemical-Reaction Mechanisms

    Science.gov (United States)

    Bittker, D. A.; Radhakrishnan, K.

    1995-01-01

    General Chemical Kinetics and Sensitivity Analysis (LSENS) computer code developed for use in solving complex, homogeneous, gas-phase, chemical-kinetics problems. Provides for efficient and accurate chemical-kinetics computations and provides for sensitivity analysis for variety of problems, including problems involving honisothermal conditions. Incorporates mathematical models for static system, steady one-dimensional inviscid flow, reaction behind incident shock wave (with boundary-layer correction), and perfectly stirred reactor. Computations of equilibrium properties performed for following assigned states: enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. Written in FORTRAN 77 with exception of NAMELIST extensions used for input.

  10. 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

  11. Chemical reaction mediated self-assembly of PTCDA into nanofibers.

    Science.gov (United States)

    Sayyad, Arshad S; Balakrishnan, Kaushik; Ajayan, Pulickel M

    2011-09-01

    Uniform and crystalline nanofibers of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), an insoluble organic semiconducting molecule, have been achieved by self-assembling the molecules using chemical reaction mediated conversion of an appropriately designed soluble precursor, perylene tetracarboxylic acid (PTCA) using carbodiimide chemistry. PMID:21814688

  12. On the steady states of weakly reversible chemical reaction networks

    OpenAIRE

    Deng, Jian; Jones, Christopher; Feinberg, Martin; Nachman, Adrian

    2011-01-01

    A natural condition on the structure of the underlying chemical reaction network, namely weak reversibility, is shown to guarantee the existence of an equilibrium (steady state) in each positive stoichiometric compatibility class for the associated mass-action system. Furthermore, an index formula is given for the set of equilibria in a given stoichiometric compatibility class.

  13. 2011 Chemical Reactions at Surfaces Gordon Research Conference

    Energy Technology Data Exchange (ETDEWEB)

    Peter Stair

    2011-02-11

    The Gordon Research Conference on Chemical Reactions at Surfaces is dedicated to promoting and advancing the fundamental science of interfacial chemistry and physics by providing surface scientists with the foremost venue for presentation and discussion of research occurring at the frontiers of their fields.

  14. 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.

  15. Complex and detailed balancing of chemical reaction networks revisited

    NARCIS (Netherlands)

    van der Schaft, Abraham; Rao, Shodhan; Jayawardhana, Bayu

    2015-01-01

    The characterization of the notions of complex and detailed balancing for mass action kinetics chemical reaction networks is revisited from the perspective of algebraic graph theory, in particular Kirchhoff’s Matrix Tree theorem for directed weighted graphs. This yields an elucidation of previously

  16. Modeling Electric Double-Layers Including Chemical Reaction Effects

    DEFF Research Database (Denmark)

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

    2014-01-01

    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...... 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...

  17. Modeling of Electric Double-Layers Including Chemical Reaction Effects

    International Nuclear Information System (INIS)

    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 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 depend on the bulk solution composition and concentration

  18. 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...

  19. Quantum mechanics of chemical reactions: Recent developments in reactive scattering and in reaction path Hamiltonians

    International Nuclear Information System (INIS)

    Two recent developments in the theory of chemical reaction dynamics are reviewed. First, it has recently been discovered that the S- matrix version of the Kohn variational principle is free of the ''Kohn anomalies'' that have plagued other versions and prevented its general use. This has considerably simplified quantum mechanical reactive scattering calculations, which provide the rigorous characterizations of bimolecular reactions. Second, a new kind of reaction path Hamiltonian has been developed, one based on the ''least motion'' path that interpolates linearly between the reactant and product geometry of the molecule (rather than the previously used minimum energy, or ''intrinsic'' reaction path). The form of Hamiltonian which results is much simpler than the original reaction path Hamiltonian, but more important is the fact that it provides a more physically correct description of hydrogen atom transfer reactions. 44 refs., 4 figs

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

    DEFF Research Database (Denmark)

    Andersen, Jens Enevold Thaulov

    2000-01-01

    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...... 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.......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 attractive...

  1. 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...

  2. A thermodynamic force generated by chemical gradient and adsorption reaction

    CERN Document Server

    Sugawara, Takeshi

    2009-01-01

    Biological units such as macromolecules, organelles, and cells are directed to a proper location under gradients of relevant chemicals. By considering a macroscopic element that has binding sites for a chemical adsorption reaction to occur on its surface, we show the existence of a thermodynamic force that is generated by the gradient and exerted on the element. By assuming local equilibrium and adopting the grand potential from thermodynamics, we derive a formula for such a thermodynamic force, which depends on the chemical potential gradient and Langmuir isotherm. The conditions under which the formula can be applied are demonstrated to hold in intracellular reactions. The role of the force in the partitioning of bacterial chromosome/plasmid during cell division is discussed.

  3. Cellular automaton model of coupled mass transport and chemical reactions

    International Nuclear Information System (INIS)

    Mass transport, coupled with chemical reactions, is modelled as a cellular automaton in which solute molecules perform a random walk on a lattice and react according to a local probabilistic rule. Assuming molecular chaos and a smooth density function, we obtain the standard reaction-transport equations in the continuum limit. The model is applied to the reactions a + b ↔c and a + b →c, where we observe interesting macroscopic effects resulting from microscopic fluctuations and spatial correlations between molecules. We also simulate autocatalytic reaction schemes displaying spontaneous formation of spatial concentration patterns. Finally, we propose and discuss the limitations of a simple model for mineral-solute interaction. (author) 5 figs., 20 refs

  4. 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. PMID:26934738

  5. Mathematical description of the nonlinear chemical reactions with oscillatory inflow to the reaction field

    Indian Academy of Sciences (India)

    Aldona Krupska

    2015-06-01

    In this paper the arduous attempt to find a mathematical solution for the nonlinear autocatalytic chemical processes with a time-varying and oscillating inflow of reactant to the reaction medium has been taken. Approximate analytical solution is proposed. Numerical solutions and analytical attempts to solve the non-linear differential equation indicates a phase shift between the oscillatory influx of intermediate reaction reagent to the medium of chemical reaction and the change of its concentration in this medium. Analytical solutions indicate that this shift may be associated with the reaction rate constants 1 and 2 and the relaxation time . The relationship between the phase shift and the oscillatory flow of reactant seems to be similar to that obtained in the case of linear chemical reactions, as described previously, however, the former is much more complex and different. In this paper, we would like to consider whether the effect of forced phase shift in the case of nonlinear and non-oscillatory chemical processes occurring particularly in the living systems have a practical application in laboratory.

  6. A chemical reaction network solver for the astrophysics code NIRVANA

    Science.gov (United States)

    Ziegler, U.

    2016-02-01

    Context. Chemistry often plays an important role in astrophysical gases. It regulates thermal properties by changing species abundances and via ionization processes. This way, time-dependent cooling mechanisms and other chemistry-related energy sources can have a profound influence on the dynamical evolution of an astrophysical system. Modeling those effects with the underlying chemical kinetics in realistic magneto-gasdynamical simulations provide the basis for a better link to observations. Aims: The present work describes the implementation of a chemical reaction network solver into the magneto-gasdynamical code NIRVANA. For this purpose a multispecies structure is installed, and a new module for evolving the rate equations of chemical kinetics is developed and coupled to the dynamical part of the code. A small chemical network for a hydrogen-helium plasma was constructed including associated thermal processes which is used in test problems. Methods: Evolving a chemical network within time-dependent simulations requires the additional solution of a set of coupled advection-reaction equations for species and gas temperature. Second-order Strang-splitting is used to separate the advection part from the reaction part. The ordinary differential equation (ODE) system representing the reaction part is solved with a fourth-order generalized Runge-Kutta method applicable for stiff systems inherent to astrochemistry. Results: A series of tests was performed in order to check the correctness of numerical and technical implementation. Tests include well-known stiff ODE problems from the mathematical literature in order to confirm accuracy properties of the solver used as well as problems combining gasdynamics and chemistry. Overall, very satisfactory results are achieved. Conclusions: The NIRVANA code is now ready to handle astrochemical processes in time-dependent simulations. An easy-to-use interface allows implementation of complex networks including thermal processes

  7. Cellular automaton model of mass transport with chemical reactions

    International Nuclear Information System (INIS)

    The transport and chemical reactions of solutes are modelled as a cellular automaton in which molecules of different species perform a random walk on a regular lattice and react according to a local probabilistic rule. The model describes advection and diffusion in a simple way, and as no restriction is placed on the number of particles at a lattice site, it is also able to describe a wide variety of chemical reactions. Assuming molecular chaos and a smooth density function, we obtain the standard reaction-transport equations in the continuum limit. Simulations on one-and two-dimensional lattices show that the discrete model can be used to approximate the solutions of the continuum equations. We discuss discrepancies which arise from correlations between molecules and how these discrepancies disappear as the continuum limit is approached. Of particular interest are simulations displaying long-time behaviour which depends on long-wavelength statistical fluctuations not accounted for by the standard equations. The model is applied to the reactions a + b ↔ c and a + b → c with homogeneous and inhomogeneous initial conditions as well as to systems subject to autocatalytic reactions and displaying spontaneous formation of spatial concentration patterns. (author) 9 figs., 34 refs

  8. EFFECTIVE SOLUTION METHOD OF CHEMICAL REACTION KINETICS WITH DIFFUSE

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The time integration method with four-order accuracy, self-starting and implicit for the diffuse chemical reaction kinetics equation or the transient instantaneous temperature filed equation was presented. The examples show that both accuracy and stability are better than Runge-Kutta method with four-order. The coefficients of the equation are stored with sparse matrix pattern, so an algorithm is presented which combines a compact storage scheme with reduced computation cost. The computation of the competitive and consecutive reaction in the rotating packed bed, taken as examples,shows that the method is effective.

  9. 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.

  10. Crossed molecular beam studies of atmospheric chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jingsong

    1993-04-01

    The dynamics of several elementary chemical reactions that are important in atmospheric chemistry are investigated. The reactive scattering of ground state chlorine or bromine atoms with ozone molecules and ground state chlorine atoms with nitrogen dioxide molecules is studied using a crossed molecular beams apparatus with a rotatable mass spectrometer detector. The Cl + O{sub 3} {yields} ClO + O{sub 2} reaction has been studied at four collision energies ranging from 6 kcal/mole to 32 kcal/mole. The derived product center-of-mass angular and translational energy distributions show that the reaction has a direct reaction mechanism and that there is a strong repulsion on the exit channel. The ClO product is sideways and forward scattered with respect to the Cl atom, and the translational energy release is large. The Cl atom is most likely to attack the terminal oxygen atom of the ozone molecule. The Br + O{sub 3} {yields} ClO + O{sub 2} reaction has been studied at five collision energies ranging from 5 kcal/mole to 26 kcal/mole. The derived product center-of-mass angular and translational energy distributions are quite similar to those in the Cl + O{sub 3} reaction. The Br + O{sub 3} reaction has a direct reaction mechanism similar to that of the Cl + O{sub 3} reaction. The electronic structure of the ozone molecule seems to play the central role in determining the reaction mechanism in atomic radical reactions with the ozone molecule. The Cl + NO{sub 2} {yields} ClO + NO reaction has been studied at three collision energies ranging from 10.6 kcal/mole to 22.4 kcal/mole. The center-of-mass angular distribution has some forward-backward symmetry, and the product translational energy release is quite large. The reaction proceeds through a short-lived complex whose lifetime is less than one rotational period. The experimental results seem to show that the Cl atom mainly attacks the oxygen atom instead of the nitrogen atom of the NO{sub 2} molecule.

  11. Simulation of underexpanded supersonic jet flows with chemical reactions

    Institute of Scientific and Technical Information of China (English)

    Fu Debin; Yu Yong; Niu Qinglin

    2014-01-01

    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.

  12. Tabletop imaging of structural evolutions in chemical reactions

    CERN Document Server

    Ibrahim, Heide; Beaulieu, Samuel; Schmidt, Bruno E; Thiré, Nicolas; Bisson, Éric; Hebeisen, Christoph T; Wanie, Vincent; Giguére, Mathieu; Kieffer, Jean-Claude; Sanderson, Joseph; Schuurman, Michael S; Légaré, François

    2014-01-01

    The introduction of femto-chemistry has made it a primary goal to follow the nuclear and electronic evolution of a molecule in time and space as it undergoes a chemical reaction. Using Coulomb Explosion Imaging we have shot the first high-resolution molecular movie of a to and fro isomerization process in the acetylene cation. So far, this kind of phenomenon could only be observed using VUV light from a Free Electron Laser [Phys. Rev. Lett. 105, 263002 (2010)]. Here we show that 266 nm ultrashort laser pulses are capable of initiating rich dynamics through multiphoton ionization. With our generally applicable tabletop approach that can be used for other small organic molecules, we have investigated two basic chemical reactions simultaneously: proton migration and C=C bond-breaking, triggered by multiphoton ionization. The experimental results are in excellent agreement with the timescales and relaxation pathways predicted by new and definitively quantitative ab initio trajectory simulations.

  13. Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

    Science.gov (United States)

    David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

    1997-01-01

    Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

  14. Implementation of a vibrationally linked chemical reaction model for DSMC

    Science.gov (United States)

    Carlson, A. B.; Bird, Graeme A.

    1994-01-01

    A new procedure closely linking dissociation and exchange reactions in air to the vibrational levels of the diatomic molecules has been implemented in both one- and two-dimensional versions of Direct Simulation Monte Carlo (DSMC) programs. The previous modeling of chemical reactions with DSMC was based on the continuum reaction rates for the various possible reactions. The new method is more closely related to the actual physics of dissociation and is more appropriate to the particle nature of DSMC. Two cases are presented: the relaxation to equilibrium of undissociated air initially at 10,000 K, and the axisymmetric calculation of shuttle forebody heating during reentry at 92.35 km and 7500 m/s. Although reaction rates are not used in determining the dissociations or exchange reactions, the new method produces rates which agree astonishingly well with the published rates derived from experiment. The results for gas properties and surface properties also agree well with the results produced by earlier DSMC models, equilibrium air calculations, and experiment.

  15. Size Dependence of Chemical Reactions in Nanoscale Aerosol Particles

    Czech Academy of Sciences Publication Activity Database

    Levdansky, V.V.; Smolík, Jiří; Moravec, Pavel

    Helsinki : -, 2010, P2L1. ISBN N. [International Aerosol Conference IAC 2010. Helsinki (FI), 29.08.2010-03.09.2010] R&D Projects: GA ČR GA104/07/1093; GA ČR GA101/09/1633; GA AV ČR(CZ) IAA400720804 Institutional research plan: CEZ:AV0Z40720504 Keywords : size effect * nanoparticles * chemical reactions Subject RIV: CF - Physical ; Theoretical Chemistry www.iac2010.fi

  16. Variable elimination in chemical reaction networks with mass action kinetics

    OpenAIRE

    Feliu, Elisenda; Wiuf, Carsten

    2011-01-01

    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 of variables. The procedure reduces the variables in the system to a set of "core" variables by eliminating variables corresponding to a set of non-interacting species. The steady states are paramet...

  17. Effects of Confinement on Chemical Reaction Equilibrium in Nanoporous Materials

    Czech Academy of Sciences Publication Activity Database

    Smith, W.R.; Lísal, Martin; Brennan, J.K.

    2006-01-01

    Roč. 3984, - (2006), s. 743-751. ISSN 0302-9743 R&D Projects: GA ČR(CZ) GA203/05/0725; GA AV ČR 1ET400720507 Grant ostatní: NRCC(CA) OGP 1041 Institutional research plan: CEZ:AV0Z40720504 Keywords : nanoporous materials * chemical reaction equilibrium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.402, year: 2005

  18. Simulation of chemical reaction dynamics on an NMR quantum computer

    OpenAIRE

    Lu, Dawei; Xu, Nanyang; Xu, Ruixue; Chen, Hongwei; Gong, Jiangbin; Peng, Xinhua; Du, Jiangfeng

    2011-01-01

    Quantum simulation can beat current classical computers with minimally a few tens of qubits and will likely become the first practical use of a quantum computer. One promising application of quantum simulation is to attack challenging quantum chemistry problems. Here we report an experimental demonstration that a small nuclear-magnetic-resonance (NMR) quantum computer is already able to simulate the dynamics of a prototype chemical reaction. The experimental results agree well with classical ...

  19. Mechanisms of chemical reaction initiated by recoil implantation

    International Nuclear Information System (INIS)

    Mechanisms of chemical reactions initiated by recoil implantation were studied in the systems 51Cr+M(acac)3 yields 51Cr(acac)3 where M is a trivalent metal. The yield of 51Cr(acac)3 increased linearly with an increase of inverse of the force constant of metal-oxygen bonding K(M-O). This indicates that there is competition between the implanted 51Cr atom and M. However, exception for this trend was the case of Co(acac)3 catcher, for which the yield of 51Cr(acac)3 was much higher than that expected for a competition reaction. Complex features of the replacement reaction caused by implantation are discussed

  20. Control of Ultracold Chemical Reactions Through Conical Intersections

    Science.gov (United States)

    Makrides, Constantinos; Petrov, Alexander; Kotochigova, Svetlana

    2016-05-01

    The pioneering work on obtaining a quantum degenerate sample of ground state KRb molecules is one of the great successes in ultracold physics. The early experimental and theoretical investigations to describe quantum chemical reactions of ultracold KRb molecules with residual ultracold K atoms have been based on probing their inelastic collision loss rates. A natural progression towards control of molecular reactivity would be to study the potential landscape of the collisional complex with the inherited degeneracies and intersections between two lowest electronic states. The topology of these surfaces provide us with a qualitative understanding of the reaction mechanism. Here we study how the ability to prepare unique initial states combined with the presence of conical intersections can be used to control the outcome of ultracold chemical reactions of alkali-metal atoms and molecules. We locate and determine properties of conical intersections for the KRbK molecular system and determine signatures of non-adiabatic passage through the conical intersection to distinguish between relaxation and reaction pathways. This work is supported by the ARO-MURI and NSF Grants.

  1. 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.

  2. The role of chemical reaction in waste-form performance

    International Nuclear Information System (INIS)

    The dissolution rate of waste solids in a geologic repository is a complex function of waste form geometry, chemical raction rate, exterior flow field, and chemical environment. We present here an analysis to determine the stady-state mass transfer rate, over the entire range of flow conditions relevant to geologic disposal of nuclear waste. The equations for steady-state mass transfer with a chemical-reaction-rate boundary condition are solved by three different mathematical techniques which supplement each other. This theory is illustrated with laboratory leach data for borosilicate-glass and a spherical spent-fuel waste form under typical repository conditions. For borosilicate glass waste in the temperature range of 57/degree/C to 250/degree/C, dissolution rate in a repository is determined for a wide range of chemical reaction rates and for Peclet numbers from zero to well over 100, far beyond any Peclet values expected in a repository. Spent-fuel dissolution in a repository is also investigated, based on the limited leach data now available. 10 refs., 4 figs., 1 tab

  3. Physio-chemical reactions in recycle aggregate concrete.

    Science.gov (United States)

    Tam, Vivian W Y; Gao, X F; Tam, C M; Ng, K M

    2009-04-30

    Concrete waste constitutes the major proportion of construction waste at about 50% of the total waste generated. An effective way to reduce concrete waste is to reuse it as recycled aggregate (RA) for the production of recycled aggregate concrete (RAC). This paper studies the physio-chemical reactions of cement paste around aggregate for normal aggregate concrete (NAC) and RAC mixed with normal mixing approach (NMA) and two-stage mixing approach (TSMA) by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Four kinds of physio-chemical reactions have been recorded from the concrete samples, including the dehydration of C(3)S(2)H(3), iron-substituted ettringite, dehydroxylation of CH and development of C(6)S(3)H at about 90 degrees C, 135 degrees C, 441 degrees C and 570 degrees C, respectively. From the DSC results, it is confirmed that the concrete samples with RA substitution have generated less amount of strength enhancement chemical products when compared to those without RA substitution. However, the results from the TSMA are found improving the RAC quality. The pre-mix procedure of the TSMA can effectively develop some strength enhancing chemical products including, C(3)S(2)H(3), ettringite, CH and C(6)S(3)H, which shows that RAC made from the TSMA can improve the hydration processes. PMID:18718710

  4. Computational analysis of the mechanism of chemical reactions in terms of reaction phases: hidden intermediates and hidden transition States.

    Science.gov (United States)

    Kraka, Elfi; Cremer, Dieter

    2010-05-18

    Computational approaches to understanding chemical reaction mechanisms generally begin by establishing the relative energies of the starting materials, transition state, and products, that is, the stationary points on the potential energy surface of the reaction complex. Examining the intervening species via the intrinsic reaction coordinate (IRC) offers further insight into the fate of the reactants by delineating, step-by-step, the energetics involved along the reaction path between the stationary states. For a detailed analysis of the mechanism and dynamics of a chemical reaction, the reaction path Hamiltonian (RPH) and the united reaction valley approach (URVA) are an efficient combination. The chemical conversion of the reaction complex is reflected by the changes in the reaction path direction t(s) and reaction path curvature k(s), both expressed as a function of the path length s. This information can be used to partition the reaction path, and by this the reaction mechanism, of a chemical reaction into reaction phases describing chemically relevant changes of the reaction complex: (i) a contact phase characterized by van der Waals interactions, (ii) a preparation phase, in which the reactants prepare for the chemical processes, (iii) one or more transition state phases, in which the chemical processes of bond cleavage and bond formation take place, (iv) a product adjustment phase, and (v) a separation phase. In this Account, we examine mechanistic analysis with URVA in detail, focusing on recent theoretical insights (with a variety of reaction types) from our laboratories. Through the utilization of the concept of localized adiabatic vibrational modes that are associated with the internal coordinates, q(n)(s), of the reaction complex, the chemical character of each reaction phase can be identified via the adiabatic curvature coupling coefficients, A(n,s)(s). These quantities reveal whether a local adiabatic vibrational mode supports (A(n,s) > 0) or resists

  5. Automatic learning for the classification of chemical reactions and in statistical thermodynamics

    OpenAIRE

    Latino, Diogo Alexandre Rosa Serra

    2008-01-01

    This Thesis describes the application of automatic learning methods for a) the classification of organic and metabolic reactions, and b) the mapping of Potential Energy Surfaces(PES). The classification of reactions was approached with two distinct methodologies: a representation of chemical reactions based on NMR data, and a representation of chemical reactions from the reaction equation based on the physico-chemical and topological features of chemical bonds. NMR-based classification of ...

  6. 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. PMID:26363083

  7. Chemical reaction and dust formation studies in laboratory hydrocarbon plasmas.

    Science.gov (United States)

    Hippler, Rainer; Majumdar, Abhijit; Thejaswini, H. C.

    Plasma chemical reaction studies with relevance to, e.g., Titan's atmosphere have been per-formed in various laboratory plasmas [1,2]. Chemical reactions in a dielectric barrier discharge at medium pressure of 250-300 mbar have been studied in CH4 /N2 and CH4 /Ar gas mixtures by means of mass spectrometry. The main reaction scheme is production of H2 by fragmenta-tion of CH4 , but also production of larger hydrocarbons like Cn Hm with n up to 10 including formation of different functional CN groups is observed. [1] A. Majumdar and R. Hippler, Development of dielectric barrier discharge plasma processing apparatus for mass spectrometry and thin film deposition, Rev. Sci. Instrum. 78, 075103 (2007) [2] H.T. Do, G. Thieme, M. Frühlich, H. Kersten, and R. Hippler, Ion Molecule and Dust Particle Formation in Ar/CH4 , Ar/C2 H2 and Ar/C3 H6 Radio-frequency Plasmas, Contrib. Plasma Phys. 45, No. 5-6, 378-384 (2005)

  8. Holistic Metrics for Assessment of the Greenness of Chemical Reactions in the Context of Chemical Education

    Science.gov (United States)

    Ribeiro, M. Gabriela T. C.; Machado, Adelio A. S. C.

    2013-01-01

    Two new semiquantitative green chemistry metrics, the green circle and the green matrix, have been developed for quick assessment of the greenness of a chemical reaction or process, even without performing the experiment from a protocol if enough detail is provided in it. The evaluation is based on the 12 principles of green chemistry. The…

  9. Mass transfer with complex reversible chemical reactions—II. parallel reversible chemical reactions

    NARCIS (Netherlands)

    Versteeg, G.F.; Kuipers, J.A.M.; Beckum, F.P.H. van; Swaaij, W.P.M. van

    1990-01-01

    An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and co

  10. A quantum informational approach for dissecting chemical reactions

    CERN Document Server

    Duperrouzel, Corinne; Boguslawski, Katharina; Barcza, Gergerly; Legeza, Örs; Ayers, Paul W

    2014-01-01

    We present a conceptionally different approach to dissect bond-formation processes in metal-driven catalysis using concepts from quantum information theory. Our method uses the entanglement and correlation among molecular orbitals to analyze changes in electronic structure that accompany chemical processes. As a proof-of-principle example, the evolution of nickel-ethene bond-formation is dissected which allows us to monitor the interplay of back-bonding and $\\pi$-donation along the reaction coordinate. Furthermore, the reaction pathway of nickel-ethene complexation is analyzed using quantum chemistry methods revealing the presence of a transition state. Our study supports the crucial role of metal-to-ligand back-donation in the bond-forming process of nickel-ethene.

  11. Chemical reactions of mercury in combustion flue gases

    International Nuclear Information System (INIS)

    Atmospheric Hg is present in different physical and chemical forms, which determine its atmospheric transformation and transport capacities. The chemistry of Hg in flue gases is thus of importance for the deposition pattern around point source emissions. In order to apply Hg cleaning methods in flue gases its speciation is also of importance. To investigate this under realistic conditions, a 17 kW propane fired flue gas generator was used, while the kinetics of specific Hg reactions were investigated in a continuous flow reactor. Elemental Hg is readily oxidized by Cl2 and HCl both at room and at elevated temperatures (up to 900 degree C) but not by NH3, N2O, SO2 or H2S. It reacts with O2 if a catalyst, such as activated carbon, is present. A slow reaction between Hg and NO2 has also been noted. 19 refs., 8 figs., 3 tabs

  12. Thermal energy storage. [by means of chemical reactions

    Science.gov (United States)

    Grodzka, P. G.

    1975-01-01

    The principles involved in thermal energy storage by sensible heat, chemical potential energy, and latent heat of fusion are examined for the purpose of evolving selection criteria for material candidates in the low ( 0 C) and high ( 100 C) temperature ranges. The examination identifies some unresolved theoretical considerations and permits a preliminary formulation of an energy storage theory. A number of candidates in the low and high temperature ranges are presented along with a rating of candidates or potential candidates. A few interesting candidates in the 0 to 100 C region are also included. It is concluded that storage by means of reactions whose reversibility can be controlled either by product removal or by catalytic means appear to offer appreciable advantages over storage with reactions whose reversability cannot be controlled. Among such advantages are listed higher heat storage capacities and more favorable options regarding temperatures of collection, storage, and delivery. Among the disadvantages are lower storage efficiencies.

  13. 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.

  14. Transient assembly of active materials fueled by a chemical reaction

    Science.gov (United States)

    Boekhoven, Job; Hendriksen, Wouter E.; Koper, Ger J. M.; Eelkema, Rienk; van Esch, Jan H.

    2015-09-01

    Fuel-driven self-assembly of actin filaments and microtubules is a key component of cellular organization. Continuous energy supply maintains these transient biomolecular assemblies far from thermodynamic equilibrium, unlike typical synthetic systems that spontaneously assemble at thermodynamic equilibrium. Here, we report the transient self-assembly of synthetic molecules into active materials, driven by the consumption of a chemical fuel. In these materials, reaction rates and fuel levels, instead of equilibrium composition, determine properties such as lifetime, stiffness, and self-regeneration capability. Fibers exhibit strongly nonlinear behavior including stochastic collapse and simultaneous growth and shrinkage, reminiscent of microtubule dynamics.

  15. The hunt for the dynamical resonances in chemical reaction dynamics: a perspective on historical advances

    OpenAIRE

    Yu Angyang; Zhonghua Yang

    2015-01-01

    The theoretical background and basic definition of the resonances in chemical reaction dynamics have been introduced in this article. The historical breakthrough in the experimental search for the reaction resonances has been reviewed in this report, with an emphasis on the crossed molecular beam apparatus. The research of the chemical reaction resonances has attracted many scientists’ attention from 80s of last century. The chemical reaction resonances in the F+H2 reaction were firstly obser...

  16. 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.

  17. The quantum dynamics of electronically nonadiabatic chemical reactions

    Science.gov (United States)

    Truhlar, Donald G.

    1993-01-01

    Considerable progress was achieved on the quantum mechanical treatment of electronically nonadiabatic collisions involving energy transfer and chemical reaction in the collision of an electronically excited atom with a molecule. In the first step, a new diabatic representation for the coupled potential energy surfaces was created. A two-state diabatic representation was developed which was designed to realistically reproduce the two lowest adiabatic states of the valence bond model and also to have the following three desirable features: (1) it is more economical to evaluate; (2) it is more portable; and (3) all spline fits are replaced by analytic functions. The new representation consists of a set of two coupled diabatic potential energy surfaces plus a coupling surface. It is suitable for dynamics calculations on both the electronic quenching and reaction processes in collisions of Na(3p2p) with H2. The new two-state representation was obtained by a three-step process from a modified eight-state diatomics-in-molecules (DIM) representation of Blais. The second step required the development of new dynamical methods. A formalism was developed for treating reactions with very general basis functions including electronically excited states. Our formalism is based on the generalized Newton, scattered wave, and outgoing wave variational principles that were used previously for reactive collisions on a single potential energy surface, and it incorporates three new features: (1) the basis functions include electronic degrees of freedom, as required to treat reactions involving electronic excitation and two or more coupled potential energy surfaces; (2) the primitive electronic basis is assumed to be diabatic, and it is not assumed that it diagonalizes the electronic Hamiltonian even asymptotically; and (3) contracted basis functions for vibrational-rotational-orbital degrees of freedom are included in a very general way, similar to previous prescriptions for locally

  18. The quantum dynamics of electronically nonadiabatic chemical reactions

    Science.gov (United States)

    Truhlar, Donald G.

    1993-04-01

    Considerable progress was achieved on the quantum mechanical treatment of electronically nonadiabatic collisions involving energy transfer and chemical reaction in the collision of an electronically excited atom with a molecule. In the first step, a new diabatic representation for the coupled potential energy surfaces was created. A two-state diabatic representation was developed which was designed to realistically reproduce the two lowest adiabatic states of the valence bond model and also to have the following three desirable features: (1) it is more economical to evaluate; (2) it is more portable; and (3) all spline fits are replaced by analytic functions. The new representation consists of a set of two coupled diabatic potential energy surfaces plus a coupling surface. It is suitable for dynamics calculations on both the electronic quenching and reaction processes in collisions of Na(3p2p) with H2. The new two-state representation was obtained by a three-step process from a modified eight-state diatomics-in-molecules (DIM) representation of Blais. The second step required the development of new dynamical methods. A formalism was developed for treating reactions with very general basis functions including electronically excited states. Our formalism is based on the generalized Newton, scattered wave, and outgoing wave variational principles that were used previously for reactive collisions on a single potential energy surface, and it incorporates three new features: (1) the basis functions include electronic degrees of freedom, as required to treat reactions involving electronic excitation and two or more coupled potential energy surfaces; (2) the primitive electronic basis is assumed to be diabatic, and it is not assumed that it diagonalizes the electronic Hamiltonian even asymptotically; and (3) contracted basis functions for vibrational-rotational-orbital degrees of freedom are included in a very general way, similar to previous prescriptions for locally

  19. The hunt for the dynamical resonances in chemical reaction dynamics: a perspective on historical advances

    Directory of Open Access Journals (Sweden)

    Yu Angyang

    2015-06-01

    Full Text Available The theoretical background and basic definition of the resonances in chemical reaction dynamics have been introduced in this article. The historical breakthrough in the experimental search for the reaction resonances has been reviewed in this report, with an emphasis on the crossed molecular beam apparatus. The research of the chemical reaction resonances has attracted many scientists’ attention from 80s of last century. The chemical reaction resonances in the F+H2 reaction were firstly observed by the researchers of the Chinese Academy of Sciences in 2006. Besides, the partial wave resonances in the chemical reactions have been observed for the first time in 2010.

  20. Chemical Reactions in the Processing of Mosi2 + Carbon Compacts

    Science.gov (United States)

    Jacobson, Nathan S.; Lee, Kang N.; Maloy, Stuart A.; Heuer, Arthur H.

    1993-01-01

    Hot-pressing of MoSi2 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 pct oxygen MoSi2 powder and a 0.59 wt pct oxygen MoSi2 powder, both with additions of 2 wt pct carbon, were examined. The reduction of the siliceous grain boundary phase was examined at 1350 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 MoSi2 + carbon mixtures were then heated at the hot-pressing temperature of 2100 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. Variable elimination in chemical reaction networks with mass action kinetics

    CERN Document Server

    Feliu, Elisenda

    2011-01-01

    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 of variables. The procedure reduces the variables in the system to a set of "core" variables by eliminating variables corresponding to a set of non-interacting species. The steady states are parameterized algebraically by the core variables, and a graphical condition is given for when a steady state with positive core variables necessarily have all variables positive. Further, we characterize graphically the sets of eliminated variables that are constrained by a conservation law and show that this conservation law takes a specific form.

  2. 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.

  3. 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.

  4. Radiation induced chemical reaction of carbon monoxide and hydrogen mixture

    International Nuclear Information System (INIS)

    Previous studies of radiation induced chemical reactions of CO-H2 mixture have revealed that the yields of oxygen containing products were larger than those of hydrocarbons. In the present study, methane was added to CO-H2 mixture in order to increase further the yields of the oxygen containing products. The yields of most products except a few products such as formaldehyde increased with the addition of small amount of methane. Especially, the yields of trioxane and tetraoxane gave the maximum values when CO-H2 mixture containing 1 mol% methane was irradiated. When large amounts of methane were added to the mixture, the yields of aldehydes and carboxylic acids having more than two carbon atoms increased, whereas those of trioxane and tetraoxane decreased. From the study at reaction temperature over the range of 200 to 473 K, it was found that the yields of aldehydes and carboxylic acids showed maxima at 323 K. The studies on the effects of addition of cationic scavenger (NH3) and radical scavenger (O2) on the products yields were also carried out on the CO-H2-CH4 mixture. (author)

  5. 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.

  6. Chloroaluminum phthalocyanine thin films: chemical reaction and molecular orientation.

    Science.gov (United States)

    Latteyer, Florian; Peisert, Heiko; Uihlein, Johannes; Basova, Tamara; Nagel, Peter; Merz, Michael; Schuppler, Stefan; Chassé, Thomas

    2013-05-01

    The chemical transformation of the polar chloroaluminum phthalocyanine, AlClPc, to μ-(oxo)bis(phthalocyaninato)aluminum(III), (PcAl)2O, in thin films on indium tin oxide is studied and its influence on the molecular orientation is discussed. The studies were conducted using complementary spectroscopic techniques: Raman spectroscopy, X-ray photoelectron spectroscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. In addition, density functional theory calculations were performed in order to identify specific vibrations and to monitor the product formation. The thin films of AlClPc were annealed in controlled environmental conditions to obtain (PcAl)2O. It is shown that the chemical transformation in the thin films can proceed only in the presence of water. The influence of the reaction and the annealing on the molecular orientation was studied with Raman spectroscopy and NEXAFS spectroscopy in total electron yield and partial electron yield modes. The comparison of the results obtained from these techniques allows the determination of the molecular orientation of the film as a function of the probing depth. PMID:23494276

  7. Chemical reactions of excited nitrogen atoms for short wavelength chemical lasers. Final technical report

    Energy Technology Data Exchange (ETDEWEB)

    1989-12-15

    Accomplishments of this program include the following: (1) Scalable, chemical generation of oxygen atoms by reaction of fluorine atoms and water vapor. (2) Production of nitrogen atom densities of 1 {times} 10{sup 1}5 cm{sup {minus}3} with 5% electrical efficiency by injecting trace amounts of fluorine into microwave discharged nitrogen. (3) Production of cyanide radicals by reaction of high densities of N atoms with cyanogen. (4) Production of carbon atoms by reaction of nitrogen atoms with cyanogen or with fluorine atoms and hydrogen cyanide. (5) Confirmation that the reaction of carbon atoms and carbonyl sulfide produces CS(a{sup 3} {Pi}{sub r}), as predicted by conservation of electron spin and orbital angular momenta and as proposed by others under another SWCL program. (6) Production of cyanide radicals by injection of cyanogen halides into active nitrogen and use as spectroscopic calibration source. (7) Demonstration that sodium atoms react with cyanogen chloride, bromide and iodide and with cyanuric trifluoride to produce cyanide radicals. (8) Demonstration of the potential utility of the fluorine atom plus ammonia reaction system in the production of NF(b{sup l}{Sigma}{sup +}) via N({sup 2}D) + F{sub 2}.

  8. Chemical Reaction and Flow Modeling in Fullerene and Nanotube Production

    Science.gov (United States)

    Scott, Carl D.; Farhat, Samir; Greendyke, Robert B.

    2004-01-01

    The development of processes to produce fullerenes and carbon nanotubes has largely been empirical. Fullerenes were first discovered in the soot produced by laser ablation of graphite [1]and then in the soot of electric arc evaporated carbon. Techniques and conditions for producing larger and larger quantities of fullerenes depended mainly on trial and error empirical variations of these processes, with attempts to scale them up by using larger electrodes and targets and higher power. Various concepts of how fullerenes and carbon nanotubes were formed were put forth, but very little was done based on chemical kinetics of the reactions. This was mainly due to the complex mixture of species and complex nature of conditions in the reactors. Temperatures in the reactors varied from several thousand degrees Kelvin down to near room temperature. There are hundreds of species possible, ranging from atomic carbon to large clusters of carbonaceous soot, and metallic catalyst atoms to metal clusters, to complexes of metals and carbon. Most of the chemical kinetics of the reactions and the thermodynamic properties of clusters and complexes have only been approximated. In addition, flow conditions in the reactors are transient or unsteady, and three dimensional, with steep spatial gradients of temperature and species concentrations. All these factors make computational simulations of reactors very complex and challenging. This article addresses the development of the chemical reaction involved in fullerene production and extends this to production of carbon nanotubes by the laser ablation/oven process and by the electric arc evaporation process. In addition, the high-pressure carbon monoxide (HiPco) process is discussed. The article is in several parts. The first one addresses the thermochemical aspects of modeling; and considers the development of chemical rate equations, estimates of reaction rates, and thermodynamic properties where they are available. The second part

  9. Study on the key problems of interaction between microwave and chemical reaction

    Institute of Scientific and Technical Information of China (English)

    YANG Xiaoqing; HUANG Kama

    2007-01-01

    Microwave has been found as an efficient heating method in chemical industry.However,in present days the interaction between microwave and chemical reactions has not been deeply understood,which restricts a wider application of high power microwave in chemical industry.In this Paper,the key problems of interaction between microwave and chemical reaction are investigated,such as complex effective permittivity of chemical reaction,simulation of microwave heating on chemical reaction and non-thermal effect of microwave,which will enhance further knowledge of the mechanism of interaction between microwave and chemical reaction.Moreover,such an analysis is beneficial for handling with difficulties in application of microwave chemical industry.

  10. Heat, Mass and Charge Transport, and Chemical Reactions at Surfaces

    Directory of Open Access Journals (Sweden)

    Signe Kjelstrup

    2005-03-01

    Full Text Available In this work we derive the excess entropy production rate for heat, mass and charge transport into, out of and across a surface, using as basic variables the excess densities proposed by Gibbs. With the help of these variables we define the surface as an autonomous system (i.e. a surface in local equilibrium and find its excess entropy production rate. This then determines the conjugate fluxes and forces. Equivalent forms of the entropy production rate are given. The forms contain finite differences of intensive variables into and across the surface as driving forces. The general form of the force-flux relations is given. The expressions for the fluxes serve as boundary conditions for integration across heterogeneous systems. Two examples are discussed in more detail. The first example is the practically important coupled transport of heat and mass into and through a liquid-vapor surface. The second example concerns phenomena at electrode surfaces: the coupled transport of heat, mass and charge and a chemical reaction. By assuming that the two sides of the surface can be described as resistances in series, we are able to reduce the number of unknown transport coefficients considerably. For both examples it is shown that the coupling coefficients for heat and mass flow are large at the surface, when the homogeneous phases have a large enthalpy difference. As a consequence it is not sufficient to use, for instance, Fourier’s law for transport of heat across surfaces.

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

    International Nuclear Information System (INIS)

    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

  12. Mixing and chemical reaction in sheared and nonsheared homogeneous turbulence

    Science.gov (United States)

    Leonard, Andy D.; Hill, James C.

    1992-01-01

    Direct numerical simulations were made to examine the local structure of the reaction zone for a moderately fast reaction between unmixed species in decaying, homogeneous turbulence and in a homogeneous turbulent shear flow. Pseudospectral techniques were used in domains of 64 exp 3 and higher wavenumbers. A finite-rate, single step reaction between non-premixed reactants was considered, and in one case temperature-dependent Arrhenius kinetics was assumed. Locally intense reaction rates that tend to persist throughout the simulations occur in locations where the reactant concentration gradients are large and are amplified by the local rate of strain. The reaction zones are more organized in the case of a uniform mean shear than in isotropic turbulence, and regions of intense reaction rate appear to be associated with vortex structures such as horseshoe vortices and fingers seen in mixing layers. Concentration gradients tend to align with the direction of the most compressive principal strain rate, more so in the isotropic case.

  13. Chemical Reaction of In-situ Processing of NiAl/Al2O3 Composite by Using Thermite Reaction

    Institute of Scientific and Technical Information of China (English)

    LIU Yin; FAN Xiaonan; ZHANG Mingxu; QIN Xiaoying

    2005-01-01

    NiAl / Al2O3 composite were synthesized by thermite reaction of nickel oxide and aluminum powder mixtures. The phase, the microstructure of the composite, as well as the thermite reaction mechanism, were investigated by X-ray diffractometry ( XRD ), scanning electron microscopy (SEM) combined with differential scanning calorimetry ( DSC). The experimental results show that the thermite reaction leads to the interpenetrating network structure of NiAl/Al2O3 at 1223K for 60min and the chemical reaction apparent activation energy is Eap = 166.960± 13.496 kJ· mol-1 in the NiO/Al system.

  14. Mapping Students' Conceptual Modes When Thinking about Chemical Reactions Used to Make a Desired Product

    Science.gov (United States)

    Weinrich, M. L.; Talanquer, V.

    2015-01-01

    The central goal of this qualitative research study was to uncover major implicit assumptions that students with different levels of training in the discipline apply when thinking and making decisions about chemical reactions used to make a desired product. In particular, we elicited different ways of conceptualizing why chemical reactions happen…

  15. Motivational Factors Contributing to Turkish High School Students' Achievement in Gases and Chemical Reactions

    Science.gov (United States)

    Kadioglu, Cansel; Uzuntiryaki, Esen

    2008-01-01

    This study aimed to investigate the contribution of motivational factors to 10th grade students' achievement in gases and chemical reactions in chemistry. Three hundred fifty nine 10th grade students participated in the study. The Gases and Chemical Reactions Achievement Test and the Motivated Strategies for Learning Questionnaire were…

  16. 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.

  17. 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…

  18. A Novel Oscillating Chemical Reaction Using Ninhydrin as Single Organic Substrate

    Institute of Scientific and Technical Information of China (English)

    Fu Wei YANG; Jin Zhang GAO; Wu YANG; Kan Jun SUN

    2006-01-01

    A novel oscillating chemical reaction using ninhydrin as a single organic substrate was represented in this paper. It distinguished from the classically catalyzed BZ oscillating chemical reaction due to there was no active methene (CH2=) and/or enol structure in the ninhydrin molecule, which served as single organic substrate. This suggested that the substrates used in catalyzed BZ reaction were not always the organic compounds containing active methene (CH2=) and/or enol structure and bromination process in this kind of catalyzed chemical oscillating reaction was not also necessary.

  19. Formation of slow molecules in chemical reactions in crossed molecular beams

    Science.gov (United States)

    Tscherbul, T. V.; Barinovs, Ğ.; Kłos, J.; Krems, R. V.

    2008-08-01

    We demonstrate that chemical reactions in collisions of molecular beams can generally produce low-velocity molecules in the laboratory-fixed frame. Our analysis shows that collisions of beams may simultaneously yield slow reactant molecules and slow products. The reaction products are formed in selected rovibrational states and scattered in a specific direction, which can be controlled by tuning the kinetic energies of the incident beams and the angle between the beams. Our calculations indicate that chemical reactions of polar alkali-metal dimers are barrierless and we suggest that chemical reactions involving alkali-metal dimers may be particularly suitable for producing slow molecules in crossed beams.

  20. Chemical reactions of ultracold alkali dimers in the lowest-energy $^3\\Sigma$ state

    CERN Document Server

    Tomza, Michał; Moszynski, Robert; Krems, Roman V

    2013-01-01

    We show that the interaction of polar alkali dimers in the quintet spin state leads to the formation of a deeply bound reaction complex. The reaction complex can decompose adiabatically into homonuclear alkali dimers (for all molecules except KRb) and into alkali trimers (for all molecules). We show that there are no barriers for these chemical reactions. This means that all alkali dimers in the $a^3\\Sigma^+$ state are chemically unstable at ultracold temperature, and the use of an optical lattice to segregate the molecules and suppress losses may be necessary. In addition, we calculate the minimum energy path for the chemical reactions of alkali hydrides. We find that the reaction of two molecules is accelerated by a strong attraction between the alkali atoms, leading to a barrierless process that produces hydrogen atoms with large kinetic energy. We discuss the unique features of the chemical reactions of ultracold alkali dimers in the $a^3\\Sigma^+$ electronic state.

  1. Chemical modeling of irreversible reactions in nuclear waste-water-rock systems

    International Nuclear Information System (INIS)

    Chemical models of aqueous geochemical systems are usually built on the concept of thermodynamic equilibrium. Though many elementary reactions in a geochemical system may be close to equilibrium, others may not be. Chemical models of aqueous fluids should take into account that many aqueous redox reactions are among the latter. The behavior of redox reactions may critically affect migration of certain radionuclides, especially the actinides. In addition, the progress of reaction in geochemical systems requires thermodynamic driving forces associated with elementary reactions not at equilibrium, which are termed irreversible reactions. Both static chemical models of fluids and dynamic models of reacting systems have been applied to a wide spectrum of problems in water-rock interactions. Potential applications in nuclear waste disposal range from problems in geochemical aspects of site evaluation to those of waste-water-rock interactions. However, much further work in the laboratory and the field will be required to develop and verify such applications of chemical modeling

  2. 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…

  3. Evolution of DNA and RNA as catalysts for chemical reactions.

    Science.gov (United States)

    Jäschke, A; Seelig, B

    2000-06-01

    In vitro selection from combinatorial nucleic acid libraries has provided new RNA and DNA molecules that have catalytic properties. Catalyzed reactions now go far beyond self-modifying reactions of nucleic acid molecules. The future application of in vitro selected RNA and DNA catalysts in bioorganic synthesis appears promising. PMID:10826969

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

    DEFF Research Database (Denmark)

    Petrunin, Victor V.

    2011-01-01

    alignment are taking place, guiding all the molecules towards the intersections with the ground state PES, where transitions to the ground state PES will occur with minimum energy dissipation. The accumulated kinetic energy may be used to overcome the chemical reaction barrier. While recombination chemical...... be readily produced. Products of chemical adsorption and/or chemical reactions induced within adsorbates are aggregated on the surface and observed by light scattering. We will demonstrate how pressure and spectral dependencies of the chemical outcomes, polarization of the light and interference of...... two laser 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....

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

    Science.gov (United States)

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

    2014-06-01

    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, incorporating dynamic aspects of chemical processes, linking a visualization to the associated chemical phenomenon, and connecting between the visualization and chemistry concepts. We also compared students who were able to create dynamic visualizations with those who only created static visualizations. The results indicated a relationship between students constructing a dynamic view of chemical reaction processes and their understanding of chemical reactions. This study provides insights into the use of visualizations to support instruction and assessment to facilitate students' integrated understanding of chemical reactions.

  6. Dynamical resonance in F+H2 chemical reaction and rotational excitation effect

    Institute of Scientific and Technical Information of China (English)

    YANG XueMing; XIE DaiQian; ZHANG DongHui

    2007-01-01

    Reaction resonance is a frontier topic in chemical dynamics research, and it is also essential to the understanding of mechanisms of elementary chemical reactions. This short article describes an important development in the frontier of research. Experimental evidence of reaction resonance has been detected in a full quantum state resolved reactive scattering study of the F+H2 reaction. Highly accurate full quantum scattering theoretical modeling shows that the reaction resonance is caused by two Feshbach resonance states. Further studies show that quantum interference is present between the two resonance states for the forward scattering product. This study is a significant step forward in our understanding of chemical reaction resonance in the benchmark F+H2 system. Further experimental studies on the effect of H2 rotational excitation on dynamical resonance have been carried out. Dynamical resonance in the F+H2 (j = 1) reaction has also been observed.

  7. Detonation wave solutions and linear stability in a four component gas with bimolecular chemical reaction

    OpenAIRE

    Carvalho, Filipe; De Silva, A.W.; Soares, A. J.

    2015-01-01

    We consider a four component gas undergoing a bimolecular chemical reaction of type A1 + A2 = A3 + A4, described by the Boltzmann equation (BE) for chemically reactive mixtures. We adopt hard-spheres elastic cross sections and modified line-of-centers reactive cross sections depending on both the activation energy and geometry of the reactive collisions. Then we consider the hydrodynamic limit specified by the reactive Euler equations, in an earlier stage of the chemical reaction, when the ga...

  8. A new type of power energy for accelerating chemical reactions: the nature of a microwave-driving force for accelerating chemical reactions.

    Science.gov (United States)

    Zhou, Jicheng; Xu, Wentao; You, Zhimin; Wang, Zhe; Luo, Yushang; Gao, Lingfei; Yin, Cheng; Peng, Renjie; Lan, Lixin

    2016-01-01

    The use of microwave (MW) irradiation to increase the rate of chemical reactions has attracted much attention recently in nearly all fields of chemistry due to substantial enhancements in reaction rates. However, the intrinsic nature of the effects of MW irradiation on chemical reactions remains unclear. Herein, the highly effective conversion of NO and decomposition of H2S via MW catalysis were investigated. The temperature was decreased by several hundred degrees centigrade. Moreover, the apparent activation energy (Ea') decreased substantially under MW irradiation. Importantly, for the first time, a model of the interactions between microwave electromagnetic waves and molecules is proposed to elucidate the intrinsic reason for the reduction in the Ea' under MW irradiation, and a formula for the quantitative estimation of the decrease in the Ea' was determined. MW irradiation energy was partially transformed to reduce the Ea', and MW irradiation is a new type of power energy for speeding up chemical reactions. The effect of MW irradiation on chemical reactions was determined. Our findings challenge both the classical view of MW irradiation as only a heating method and the controversial MW non-thermal effect and open a promising avenue for the development of novel MW catalytic reaction technology. PMID:27118640

  9. A new type of power energy for accelerating chemical reactions: the nature of a microwave-driving force for accelerating chemical reactions

    Science.gov (United States)

    Zhou, Jicheng; Xu, Wentao; You, Zhimin; Wang, Zhe; Luo, Yushang; Gao, Lingfei; Yin, Cheng; Peng, Renjie; Lan, Lixin

    2016-01-01

    The use of microwave (MW) irradiation to increase the rate of chemical reactions has attracted much attention recently in nearly all fields of chemistry due to substantial enhancements in reaction rates. However, the intrinsic nature of the effects of MW irradiation on chemical reactions remains unclear. Herein, the highly effective conversion of NO and decomposition of H2S via MW catalysis were investigated. The temperature was decreased by several hundred degrees centigrade. Moreover, the apparent activation energy (Ea’) decreased substantially under MW irradiation. Importantly, for the first time, a model of the interactions between microwave electromagnetic waves and molecules is proposed to elucidate the intrinsic reason for the reduction in the Ea’ under MW irradiation, and a formula for the quantitative estimation of the decrease in the Ea’ was determined. MW irradiation energy was partially transformed to reduce the Ea’, and MW irradiation is a new type of power energy for speeding up chemical reactions. The effect of MW irradiation on chemical reactions was determined. Our findings challenge both the classical view of MW irradiation as only a heating method and the controversial MW non-thermal effect and open a promising avenue for the development of novel MW catalytic reaction technology. PMID:27118640

  10. Low-temperature solid-phase chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Baluev, A.V.; Mityakhina, V.S.; Rogozev, B.I.; Silin, M.Yu.

    1987-06-01

    This paper is concerned with the possibility of solid-phase reactions carried out at 20-25 degrees C. A variety of solid complexes are ground and tested for their reaction capacity in the solid phase with acid phosphates, including complexes of iron, cesium, sodium, tin, and uranyl, using Moessbauer and infrared spectroscopy and thermal analysis. The reactions are considered viable not only because they avoid the expenditure of energy otherwise needed to heat the reactants but also because they provide a new method for the preparation of complex coordination compounds.

  11. 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 mu

  12. Vicher: A Virtual Reality Based Educational Module for Chemical Reaction Engineering.

    Science.gov (United States)

    Bell, John T.; Fogler, H. Scott

    1996-01-01

    A virtual reality application for undergraduate chemical kinetics and reactor design education, Vicher (Virtual Chemical Reaction Model) was originally designed to simulate a portion of a modern chemical plant. Vicher now consists of two programs: Vicher I that models catalyst deactivation and Vicher II that models nonisothermal effects in…

  13. 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.

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

    OpenAIRE

    Allen, Joshua W.; Green, William H; Suleimanov, Yu. V.

    2013-01-01

    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 ...

  15. Analysis of weblike network structures of directed graphs for chemical reactions in methane plasmas

    International Nuclear Information System (INIS)

    Chemical reactions of molecular gases like methane are so complicated that a chart of decomposed and/or synthesized species originating from molecules in plasma resembles a weblike network in which we write down species and reactions among them. Here we consider properties of the network structures of chemical reactions in methane plasmas. In the network, atoms/molecules/radical species are assumed to form nodes and chemical reactions correspond to directed edges in the terminology of graph theory. Investigation of the centrality index reveals importance of CH3 in the global chemical reaction, and difference of an index for each radical species between cases with and without electrons clarifies that the electrons are at an influential position to tighten the network structure

  16. 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.

  17. 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

    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...

  18. Heterogeneously Catalysed Chemical Reactions in Carbon Dioxide Medium

    DEFF Research Database (Denmark)

    Musko, Nikolai E.

    determination of phase equilibria is very time consuming, expensive, and very often reveals very little information. However, these problems can be overcome when thermodynamic modelling is applied. The Cubic-Plus-Association Equation of State (CPA) was used throughout this study; therefore this model is...... studied. Furthermore, the “one-pot” synthesis with 2-butenal was performed using bifunctional and mixed catalysts. The reactions were studied in different reactor types and reaction conditions were optimised using CPA calculations. Extensive catalyst characterisation was carried out in order to understand...... equilibria of the reaction mixture can make the process economically more feasible. Many different thermodynamic models of different capability and applicability have been applied for this task. The CPA model is an advanced model that accounts for complex interactions between associating molecules like water...

  19. 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.

  20. Theoretical Studies of Chemical Reactions following Electronic Excitation

    Science.gov (United States)

    Chaban, Galina M.

    2003-01-01

    The use of multi-configurational wave functions is demonstrated for several processes: tautomerization reactions in the ground and excited states of the DNA base adenine, dissociation of glycine molecule after electronic excitation, and decomposition/deformation of novel rare gas molecules HRgF. These processes involve bond brealung/formation and require multi-configurational approaches that include dynamic correlation.

  1. 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.

  2. 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 attractive...... tool of automated analytical chemistry. The need for an even lower consumption of chemicals and for computer analysis has motivated a study of the FIA peak itself, that is, a theoretical model was developed, that provides detailed knowledge of the FIA profile. It was shown that the flow in a FIA...

  3. 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.

  4. 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 ...

  5. Theory for Diffusion-Limited Oscillating Chemical Reactions

    OpenAIRE

    Bussemaker, H. J.; Brito López, Ricardo

    1996-01-01

    A kinetic description of lattice-gas automaton models for reaction-diffusion systems is presented. It provides corrections to the mean-field rate equations in the diffusion-limited regime. When applied to the two-species Maginu model, the theory gives an excellent quantitative prediction of the effect of slow diffusion on the periodic oscillations of the average concentrations in a spatially homogeneous state.

  6. Carbon compounds in the atmosphere and their chemical reactions

    OpenAIRE

    Martišová, Petra

    2013-01-01

    The essay dissert on compounds of carbon in the atmosphere and its reaction. The most important are carbon dioxide, carbon monoxide and methane. Included among important compounds of carbon are volatile organic substances, polycyclic aromatic hydrocarbon and dioxin. Carbon dioxide and methane representing greenhouse gases have also indispensable meaning. As they, together with water vapour, nitrogen monoxide and other gases are causing the major part of greenhouse effect. Primarily because of...

  7. Effects of chemical reactions on the performance of gas dynamic lasers

    Energy Technology Data Exchange (ETDEWEB)

    Rom, J.; Stricker, J.

    1974-01-01

    It is shown that chemical reactions in the stagnation region of a gasdynamic laser in the shock tube may not be completed during the available test time. Therefore, analysis of data obtained in the shock tube must account for the instantaneous composition which may be effected by chemical reactions. A CO/sub 2/--N/sub 2/ gasdynamic laser experimental program in the shock tube including addition of H/sub 2/ into the system is described. This experiment involves reasonably complicated chemical reactions. These chemical reactions result in H/sub 2/O production under certain conditions. The comparison of the experimental results with the calculated results shows that such measurements can also be used to evaluate the energy transfer rates. The small-signal gain measurements indicate that the hydrogen is much more effective in depopulating the ..nu.. sub 3 level to ..nu.. sub 2 than previously assumed.

  8. Magnetohydrodynamic (MHD) stretched flow of nanofluid with power-law velocity and chemical reaction

    Science.gov (United States)

    Hayat, Tasawar; Rashid, Madiha; Imtiaz, Maria; Alsaedi, Ahmed

    2015-11-01

    This paper deals with the boundary layer flow of nanofluid over power-law stretched surface. Analysis has been carried out in the presence of applied magnetic field and chemical reaction. Heat and mass transfer characteristics are studied using heat and mass convective conditions. The governing partial differential equations are transferred to the nonlinear ordinary differential equations. Convergent series solutions are obtained for fluid velocity, temperature and concentrations fields. Influences of pertinent parameters including Hartman number, thermal and concentration Biot numbers and chemical reaction parameters are discussed on the velocity, temperature and concentration profiles. Graphical result are presented and discussed. Computations for local Nusselt and Sherwood numbers are carried out. It is observed that the heat transfer rate is enhanced by increasing power-law index, thermal Biot number and chemical reaction parameter while mass transfer rate increases for power-law index and chemical reaction parameter.

  9. 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.

  10. 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...

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

    OpenAIRE

    Ge, Hao; Qian, Hong

    2016-01-01

    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 chemistry kinetics). In doing so, the equilibrium thermodynamics is then naturally generalized to nonequilibrium settings without detailed balance. The kinetic model...

  12. Properties of Random Complex Chemical Reaction Networks and Their Relevance to Biological Toy Models

    OpenAIRE

    Bigan, Erwan; Steyaert, Jean-Marc; Douady, Stéphane

    2013-01-01

    We investigate the properties of large random conservative chemical reaction networks composed of elementary reactions endowed with either mass-action or saturating kinetics, assigning kinetic parameters in a thermodynamically-consistent manner. We find that such complex networks exhibit qualitatively similar behavior when fed with external nutrient flux. The nutrient is preferentially transformed into one specific chemical that is an intrinsic property of the network. We propose a self-consi...

  13. Three model space experiments on chemical reactions. [Gibbs adsorption, equilibrium shift and electrodeposition

    Science.gov (United States)

    Grodzka, P.; Facemire, B.

    1977-01-01

    Three investigations conducted aboard Skylab IV and Apollo-Soyuz involved phenomena that are of interest to the biochemistry community. The formaldehyde clock reaction and the equilibrium shift reaction experiments conducted aboard Apollo Soyuz demonstrate the effect of low-g foams or air/liquid dispersions on reaction rate and chemical equilibrium. The electrodeposition reaction experiment conducted aboard Skylab IV demonstrate the effect of a low-g environment on an electrochemical displacement reaction. The implications of the three space experiments for various applications are considered.

  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....... applied 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. Vapor–Liquid Equilibrium Coupled with Chemical Reaction (Transesterification)

    Czech Academy of Sciences Publication Activity Database

    Wichterle, Ivan; Aim, Karel

    - : -, 2005 - (Domanska-Zelazna, U.; Malanowski, S.), s.68-69 ISBN 83-920719-1-3. [European Symposium on Applied Thermodynamics ESAT 2005 /21./. Jurata (PL), 01.06.2005-05.06.2005] R&D Projects: GA ČR(CZ) GA203/03/1588 Institutional research plan: CEZ:AV0Z40720504 Keywords : phase equilibria * chemical equilibria * transesterification Subject RIV: CF - Physical ; Theoretical Chemistry

  16. Effects of reversible chemical reaction on Li diffusion and stresses in spherical composition-gradient electrodes

    International Nuclear Information System (INIS)

    Composition-gradient electrode materials have been proven to be one of the most promising materials in lithium-ion battery. To study the mechanism of mechanical degradation in spherical composition-gradient electrodes, the finite deformation theory and reversible chemical theory are adopted. In homogeneous electrodes, reversible electrochemical reaction may increase the magnitudes of stresses. However, reversible electrochemical reaction has different influences on stresses in composition-gradient electrodes, resulting from three main inhomogeneous factors—forward reaction rate, backward reaction rate, and reaction partial molar volume. The decreasing transition form of forward reaction rate, increasing transition form of backward reaction rate, and increasing transition form of reaction partial molar volume can reduce the magnitudes of stresses. As a result, capacity fading and mechanical degradation are reduced by taking advantage of the effects of inhomogeneous factors

  17. Ca + HF - The anatomy of a chemical insertion reaction

    Science.gov (United States)

    Jaffe, R. L.; Pattengill, M. D.; Mascarello, F. G.; Zare, R. N.

    1987-01-01

    A comprehensive first-principles theoretical investigation of the gas phase reaction Ca + HF - CaF + H is reported. Ab initio potential energy calculations are first discussed, along with characteristics of the computed potential energy surface. Next, the fitting of the computed potential energy points to a suitable analytical functional form is described, and maps of the fitted potential surface are displayed. The methodology and results of a classical trajectory calculation utilizing the fitted potential surface are presented. Finally, the significance of the trajectory study results is discussed, and generalizations concerning dynamical aspects of Ca + HF scattering are drawn.

  18. Selective Chemical-Lithographic Reaction Techniques Using Radiation Technology for Biological Application

    International Nuclear Information System (INIS)

    This report, titled 'selective Chemical-Lithographic Reaction Techniques Using Radiation Technology for Biological Application' contains a research summary, 1) development of selective reaction technology using irradiation of electron beams, 2) preparation of functional surfaces using selective radiation technology on carbon-based nanomaterials, and 3) development of bio-applicable biochips using combinatorial surface modification

  19. A comparison of reversible chemical reactions for solar thermochemical power generation

    OpenAIRE

    Williams, O. M.

    1980-01-01

    Reversible chemical reactions operating in a thermochemical energy transfer system have been proposed for solar electricity generation in order to solve not only the problem of energy transport from the solar collection field to a central power plant, but also potentially the long term lossless energy storage problem through underground storage of the reaction products. A number of reactions have been proposed for solar thermochemical power generation and in this paper the thermodynamic and c...

  20. Production of cold formaldehyde molecules for study and control of chemical reaction dynamics with hydroxyl radicals

    OpenAIRE

    Hudson, Eric R.; Ticknor, Christopher; Sawyer, Brian C.; Taatjes, Craig A.; Lewandowski, H. J.; Bochinski, J. R.; Bohn, John L.; Ye, Jun

    2005-01-01

    We propose a method for controlling a class of low temperature chemical reactions. Specifically, we show the hydrogen abstraction channel in the reaction of formaldehyde (H$_{2}$CO) and the hydroxyl radical (OH) can be controlled through either the molecular state or an external electric field. We also outline experiments for investigating and demonstrating control over this important reaction. To this end, we report the first Stark deceleration of the H$_{2}$CO molecule. We have decelerated ...

  1. Mechanism of the Ferrocyanide-Iodate-Sulfite Oscillatory Chemical Reaction.

    Science.gov (United States)

    Horváth, Viktor; Epstein, Irving R; Kustin, Kenneth

    2016-03-31

    Existing models of the ferrocyanide-iodate-sulfite (FIS) reaction seek to replicate the oscillatory pH behavior that occurs in open systems. These models exhibit significant differences in the amplitudes and waveforms of the concentration oscillations of such intermediates as I(-), I3(-), and Fe(CN)6(3-) under identical conditions and do not include several experimentally found intermediates. Here we report measurements of sulfite concentrations during an oscillatory cycle. Knowing the correct concentration of sulfite over the course of a period is important because sulfite is the main component that determines the buffer capacity, the pH extrema, and the amount of oxidizer (iodate) required for the transition to low pH. On the basis of this new result and recent experimental findings on the rate laws and intermediates of component processes taken from the literature, we propose a mass action kinetics model that attempts to faithfully represent the chemistry of the FIS reaction. This new comprehensive mechanism reproduces the pH oscillations and the periodic behavior in [Fe(CN)6(3-)], [I3(-)], [I(-)], and [SO3(2-)]T with characteristics similar to those seen in experiments in both CSTR and semibatch arrangements. The parameter ranges at which stationary and oscillatory behavior is exhibited also show good agreement with those of the experiments. PMID:26949219

  2. Students' Ideas about How and Why Chemical Reactions Happen: Mapping the Conceptual Landscape

    Science.gov (United States)

    Yan, Fan; Talanquer, Vicente

    2015-01-01

    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…

  3. The diagnostic of the chemical reaction zone at the detonation of condensed explosives

    CERN Document Server

    Satonkina, Nataliya P

    2016-01-01

    The highly-sensitive method is proposed for the real-time diagnostics of the von Neumann peak at detonation of brisant high explosives. The absence of the direct link between the pressure and the course of chemical reactions was shown. For TNT (trinitrotoluene), the influence of the structure of charge on the kinetics of chemical peak was demonstrated.

  4. The Technology for Intensification of Chemical Reaction Process Envisaged in the "863" Plan

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    @@ It is learned from the Ministry of Science and Technology that in order to promote the shift of China's chemical industry toward an energy efficient and environmentally friendly product mode, the technology for intensification of chemical reaction processes has been included in the National "863" Project of the "Eleventh Five-Year Plan", and the application for research project proposals is to be accepted.

  5. Rate constants for chemical reactions in high-temperature nonequilibrium air

    Science.gov (United States)

    Jaffe, R. L.

    1986-01-01

    In the nonequilibrium atmospheric chemistry regime that will be encountered by the proposed Aeroassisted Orbital Transfer Vehicle in the upper atmosphere, where air density is too low for thermal and chemical equilibrium to be maintained, the detailed high temperature air chemistry plays a critical role in defining radiative and convective heating loads. Although vibrational and electronic temperatures remain low (less than 15,000 K), rotational and translational temperatures may reach 50,000 K. Attention is presently given to the effects of multiple temperatures on the magnitudes of various chemical reaction rate constants, for the cases of both bimolecular exchange reactions and collisional excitation and dissociation reactions.

  6. The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

    Science.gov (United States)

    Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

    1993-01-01

    Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

  7. Simulation of chemical reactions in solution by a combination of classical and quantum mechanical approach

    Science.gov (United States)

    Onida, Giovanni; Andreoni, Wanda

    1995-09-01

    A classical trajectory mapping method was developed to study chemical reactions in solution and in enzymes. In this method, the trajectories were calculated on a classical potential surface and the free energy profile was obtained by mapping the classical surface to the quantum mechanical surface obtained by the semiempirical AM1 method. There is no need to perform expensive quantum mechanical calculations at each iteration step. This method was applied to proton transfer reactions both in aqueous solution and in papain. The results are encouraging, indicating the applicability of this hybrid method to chemical reactions both in solution and in enzymes.

  8. Chemical reactions in organic monomolecular layers. Condensation of hydrazine on carbonyl functions

    International Nuclear Information System (INIS)

    Evidence is given for chemical reactions of hydrazine (NH2-NH2) with different carbonyl functional groups of organic molecules in the solid state, in monomolecular layer structures. The condensation of hydrazine with these molecules leads to conjugated systems by bridging the N-N links, to cyclizations, and also to polycondensations. The reactions investigated were followed up by infrared spectrophotometry, by transmission and metallic reflection. These chemical reactions revealed in the solid phase constitute a polycondensation procedure which is valuable in obtaining organized polymers in monomolecular layers

  9. Heterogeneous nucleation - current transients under chemical reaction control

    CERN Document Server

    D'Ajello-Tettamanzy, P C; Kipervaser, Z G S

    2002-01-01

    Heterogeneous nucleation on catalytic surfaces plunged into a fluid is described through a stochastic model. To generate this non-equilibrium process we assume that the turn on of a electrostatic potential triggers a complex dynamics that includes a free Brownian motion, a reaction kinetic and a stimulated migration before the final adhesion of ions on the surface (electrode). At, when the potential is switched on, the spatial symmetry is broken and a two-stage process is developed. First the ion undergoes a change in its electrochemical character (at some region of the space) and then reacts at some specific points to stick together on the surface. The continuous addition of ions develops a material deposit connected to the current transient signals measured in electrochemical deposition processes. Unlike current models found in the literature, this procedure avoids the computation of the area covered by the diffusion zones, allowing a formalism skill to describe equally well the absorption of ions by channe...

  10. Small-angle neutron scattering studies of chemical reaction and reaction-induced self-assembly

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, H. [Advanced Science Research Center(ASRC), Japan Atomic Energy Agency (JAEA), Tokai, Ibaraki 319-1195 (Japan); Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8501 (Japan); Koizumi, S. [Advanced Science Research Center(ASRC), Japan Atomic Energy Agency (JAEA), Tokai, Ibaraki 319-1195 (Japan); Hashimoto, T. [Advanced Science Research Center(ASRC), Japan Atomic Energy Agency (JAEA), Tokai, Ibaraki 319-1195 (Japan) and Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8501 (Japan)]. E-mail: hashimoto.takeji@jaea.go.jp; Kurosaki, K. [Department of Materials Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8501 (Japan); Ohmae, M. [Department of Materials Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8501 (Japan); Kobayashi, S. [Department of Materials Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8501 (Japan)

    2006-11-15

    We have investigated a self-assembling process of cellulose artificially synthesized via enzymatic polymerization by means of in-situ and time-resolved small-angle neutron scattering (SANS). The results elucidated the following: (i) cellulose molecules were synthesized at a special reaction site of the enzyme (cellulase) located on or near the smooth surface of the self-assembled enzymes formed in the reaction medium; (ii) the synthesized molecules associated themselves via diffusion-limited aggregation (DLA) and crystallized into fibrils and (iii) the fibrils formed the aggregates, which had the surface fractal dimension D {sub s} increasing from 2 to 2.3 with the reaction time, on the smooth surface of the enzyme aggregates.

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

    DEFF Research Database (Denmark)

    Linneberg, Allan; Thyssen, Jacob Pontoppidan; Dirksen, Asger;

    2011-01-01

    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...... 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...

  12. An in-situ chemical reaction deposition of nanosized wurtzite CdS thin films

    Energy Technology Data Exchange (ETDEWEB)

    Chu Juan [School of Materials Science and Engineering, Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin University, Tianjin 300072 (China); Jin Zhengguo, E-mail: zhgjin@tju.edu.cn [School of Materials Science and Engineering, Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin University, Tianjin 300072 (China); State Key Laboratory of Silicon Materials and Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Cai Shu [School of Materials Science and Engineering, Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin University, Tianjin 300072 (China); State Key Laboratory of Silicon Materials and Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Yang Jingxia [State Key Laboratory of Silicon Materials and Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Hong Zhanglian, E-mail: hong_zhanglian@zju.edu.cn [State Key Laboratory of Silicon Materials and Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China)

    2012-01-01

    Nanocrystalline CdS thin films were deposited on glass substrates by an ammonia-free in-situ chemical reaction synthesis technique using cadmium cationic precursor solid films as reaction source and sodium sulfide based solutions as anionic reaction medium. Effects of ethanolamine addition to the cadmium cationic precursor solid films, deposition cycle numbers and annealing treatments in Ar atmosphere on structure, morphology, chemical composition and optical properties of the resultant films were investigated by X-ray diffraction, field emission scanning electron microscope, energy dispersive X-ray analysis and UV-Vis spectra measurements. The results show that CdS thin films deposited by the in-situ chemical reaction synthesis have wurtzite structure with (002) plane preferential orientation and crystallite size is in the range of 16 nm-19 nm. The growth of film thickness is almost constant with deposition cycle numbers and about 96 nm per cycle.

  13. Thermally activated reaction–diffusion-controlled chemical bulk reactions of gases and solids

    Directory of Open Access Journals (Sweden)

    S. Möller

    2015-01-01

    Full Text Available The chemical kinetics of the reaction of thin films with reactive gases is investigated. The removal of thin films using thermally activated solid–gas to gas reactions is a method to in-situ control deposition inventory in vacuum and plasma vessels. Significant scatter of experimental deposit removal rates at apparently similar conditions was observed in the past, highlighting the need for understanding the underlying processes. A model based on the presence of reactive gas in the films bulk and chemical kinetics is presented. The model describes the diffusion of reactive gas into the film and its chemical interaction with film constituents in the bulk using a stationary reaction–diffusion equation. This yields the reactive gas concentration and reaction rates. Diffusion and reaction rate limitations are depicted in parameter studies. Comparison with literature data on tokamak co-deposit removal results in good agreement of removal rates as a function of pressure, film thickness and temperature.

  14. An in-situ chemical reaction deposition of nanosized wurtzite CdS thin films

    International Nuclear Information System (INIS)

    Nanocrystalline CdS thin films were deposited on glass substrates by an ammonia-free in-situ chemical reaction synthesis technique using cadmium cationic precursor solid films as reaction source and sodium sulfide based solutions as anionic reaction medium. Effects of ethanolamine addition to the cadmium cationic precursor solid films, deposition cycle numbers and annealing treatments in Ar atmosphere on structure, morphology, chemical composition and optical properties of the resultant films were investigated by X-ray diffraction, field emission scanning electron microscope, energy dispersive X-ray analysis and UV–Vis spectra measurements. The results show that CdS thin films deposited by the in-situ chemical reaction synthesis have wurtzite structure with (002) plane preferential orientation and crystallite size is in the range of 16 nm–19 nm. The growth of film thickness is almost constant with deposition cycle numbers and about 96 nm per cycle.

  15. Numerical kinetic model including equilibrium and rate equations for chemical reactions of actinide elements

    International Nuclear Information System (INIS)

    Numerical simulation method was examined for chemical reactions of actinide elements U, Pu, Np, and Tc etc. in an aqueous nitric acid solution. It is known that the numerical calculation for the Purex process with chemical reactions and liquid flow becomes stiff, because time constant for the chemical reactions is two to three order of magnitude smaller due to the very fast reactions than that of mass transfer or of reaching distribution equilibrium. Recently in order to increase a time step Δt the partial equilibrium (P.E.) model, in which some very fast reactions are treated by the equilibrium law whereas other reactions are by the rate law, has been proposed. In the present study concentration change of the solutes in an aqueous solution with 30 chemical reactions, of which 4 are expressed by equilibrium equations, has been calculated. Description of the P.E. model and the comparison of the results and cpu time between the kinetic and the P.E. models are given. (author)

  16. From chemical reactions to evolution: Emergence of species

    Science.gov (United States)

    Carletti, T.; Fanelli, D.

    2007-01-01

    The Chemoton model constitutes a minimalistic description of a protocell unit. The original formulation assumes three coupled chemical networks, representing a proto-metabolism, a template duplication and the membrane growth. An improved version is here proposed that explicitly incorporates the effects of the volume changes, due to the membrane growth. A stochastic mechanism is also introduced that mimics a stochastic source of error in the template duplication process. Numerical simulations are performed to monitor the time evolution of a family of protocells, under the chemoton hypothesis. An open-ended Darwinian evolution under the pressure of the environment is reproduced thus allowing to conclude that differentiation into species is an emergent property of the model.

  17. Momentum balance equation for nonelectrolytes in models of coupling between chemical reaction and diffusion in membranes.

    Science.gov (United States)

    Gałdzicki, Z; Miekisz, S

    1984-04-01

    The role of viscosity in coupling between chemical reaction (complex formation) and diffusion in membranes has been investigated. The Fick law was replaced by the momentum balance equation with the viscous term. The irreversible thermodynamics admits coupling of the chemical reaction rate with the gradient of velocity. The proposed model has shown the contrary effect of viscosity and confirmed the experimental results. The chemical reaction rate increases only above the limit value of viscosity. The parameter Q (degree of complex formation) was introduced to investigate coupling. Q equals to the ratio of the chemical contribution into the flux of the complex to the total flux of the substance transported. For different values of the parameters of the model the dependence of Q upon position inside the membrane has been numerically calculated. The assumptions of the model limit it to a specific case and they only roughly model the biological situation. PMID:6537360

  18. 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.

  19. Chemical Reaction Rates from Ring Polymer Molecular Dynamics: Theory and Practical Applications

    CERN Document Server

    Suleimanov, Yury V; Guo, Hua

    2016-01-01

    This Feature Article presents an overview of the current status of Ring Polymer Molecular Dynamics (RPMD) rate theory. We first analyze theory and its connection to quantum transition state theory. We then focus on its practical application to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rates 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 rates. We also hope it will motivate further applications of RPMD to various chemical reactions.

  20. Chemical Reactions of N13 Recoils from the C12 (d, n)N13 Reaction

    International Nuclear Information System (INIS)

    Earlier studies of N13 recoils produced by the nuclear reaction C12 (d, n) N13 in CH4, CH3OH, CCl4, etc. showed that the final radioactive gaseous products were entirely cyanides such as HCN, CH3CN and ClCN. No ammonia or amines were detected. In this study the investigation has been extended to benzene and CF4. In addition reactions of N+ ions with CCl4 and CF4 have been examined in a tandem mass spectrometer. In the case of N13 recoils reacting with benzene HCN was the main product and small amounts of benzonitrile were formed. No aniline or pyridine were produced. This will be contrasted with reported studies in which active nitrogen produced by electrical discharge reacted with benzene. In the case of CF4, the only radioactive product detected was FCN. In both cases polymeric materials were produced on the walls of the reaction vessels. No other products such as NF3 were detected. Studies of the effect of rare gas additives in the case of methanol indicated that ion-molecule reactions were involved at least in part. For this reason, the reactions of N+ ions with CCI4 and CF4 were studied in a tandem mass spectrometer in the bombarding ion energy range from 2 eV to. 200 eV. In this study the relative cross-sections for various ion production were investigated as a function of energy. In addition to ions composed of carbon and chlorine, various nitrogen-containing ions such as NCl+. CNCl+ and CN+ were detected. The shapes of the cross-section curves were such as to indicate complex formation possibly (CCl4N)+, which decomposed to give the product ions. The above complex was not detected directly. (author)

  1. Automatic reaction to a chemical event detected by a low-cost wireless chemical sensing network

    OpenAIRE

    Beirne, Stephen; Lau, King-Tong; Corcoran, Brian; Diamond, Dermot

    2009-01-01

    A test-scale wireless chemical sensor network (WCSN) has been deployed within a controlled Environmental Chamber (EC). The combined signals from the WCSN were used to initiate a controllable response to the detected chemical event. When a particular sensor response pattern was obtained, a purging cycle was initiated. Sensor data were continuously checked against user-defined action limits, to determine if a chemical event had occurred. An acidic contaminant was used to demonstrate the respons...

  2. 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.

  3. Chemical Reactions and Kinetics of the Carbon Monoxide Coupling in the Presence of Hydrogen

    Institute of Scientific and Technical Information of China (English)

    Fandong Meng; Genhui Xu; Zhenhua Li; Pa Du

    2002-01-01

    The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence.

  4. Chemical reactions during the thermal processing of borazene polymers

    International Nuclear Information System (INIS)

    A class of borazene polymers was developed which consists of a two-dimensional array of six-membered borazene rings with the borons of adjacent borazene rings separated by -NH- groups. Pyrolysis of these polymers above ∼1000 degrees C leads to crystalline graphite-like boron nitride (h-BN). The thermal chemistry of thin films of one polymer deposited on KOH-etched aluminum was examined by thermal decomposition mass spectroscopy (TDMS) and thermal gravimetric analysis (TGA) and the gas evolution chemistry was found to be essentially complete at temperatures less than 400 degrees C. All products desorb with the same temperature profile and the major desorbing species are NH3 and N2, consistent with a loss of excess nitrogen and hydrogen in the polymer, and HCI from decomposition of byproducts of the synthesis step. Since the formation of ordered crystalline h-BN films requires heating to temperatures of the order of 1000 degrees C, whereas the gas evolution chemistry is complete by roughly 400 degrees C, it is concluded that gas evolution chemical processes are not rate limiting in BN ceramic production

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

    Czech Academy of Sciences Publication Activity Database

    Lísal, Martin; Brennan, J.K.; Smith, W.R.

    2006-01-01

    Roč. 124, č. 6 (2006), s. 64712.1-64712.14. ISSN 0021-9606 R&D Projects: GA ČR(CZ) GA203/05/0725; GA AV ČR(CZ) 1ET400720507; GA AV ČR(CZ) 1ET400720409 Institutional research plan: CEZ:AV0Z40720504 Keywords : nanopore * NO dimerization * reaction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.166, year: 2006

  6. Characteristics of Turbulent/non-turbulent Interface in a Turbulent Planar Jet with a Chemical Reaction

    Science.gov (United States)

    Watanabe, Tomoaki; Sakai, Yasuhiko; Nagata, Kouji; Terashima, Osamu; Ito, Yasumasa; Hayase, Toshiyuki

    2013-11-01

    Characteristics of chemical reaction (A + B --> P) near the turbulent/non-turbulent (T/NT) interface are investigated by using the direct numerical simulation of reactive planar jet. The reactants A and B are separately premixed into the jet and ambient flows, respectively. DNS is performed at three different Damköhler numbers. The conditional statistics conditioned on the distance from the T/NT interface is used to investigate the chemical reaction near the T/NT interface. The conditional mean concentration of product P shows a sharp jump near the T/NT interface, and the product P hardly exists in the non-turbulent region. This implies that the chemical reaction takes place in the turbulent region after the reactant B in the ambient flow is entrained into the turbulent region. The conditional mean scalar dissipation rate of mixture fraction has a large peak value slightly inside the T/NT interface. At the same point, the chemical reaction rate also has a peak value in the case of large Damköhler number. On the other hand, when the Damköhler number is small, the chemical reaction rate near the T/NT interface is smaller than that in the turbulent region. This work was carried out under the Collaborative Research Project of the Institute of Fluid Science, Tohoku University. Part of this work was supported by JSPS KAKENHI Grant Number 25002531 and MEXT KAKENHI Grant Numbers 25289030, 25289031, 2563005.

  7. 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. PMID:27147197

  8. Photo-induced isomerization and chemical reaction dynamics in superfluid helium droplets

    Science.gov (United States)

    Merritt, Jeremy; Douberly, Gary; Miller, Roger

    2008-03-01

    Near threshold photo-induced isomerization and photo-induced chemical reactions have long been sough after as sensitive probes of the underlying potential energy surface. One of the most important questions asked is how the initially bright quantum state couples to the reaction coordinate, and thus relates to energy transfer in general. Helium droplets have now allowed us to stabilize entrance channel clusters behind very small reaction barriers such that vibrational excitation may result in reaction. Through two examples, namely the isomerization of the 2 binary complexes of HF-HCN Douberly et al. PCCP 2005, 7,463, and the induced reaction of the gallium-HCN complex Merritt et al. JPCA 2007, DOI:10.1021/jp074981e we will show how the branching ratios for reaction and predissociation can determined and the influence of the superfluid He solvent.

  9. Coherent chemical kinetics as quantum walks. I. Reaction operators for radical pairs

    Science.gov (United States)

    Chia, A.; Tan, K. C.; Pawela, Ł.; Kurzyński, P.; Paterek, T.; Kaszlikowski, D.

    2016-03-01

    Classical chemical kinetics uses rate-equation models to describe how a reaction proceeds in time. Such models are sufficient for describing state transitions in a reaction where coherences between different states do not arise, in other words, a reaction that contains only incoherent transitions. A prominent example of a reaction containing coherent transitions is the radical-pair model. The kinetics of such reactions is defined by the so-called reaction operator that determines the radical-pair state as a function of intermediate transition rates. We argue that the well-known concept of quantum walks from quantum information theory is a natural and apt framework for describing multisite chemical reactions. By composing Kraus maps that act only on two sites at a time, we show how the quantum-walk formalism can be applied to derive a reaction operator for the standard avian radical-pair reaction. Our reaction operator predicts the same recombination dephasing rate as the conventional Haberkorn model, which is consistent with recent experiments [K. Maeda et al., J. Chem. Phys. 139, 234309 (2013), 10.1063/1.4844355], in contrast to previous work by Jones and Hore [J. A. Jones and P. J. Hore, Chem. Phys. Lett. 488, 90 (2010), 10.1016/j.cplett.2010.01.063]. The standard radical-pair reaction has conventionally been described by either a normalized density operator incorporating both the radical pair and reaction products or a trace-decreasing density operator that considers only the radical pair. We demonstrate a density operator that is both normalized and refers only to radical-pair states. Generalizations to include additional dephasing processes and an arbitrary number of sites are also discussed.

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

    CERN Document Server

    Ge, Hao

    2016-01-01

    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 chemistry 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. Discrete formulation of mixed finite element methods for vapor deposition chemical reaction equations

    Institute of Scientific and Technical Information of China (English)

    LUO Zhen-dong; ZHOU Yan-jie; ZHU Jiang

    2007-01-01

    The vapor deposition chemical reaction processes, which are of extremely extensive applications, can be classified as a mathematical modes by the following governing nonlinear partial differential equations containing velocity vector,temperature field,pressure field,and gas mass field.The mixed finite element(MFE)method is employed to study the system of equations for the vapor deposition chemical reaction processes.The semidiscrete and fully discrete MFE formulations are derived.And the existence and convergence(error estimate)of the semidiscrete and fully discrete MFE solutions are deposition chemical reaction processes,the numerical solutions of the velocity vector,the temperature field,the pressure field,and the gas mass field can be found out simultaneonsly.Thus,these researches are not only of important theoretical means,but also of extremely extensive applied vistas.

  12. Application of laser diagnostics to sodium-water chemical reaction field

    International Nuclear Information System (INIS)

    In a sodium-cooled fast reactor (SFR), liquid sodium is used as a heat transfer fluid because of its excellent heat transport capability. On the other hand, it has strong chemical reactivity with water vapor. One of the design basis accidents of the SFR is the water leakage into the liquid sodium flow by a breach of heat transfer tubes in a steam generator. Therefore the study on sodium-water chemical reactions is of paramount importance for safety reasons. This study aims to clarify the sodium-water reaction mechanisms using laser diagnostics. The sodium-water counter-flow reactions were measured using laser diagnostics such as laser induced fluorescence, CARS, Raman scattering and photo-fragmentation. The measurement results show that the sodium-water reaction proceeds mainly by the reaction Na + H2O → NaOH + H and the main product is NaOH in this reaction. Its forward and backward reaction rates tend to balance with each other and the whole reaction rate reduces as temperature increases. (author)

  13. Fluctuation Induced Structure in Chemical Reaction with Small Number of Molecules

    Science.gov (United States)

    Suzuki, Yasuhiro

    We investigate the behaviors of chemical reactions of the Lotka-Volterra model with small number of molecules; hence the occurrence of random fluctuations modifies the deterministic behavior and the law of mass action is replaced by a stochastic model. We model it by using Abstract Rewriting System on Multisets, ARMS; ARMS is a stochastic method of simulating chemical reactions and it is based on the reaction rate equation. We confirmed that the magnitude of fluctuations on periodicity of oscillations becomes large, as the number of involved molecules is getting smaller; and these fluctuations induce another structure, which have not observed in the reactions with large number of molecules. We show that the underling mechanism through investigating the coarse grained phase space of ARMS.

  14. Automated Discovery of Elementary Chemical Reaction Steps Using Freezing String and Berny Optimization Methods

    CERN Document Server

    Suleimanov, Yury V

    2015-01-01

    We present a simple protocol which allows fully automated discovery of elementary chemical reaction steps using in cooperation single- and double-ended transition-state optimization algorithms - the freezing string and Berny optimization methods, respectively. To demonstrate the utility of the proposed approach, the reactivity of several systems of combustion and atmospheric chemistry importance is investigated. The proposed algorithm allowed us to detect without any human intervention not only "known" reaction pathways, manually detected in the previous studies, but also new, previously "unknown", reaction pathways which involve significant atom rearrangements. We believe that applying such a systematic approach to elementary reaction path finding will greatly accelerate the possibility of discovery of new chemistry and will lead to more accurate computer simulations of various chemical processes.

  15. Molecular dynamics study of phase separation in fluids with chemical reactions

    Science.gov (United States)

    Krishnan, Raishma; Puri, Sanjay

    2015-11-01

    We present results from the first d =3 molecular dynamics (MD) study of phase-separating fluid mixtures (AB) with simple chemical reactions (A ⇌B ). We focus on the case where the rates of forward and backward reactions are equal. The chemical reactions compete with segregation, and the coarsening system settles into a steady-state mesoscale morphology. However, hydrodynamic effects destroy the lamellar morphology which characterizes the diffusive case. This has important consequences for the phase-separating structure, which we study in detail. In particular, the equilibrium length scale (ℓeq) in the steady state suggests a power-law dependence on the reaction rate ɛ :ℓeq˜ɛ-θ with θ ≃1.0 .

  16. Automated Discovery of Elementary Chemical Reaction Steps Using Freezing String and Berny Optimization Methods.

    Science.gov (United States)

    Suleimanov, Yury V; Green, William H

    2015-09-01

    We present a simple protocol which allows fully automated discovery of elementary chemical reaction steps using in cooperation double- and single-ended transition-state optimization algorithms--the freezing string and Berny optimization methods, respectively. To demonstrate the utility of the proposed approach, the reactivity of several single-molecule systems of combustion and atmospheric chemistry importance is investigated. The proposed algorithm allowed us to detect without any human intervention not only "known" reaction pathways, manually detected in the previous studies, but also new, previously "unknown", reaction pathways which involve significant atom rearrangements. We believe that applying such a systematic approach to elementary reaction path finding will greatly accelerate the discovery of new chemistry and will lead to more accurate computer simulations of various chemical processes. PMID:26575920

  17. 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.

  18. Structural dynamics effects on the ultrafast chemical bond cleavage of a photodissociation reaction

    OpenAIRE

    Corrales, Maria E.; Loriot, Vincent; Balerdi, Garikoitz; González-Vázquez, Jesús; de Nalda, Rebeca; Bañares, Luis; Zewail, Ahmed H.

    2014-01-01

    The correlation between chemical structure and dynamics has been explored in a series of molecules with increasing structural complexity in order to investigate its influence on bond cleavage reaction times in a photodissociation event. Femtosecond time-resolved velocity map imaging spectroscopy reveals specificity of the ultrafast carbon–iodine (C–I) bond breakage for a series of linear (unbranched) and branched alkyl iodides, due to the interplay between the pure reaction coordinate and the...

  19. New Approach to the Stability of Chemical Reaction Networks: Piecewise Linear in Rates Lyapunov Functions

    OpenAIRE

    Al-Radhawi, M. Ali; Angeli, David

    2014-01-01

    Piecewise-Linear in Rates (PWLR) Lyapunov functions are introduced for a class of Chemical Reaction Networks (CRNs). In addition to their simple structure, these functions are robust with respect to arbitrary monotone reaction rates, of which mass-action is a special case. The existence of such functions ensures the convergence of trajectories towards equilibria, and guarantee their asymptotic stability with respect to the corresponding stoichiometric compatibility class. We give the definiti...

  20. Reaction of Phosphorylated and O-Glycosylated Peptides by Chemically Targeted Identification at Ambient Temperature

    OpenAIRE

    Rusnak, Felicia; Zhou, Jie; Hathaway, Gary M.

    2004-01-01

    Conditions for carrying out chemically targeted identification of peptides containing phosphorylated or glycosylated serine residues have been investigated. Ba(OH)2 was used at ambient temperature to catalyze the β-elimination reaction at 25°C. Nucleophilic addition of 2-aminoethanethiol was performed in both parallel and tandem experiments. The method was demonstrated by the reaction of β-casein tryptic digest phosphopeptides and an O-glycosylated peptide. Contrary to an earlier report by ot...

  1. A kinetic model for chemical reactions without barriers : transport coefficients and eigenmodes

    OpenAIRE

    Alves, Giselle M.; Marques Júnior, Wilson; Soares, A. J.; Kremer, Gilberto M.

    2011-01-01

    The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solution of the Boltzmann equation is determined through an expansion in Sonine polyn...

  2. Transformation of Symmetrization Order to Nuclear-Spin Magnetization by Chemical Reaction and Nuclear Magnetic Resonance

    OpenAIRE

    Bowers, C. Russell; Weitekamp, Daniel P.

    1986-01-01

    A method of obtaining very large nuclear-spin polarizations is proposed and illustrated by density-operator calculations. The prediction is that chemical reaction and rf irradiation can convert the scalar parahydrogen state into polarization of order unity on the nuclear spins of the products of molecular-hydrogen addition reactions. A means of extending the resultant sensitivity enhancement to other spins is proposed in which the transfer of order occurs through population differences not as...

  3. On the Mathematical Structure of Balanced Chemical Reaction Networks Governed by Mass Action Kinetics

    OpenAIRE

    der Schaft, Arjan van; Rao, Shodhan; Jayawardhana, Bayu

    2011-01-01

    Motivated by recent progress on the interplay between graph theory, dynamics, and systems theory, we revisit the analysis of chemical reaction networks described by mass action kinetics. For reaction networks possessing a thermodynamic equilibrium we derive a compact formulation exhibiting at the same time the structure of the complex graph and the stoichiometry of the network, and which admits a direct thermodynamical interpretation. This formulation allows us to easily characterize the set ...

  4. On the study of nonlinear dynamics of complex chemical reaction systems

    Institute of Scientific and Technical Information of China (English)

    XIN; Houwen; HOU; Zhonghuai

    2006-01-01

    With ever-increasing attentions being paid to complex systems such as the life system, soft matter, and nano-systems, theoretical studies of non-equilibrium nonlinear problems involved in chemical dynamics are now of general interest. In this mini-review, we mainly give a brief introduction to some frontier topics in this field, namely, nonlinear state-state dynamics, nonlinear chemical dynamics on complex networks, and nonlinear dynamics in mesoscopic chemical reaction systems. Deep study of these topics will make great contribution to discovering new laws of chemical dynamics, to exploring new control methods of complex chemical processes, to figuring out the very roles of chemical processes in the life system, and to crosslinking the scientific study of chemistry, physics and biology.

  5. 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...... 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....

  6. 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...

  7. Engineering Model Reduction and Entropy-based Lyapunov Functions in Chemical Reaction Kinetics

    OpenAIRE

    Hangos, Katalin M.

    2010-01-01

    In this paper, the structural properties of chemical reaction systems obeying the mass action law are investigated and related to the physical and chemical properties of the system. An entropy-based Lyapunov function candidate serves as a tool for proving structural stability, the existence of which is guaranteed by the second law of thermodynamics. The commonly used engineering model reduction methods, the so-called quasi equilibrium and quasi steady state assumption based reductions, togeth...

  8. Product-form stationary distributions for deficiency zero chemical reaction networks

    OpenAIRE

    Anderson, David F.; Craciun, Gheorghe; Kurtz, Thomas G.

    2008-01-01

    We consider stochastically modeled chemical reaction systems with mass-action kinetics and prove that a product-form stationary distribution exists for each closed, irreducible subset of the state space if an analogous deterministically modeled system with mass-action kinetics admits a complex balanced equilibrium. Feinberg's deficiency zero theorem then implies that such a distribution exists so long as the corresponding chemical network is weakly reversible and has a deficiency of zero. The...

  9. Thermodynamic and Kinetic Investigation of a Chemical Reaction-Based Miniature Heat Pump

    OpenAIRE

    Flueckiger, Scott M.; Volle, Fabien; Garimella, S V; Mongia, Rajiv K.

    2012-01-01

    Representative reversible endothermic chemical reactions (paraldehyde depolymerization and 2-proponal dehydrogenation) are theoretically assessed for their use in a chemical heat pump design for compact thermal management applications. Equilibrium and dynamic simulations are undertaken to explore the operation of the heat pump which upgrades waste heat from near room temperature by approximately 20 in a minimized system volume. A model is developed based on system mass and energy balances cou...

  10. The phase transition and classification of critical points in the multistability chemical reactions

    Institute of Scientific and Technical Information of China (English)

    ChunhuaZHANG; FugenWU; ChunyanWU; FaOU

    2000-01-01

    In this paper, we study the phase transition and classification of critical points in multistability chemical reaction systems. Referring to the spirit of Landau's theory of phase transitions, this paper deals with the varied transitions and critical phenomena in multistable chemical systems. It is demonstrated that the higher the order of the multistability,the wider the variety of phase transitions will be. A classification scheme of critical points according to the stability criterion and the thermodynamic potential continuity is suggested.It is useful for us to study critical phenomena especially in the non-equilibrium systems including the multi-stable chemical ones.

  11. Relativistic thermodynamics of irreversible processes I. Heat conduction, diffusion, viscous flow and chemical reactions; formal part

    NARCIS (Netherlands)

    Kluitenberg, G.A.; Groot, S.R. de; Mazur, P.

    1953-01-01

    The relativistic thermodynamics of irreversible processes is developed for an isotropic mixture in which heat conduction, diffusion, viscous flow, chemical reactions and their cross-phenomena may occur. The four-vectors, representing the relative flows of matter, are defined in such a way that, in t

  12. 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,…

  13. The Effective Concepts on Students' Understanding of Chemical Reactions and Energy

    Science.gov (United States)

    Ayyildiz, Yildizay; Tarhan, Leman

    2012-01-01

    The purpose of this study was to determine the relationship between the basic concepts related to the unit of "Chemical Reactions and Energy" and the sub-concepts underlying for meaningful learning of the unit and to investigate the effectiveness of them on students' learning achievements. For this purpose, the basic concepts of the unit were…

  14. Mapping Students' Modes of Reasoning When Thinking about Chemical Reactions Used to Make a Desired Product

    Science.gov (United States)

    Weinrich, M. L.; Talanquer, V.

    2016-01-01

    The central goal of this study was to analyze the complexity of students' explanations about how and why chemical reactions happen in terms of the types of causal connections students built between expressed concepts and ideas. We were particularly interested in characterizing differences in the types of reasoning applied by students with…

  15. Impact of supersonic and subsonic aircraft on ozone: Including heterogeneous chemical reaction mechanisms

    Science.gov (United States)

    Kinnison, Douglas E.; Wuebbles, Donald J.

    1994-01-01

    Preliminary calculations suggest that heterogeneous reactions are important in calculating the impact on ozone from emissions of trace gases from aircraft fleets. In this study, three heterogeneous chemical processes that occur on background sulfuric acid aerosols are included and their effects on O3, NO(x), Cl(x), HCl, N2O5, ClONO2 are calculated.

  16. Two Experiments to Approach the Boltzmann Factor: Chemical Reaction and Viscous Flow

    Science.gov (United States)

    Fazio, Claudio; Battaglia, Onofrio R.; Guastella, Ivan

    2012-01-01

    In this paper we discuss a pedagogical approach aimed at pointing out the role played by the Boltzmann factor in describing phenomena usually perceived as regulated by different mechanisms of functioning. Experimental results regarding some aspects of a chemical reaction and of the viscous flow of some liquids are analysed and described in terms…

  17. 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...

  18. Turkish, Indian, and American Chemistry Textbooks Use of Inscriptions to Represent "Types of Chemical Reactions"

    Science.gov (United States)

    Aydin, Sevgi; Sinha, Somnath; Izci, Kemal; Volkmann, Mark

    2014-01-01

    The purpose of this study was to investigate inscriptions used in "Types of Chemical Reactions" topic in Turkish, Indian, and American chemistry textbooks. We investigated both the types of inscriptions and how they were used in textbooks to support learning. A conceptual analysis method was employed to determine how those textbooks use…

  19. Facilitating High School Students' Use of Multiple Representations to Describe and Explain Simple Chemical Reactions

    Science.gov (United States)

    Chandrasegaran, A. L.; Treagust, David F.; Mocerino, Mauro

    2011-01-01

    This study involved the evaluation of the efficacy of a planned instructional program to facilitate understanding of the macroscopic, submicroscopic and symbolic representational systems when describing and explaining chemical reactions by sixty-five Grade 9 students in a Singapore secondary school. A two-tier multiple-choice diagnostic instrument…

  20. Influence of Size Effect on Chemical Reactions on Surface of Aerosol Nanoparticles

    Czech Academy of Sciences Publication Activity Database

    Levdansky, V.V.; Smolík, Jiří; Ždímal, Vladimír; Moravec, Pavel

    Prague : Czech Aerosol Society, 2013, C028. ISBN N. [European Aerosol Conference (EAC 2013). Prague (CZ), 01.09.2013-06.09.2013] R&D Projects: GA AV ČR IAA200760905 Institutional support: RVO:67985858 Keywords : aerosol * nanoparticles * chemical reactions Subject RIV: CF - Physical ; Theoretical Chemistry http://eac2013.cz/index.php

  1. Law of Large Numbers in the Supremum Norm for a Chemical Reaction with Diffusion

    OpenAIRE

    Blount, Douglas

    1992-01-01

    A space-time jump Markov process, modeling a chemical reaction with diffusion, is compared in the supremum norm to the usual model, the solution to a partial differential equation. Conditions are given which imply the deviation converges in probability to 0 uniformly on bounded time intervals. Estimates reflecting underlying large deviation behavior are obtained.

  2. Dynamics of chemical reactions of multiply-charged cations: Information from beam scattering experiments

    Czech Academy of Sciences Publication Activity Database

    Herman, Zdeněk

    2015-01-01

    Roč. 378, FEB 2015 (2015), s. 113-126. ISSN 1387-3806 Institutional support: RVO:61388955 Keywords : Multiply-charged ions * Dynamics of chemical reactions * Beam scattering Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.972, year: 2014

  3. Impact of supersonic and subsonic aircraft on ozone: Including heterogeneous chemical reaction mechanisms

    International Nuclear Information System (INIS)

    Preliminary calculations suggest that heterogeneous reactions are important in calculating the impact on ozone from emissions of trace gases from aircraft fleets. In this study, three heterogeneous chemical processes that occur on background sulfuric acid aerosols are included and their effects on O3, NOx, Clx, HCl, N2O5, ClONO2 are calculated

  4. On the graph and systems analysis of reversible chemical reaction networks with mass action kinetics

    NARCIS (Netherlands)

    Rao, Shodhan; Jayawardhana, Bayu; Schaft, Arjan van der

    2012-01-01

    Motivated by the recent progresses on the interplay between the graph theory and systems theory, we revisit the analysis of reversible chemical reaction networks described by mass action kinetics by reformulating it using the graph knowledge of the underlying networks. Based on this formulation, we

  5. On detonation initiation by a temperature gradient for a detailed chemical reaction models

    International Nuclear Information System (INIS)

    The evolution from a temperature gradient to a detonation is investigated for combustion mixture whose chemistry is governed by a detailed chemical kinetics. We show that a detailed chemical reaction model has a profound effect on the spontaneous wave concept for detonation initiation by a gradient of reactivity. The evolution to detonation due to a temperature gradient is considered for hydrogen-oxygen and hydrogen-air mixtures at different initial pressures. It is shown that the minimal length of the temperature gradient for which a detonation can be ignited is much larger than that predicted from a one-step chemical model. - Highlights: → We study detonation initiation by temperature gradient for detailed chemical models. → Detailed chemical models have a profound effect on the spontaneous wave concept. → Initiating detonation by temperature gradient differs from one-step model. → In real fuels DDT can not be initiated by temperature gradient.

  6. Stability of a laminar premixed supersonic free shear layer with chemical reactions

    Science.gov (United States)

    Menon, S.; Anderson, J. D., Jr.; Pai, S. I.

    1984-01-01

    The stability of a two-dimensional compressible supersonic flow in the wake of a flat plate is discussed. The fluid is a multi-species mixture which is undergoing finite rate chemical reactions. The spatial stability of an infinitesimal disturbance in the fluid is considered. Numerical solutions of the eigenvalue stability equations for both reactive and nonreactive supersonic flows are presented and discussed. The chemical reactions have significant influence on the stability behavior. For instance, a neutral eigenvalue is observed near the freestream Mach number of 2.375 for the nonreactive case, but disappears when the reaction is turned on. For reactive flows, the eigenvalues are not very dependent on the free stream Mach number.

  7. 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.

  8. On a theory of stability for nonlinear stochastic chemical reaction networks

    International Nuclear Information System (INIS)

    We present elements of a stability theory for small, stochastic, nonlinear chemical reaction networks. Steady state probability distributions are computed with zero-information (ZI) closure, a closure algorithm that solves chemical master equations of small arbitrary nonlinear reactions. Stochastic models can be linearized around the steady state with ZI-closure, and the eigenvalues of the Jacobian matrix can be readily computed. Eigenvalues govern the relaxation of fluctuation autocorrelation functions at steady state. Autocorrelation functions reveal the time scales of phenomena underlying the dynamics of nonlinear reaction networks. In accord with the fluctuation-dissipation theorem, these functions are found to be congruent to response functions to small perturbations. Significant differences are observed in the stability of nonlinear reacting systems between deterministic and stochastic modeling formalisms

  9. Chemical cleavage reactions of DNA on solid support: application in mutation detection

    Directory of Open Access Journals (Sweden)

    Cotton Richard GH

    2003-05-01

    Full Text Available Abstract Background The conventional solution-phase Chemical Cleavage of Mismatch (CCM method is time-consuming, as the protocol requires purification of DNA after each reaction step. This paper describes a new version of CCM to overcome this problem by immobilizing DNA on silica solid supports. Results DNA test samples were loaded on to silica beads and the DNA bound to the solid supports underwent chemical modification reactions with KMnO4 (potassium permanganate and hydroxylamine in 3M TEAC (tetraethylammonium chloride solution. The resulting modified DNA was then simultaneously cleaved by piperidine and removed from the solid supports to afford DNA fragments without the requirement of DNA purification between reaction steps. Conclusions The new solid-phase version of CCM is a fast, cost-effective and sensitive method for detection of mismatches and mutations.

  10. Density functional theory of chemical reactivity indices in some ion-molecule reaction systems

    International Nuclear Information System (INIS)

    Three isoelectronic reactions, proton transfer (PT), hydrogen abstraction (HA), and electron transfer (ET), of NH3+ with NH3, H2O, and HF have been studied using ab initio molecular orbital calculations. For the reaction of NH3+ + H2O, the energy of the transition state (TS) is higher than that of the reactants. This is consistent with the experimental observation that the rate constant is less than the average dipole orientation (ADO) rate constant. It seems reasonable that the reaction rate for the reaction NH3+ + H2O would hardly depend on the V2 mode of NH3+ at least for low-lying excited states (Eint≤ 0.714 eV) of the V2 mode, because the V2 contributes mainly to the normal mode orthogonal to the reaction coordinate at the TS. This is consistent with experimental observation. A similiar prediction can be made for the NH3+ + HF reaction. The electron transfer processes for the HA reactions have been examined in terms of the intrinsic reaction coordinate (IRC). The order of reactivity with NH3+ is NH3>H2O>HF. It is found that the degree of the electron transfer and the reactivity are correlated with the absolute hardness η of NH3, H2O, and HF. this is accord with the softness as the chemical reactivity index in the density functional theory. 25 refs., 6 fig., 4 tab

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

    International Nuclear Information System (INIS)

    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

  12. Ion-molecule reactions of oxygenated chemical ionization reagents with vincamine.

    Science.gov (United States)

    Bauerle, G F; Hall, B J; Tran, N V; Brodbelt, J S

    1996-03-01

    The ion-molecule reactions of ions from acetone, dimethyl ether, 2-methoxyethanol, and vinyl methyl ether with vincamine were investigated. Reactions with dimethyl ether result in [M+13](+) and [M+45](+) products, reactions with 2-methoxyethanol produce [M+13](+) and [M+89](+) ions, and reactions with acetone or vinyl methyl ether ions generate predominantly [M+43](+) ions. Collision-activated dissociation and deuterium labeling experiments allowed speculation about the product structures and mechanisms of dissociation. The methylene substitution process was shown to occur at the hydroxyl oxygen and the phenyl ring of vincamine for dimethyl ether reactions, but the methylene substitution process was not favored at the hydroxyl oxygen for the 2-methoxyethanol reactions, instead favored at the 12 phenyl position. The reaction site is likely different for the 2-methoxyethanol ion due to its capability for secondary hydrogen-bonding interactions. For the [M+45](+) and [M+89](+) ions, evidence suggests that charge-remote fragmentation processes occur from these products. In general, the use of dimethyl ether ions or 2-methoxyethanol ions for ionmolecule reactions prove highly diagnostic for the characterization of vincamine; both molecular weight and structural information are obtained. Limits of detection for vincamine with dimethyl ether chemical ionization via this technique on a benchtop ion trap gas chromatography-tandem mass spectrometer are in the upper parts per trillion range. PMID:24203296

  13. Chemical kinetic analysis of hydrogen-air ignition and reaction times

    Science.gov (United States)

    Rogers, R. C.; Schexnayder, C. J., Jr.

    1981-01-01

    An anaytical study of hydrogen air kinetics was performed. Calculations were made over a range of pressure from 0.2 to 4.0 atm, temperatures from 850 to 2000 K, and mixture equivalence ratios from 0.2 to 2.0. The finite rate chemistry model included 60 reactions in 20 species of the H2-O2-N2 system. The calculations also included an assessment of how small amounts of the chemicals H2O, NOx, H2O2, and O3 in the initial mixture affect ignition and reaction times, and how the variation of the third body efficiency of H2O relative of N2 in certain key reactions may affect reaction time. The results indicate that for mixture equivalence ratios between 0.5 and 1.7, ignition times are nearly constant; however, the presence of H2O and NO can have significant effects on ignition times, depending on the mixture temperature. Reaction time is dominantly influenced by pressure but is nearly independent of initial temperature, equivalence ratio, and the addition of chemicals. Effects of kinetics on reaction at supersonic combustor conditions are discussed.

  14. Effect of Chemical Reactions on the Hydrologic Properties of Fractured and Rubbelized Glass Media

    International Nuclear Information System (INIS)

    Understanding the effect of chemical reactions on the hydrologic properties of geological media, such as porosity, permeability and dispersivity, is critical to many natural and engineered sub-surface systems. Influence of glass corrosion (precipitation and dissolution) reactions on fractured and rubbelized (crushed) forms HAN28 and LAWBP1, two candidate waste glass forms for a proposed immobilized low-activity waste (ILAW) disposal facility at the Hanford, WA site, was investigated. Flow and tracer transport experiments were conducted using fractured and rubbelized forms, before and after subjecting them to corrosion using Vapor Hydration Testing (VHT) at 200 C temperature and 200 psig pressure, causing the precipitation of alteration products. Data were analyzed using analytical expressions and CXTFIT, a transport parameter optimization code, for the estimation of the hydrologic characteristics before and after VHT. It was found that glass reactions significantly influence the hydrologic properties of ILAW glass media. Hydrologic properties of rubbelized glass decreased due to precipitation reactions, whereas those of fractured glass media increased due to reaction which led to unconfined expansion of fracture aperture. The results are unique and useful to better understand the effect of chemical reactions on the hydrologic properties of fractured and rubbelized stony media in general and glass media in particular

  15. Chemical reactions at metallic and metal/semiconductor interfaces stimulated by pulsed laser annealing

    Science.gov (United States)

    Petit, E. J.; Caudano, R.

    1992-01-01

    Multilayer Al/Sb thin films have been evaporated on GaSb single crystals in ultra-high vacuum and pulsed-laser irradiated in-situ above the energy density threshold for surface melting. Superficial and interfacial chemical reactions have been characterized in-situ by Auger electron spectroscopy; and later, by X-ray photoelectron spectroscopy profiling, Rutherford backscattering spectrometry and scanning electron microscopy. The chemical reaction between the Al and Sb films is considered as a model reaction for laser-assisted synthesis of high-purity intermetallic compounds. The observation of a strong interfacial reaction between the melted film and the substrate is also a subject of great concern for optical data recording and laser alloying of ohmic contacts on semiconductors. We show that a suitable choice of the substrate and adding a low surface tension element into the metallic film can improve its stability during melting, and prevent inhomogeneous reaction and formation of holes, cracks and particles. Finally, other solutions are suggested to improve the control of these reactions.

  16. Nonequilibrium thermodynamic formalism of nonlinear chemical reaction systems with Waage-Guldberg's law of mass action

    Science.gov (United States)

    Ge, Hao; Qian, Hong

    2016-06-01

    Macroscopic entropy production rate σ (tot) in the general nonlinear isothermal chemical reaction system with mass action kinetics is decomposed into a free energy dissipation rate and a house-keeping heat dissipation rate: σ (tot) =σ (fd) +σ (hk) ; σ (fd) = -d A /d t , where A is a generalized free energy function. This yields a novel nonequilibrium free energy balance equation d A /d t = -σ (tot) +σ (hk) , which is on a par with celebrated entropy balance equation d S /d t =σ (tot) +η (ex) where η (ex) is the rate of entropy exchange with the environment. For kinetic systems with complex balance, σ (fd) and σ (hk) are the macroscopic limits of stochastic free energy dissipation rate and house-keeping heat dissipation rate, which are both nonnegative, in the Delbrück-Gillespie description of the stochastic chemical kinetics. A full kinetic and thermodynamic theory of chemical reaction systems that transcends mesoscopic and macroscopic levels emerges.

  17. Chemical Synthesis of Proanthocyanidins in Vitro and Their Reactions in Aging Wines

    Directory of Open Access Journals (Sweden)

    Qiu-Hong Pan

    2008-12-01

    Full Text Available Proanthocyanidins are present in many fruits and plant products like grapes and wine, and contribute to their taste and health benefits. In the past decades of years, substantial progresses has been achieved in the identification of composition and structure of proanthocyanidins, but the debate concerning the existence of an enzymatic or nonenzymatic mechanism for proanthocyanidin condensation still goes on. Substantial attention has been paid to elucidating the potential mechanism of formation by means of biomimetic and chemical synthesis in vitro. The present paper aims at summarizing the research status on chemical synthesis of proanthocyanidins, including non-enzymatic synthesis of proanthocyanidin precursors, chemical synthesis of proanthocyanidins with direct condensation of flavanols and stereoselective synthesis of proanthocyanidins. Proanthocyanidin-involved reactions in aging wines are also reviewed such as direct and indirect reactions among proanthocyanidins, flavanols and anthocyanins. Topics for future research in this field are also put forward in this paper.

  18. Two-scale large deviations for chemical reaction kinetics through second quantization path integral

    Science.gov (United States)

    Li, Tiejun; Lin, Feng

    2016-04-01

    Motivated by the study of rare events for a typical genetic switching model in systems biology, in this paper we aim to establish the general two-scale large deviations for chemical reaction systems. We build a formal approach to explicitly obtain the large deviation rate functionals for the considered two-scale processes based upon the second quantization path integral technique. We get three important types of large deviation results when the underlying two timescales are in three different regimes. This is realized by singular perturbation analysis to the rate functionals obtained by the path integral. We find that the three regimes possess the same deterministic mean-field limit but completely different chemical Langevin approximations. The obtained results are natural extensions of the classical large volume limit for chemical reactions. We also discuss its implication on the single-molecule Michaelis-Menten kinetics. Our framework and results can be applied to understand general multi-scale systems including diffusion processes.

  19. Review and analysis of high temperature chemical reactions and the effect of non-equilibrium conditions

    Science.gov (United States)

    Johnson, R. E.

    1986-01-01

    Chemical reactions at high temperatures have been considered extensively because of their importance to the heating effects on re-entry of space vehicles. Data on these reactions however, are not abundant and even when found there are discrepancies in data collected by various investigators. In particular, data for recombination reactions are calculated from the dissociation reactions or vice versa through the equilibrium constant. This involves the use of the principle of detailed balancing. This principle is discussed in reference to conditions where it is valid as well as to those where it is not valid. Related topics that merit further study or for which applicable information was available are briefly mentioned in an appendix to this report.

  20. Kinetics and thermodynamics of chemical reactions in Li/SOCl2 cells

    Science.gov (United States)

    Hansen, Lee D.; Frank, Harvey

    1987-01-01

    Work is described that was designed to determine the kinetic constants necessary to extrapolate kinetic data on Li/SOCl2 cells over the temperature range from 25 to 75 C. A second objective was to characterize as far as possible the chemical reactions that occur in the cells since these reactions may be important in understanding the potential hazards of these cells. The kinetics of the corrosion processes in undischarged Li/SOCl2 cells were determined and separated according to their occurrence at the anode and cathode; the effects that switching the current on and off has on the corrosion reactions was determined; and the effects of discharge state on the kinetics of the corrosion process were found. A thermodynamic analysis of the current-producing reactions in the cell was done and is included.

  1. 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.

  2. Assessment of existing H2/O2 chemical reaction mechanisms at reheat gas turbine conditions

    CERN Document Server

    Weydahl, Torleif; Seljeskog, Morten; Haugen, Nils Erland L

    2011-01-01

    This paper provides detailed comparisons of chemical reaction mechanisms of H2 applicable at high preheat temperatures and pressures relevant to gas turbine and particularly Alstom's reheat gas turbine conditions. It is shown that the available reaction mechanisms exhibit large differences in several important elementary reaction coefficients. The reaction mechanisms are assessed by comparing ignition delay and laminar flame speed results obtained from CHEMKIN with available data, however, the amount of data at these conditions is scarce and a recommended candidate among the mechanisms can presently not be selected. Generally, the results with the GRI-Mech and Leeds mechanisms deviate from the Davis, Li, O'Conaire, Konnov and San Diego mechanisms, but there are also significant deviations between the latter five mechanisms that altogether are better adapted to hydrogen. The differences in ignition delay times between the dedicated hydrogen mechanisms (O'Conaire, Li and Konnov) range from approximately a maxim...

  3. Parent type chemical species formed by recoil implantation reaction in tris(β-diketonato)metal(III)

    International Nuclear Information System (INIS)

    Chemical reactions induced by recoil implantation were studied focussing on parent type species in tris(β-diketonato)metal(III) complexes. The yield of the substitution reaction *M + M(acac)3 → *M(acac)3 + M was dependent on the force constant ratio K(*M-O)/K(M-O), showing that competition occurred between *M and M in the cage of the acetylacetonate complex. In the case of *Cr implantation in Co(acac)3, an exceptionally large yield could be explained by formation of Co(acac)2, whose central metal easily exchanges with *Cr, and by pickup of acac. When different β-diketonate complexes were examined in the reaction *Cr + M(β-dik)3 → *Cr(β-dik)3 + M the yield was dependent on the stability of the M(β-dik)3 complexes. A reaction model to explain these results reasonably was presented. (orig.)

  4. Ab Initio Calculation of Rate Constants for Molecule-Surface Reactions with Chemical Accuracy.

    Science.gov (United States)

    Piccini, GiovanniMaria; Alessio, Maristella; Sauer, Joachim

    2016-04-18

    The ab initio prediction of reaction rate constants for systems with hundreds of atoms with an accuracy that is comparable to experiment is a challenge for computational quantum chemistry. We present a divide-and-conquer strategy that departs from the potential energy surfaces obtained by standard density functional theory with inclusion of dispersion. The energies of the reactant and transition structures are refined by wavefunction-type calculations for the reaction site. Thermal effects and entropies are calculated from vibrational partition functions, and the anharmonic frequencies are calculated separately for each vibrational mode. This method is applied to a key reaction of an industrially relevant catalytic process, the methylation of small alkenes over zeolites. The calculated reaction rate constants (free energies), pre-exponential factors (entropies), and enthalpy barriers show that our computational strategy yields results that agree with experiment within chemical accuracy limits (less than one order of magnitude). PMID:27008460

  5. Method of Investigating Fast Chemical Reactions Based on μ+-Meson Depolarization

    International Nuclear Information System (INIS)

    When a μ+-meson is slowed down in a substance the hydrogenoid muonium atom formed enters into chemical reactions similar to the corresponding interactions of atomic hydrogen. The observed angular distribution effect of the meson decay is associated with the chemical state of the meson. The absolute constants of the rate of the chemical reactions are determined in relation to the known nuclear physical decay characteristics. The method is independent of the state of aggregation of the substance and can be applied at essentially any temperature. Quantitative identification of the classes of the substances obtained (radical and molecular products are determined separately) is possible, as is individual determination based on variations in the precession of the system of spins in the magnetic field using a number of diatomic molecules as an example. The authors consider the possibility of studying the structural parameters of the radicals and molecules, and of estimating the lifetime of the short-lived intermediate compounds. The elementary steps in fast chemical reactions are investigated. (author)

  6. Coupling of hydrologic transport and chemical reactions in a stream affected by acid mine drainage

    Science.gov (United States)

    Kimball, B.A.; Broshears, R.E.; Bencala, K.E.; McKnight, Diane M.

    1994-01-01

    Experiments in St. Kevin Gulch, an acid mine drainage stream, examined the coupling of hydrologic transport to chemical reactions affecting metal concentrations. Injection of LiCl as a conservative tracer was used to determine discharge and residence time along a 1497-m reach. Transport of metals downstream from inflows of acidic, metal-rich water was evaluated based on synoptic samples of metal concentrations and the hydrologic characteristics of the stream. Transport of SO4 and Mn was generally conservative, but in the subreaches most affected by acidic inflows, transport was reactive. Both 0.1-??m filtered and particulate Fe were reactive over most of the stream reach. Filtered Al partitioned to the particulate phase in response to high instream concentrations. Simulations that accounted for the removal of SO4, Mn, Fe, and Al with first-order reactions reproduced the steady-state profiles. The calculated rate constants for net removal used in the simulations embody several processes that occur on a stream-reach scale. The comparison between rates of hydrologie transport and chemical reactions indicates that reactions are only important over short distances in the stream near the acidic inflows, where reactions occur on a comparable time scale with hydrologic transport and thus affect metal concentrations.

  7. Open chemical reaction networks, steady-state loads and Braess-like paradox

    CERN Document Server

    Banerjee, Kinshuk

    2014-01-01

    Open chemical reaction systems involve matter-exchange with the surroundings. As a result, species can accumulate inside a system during the course of the reaction. We study the role of network topology in governing the concentration build-up inside a fixed reaction volume at steady state, particularly focusing on the effect of additional paths. The problem is akin to that in traffic networks where an extra route, surprisingly, can increase the overall travel time. This is known as the Braess' paradox. Here, we report chemical analogues of such a paradox in suitably chosen reaction networks, where extra reaction step(s) can inflate the total concentration, denoted as `load', at steady state. It is shown that, such counter-intuitive behavior emerges in a qualitatively similar pattern in networks of varying complexities. We then explore how such extra routes affect the load in a biochemical scheme of uric acid degradation. From a thorough analysis of this network, we propose a functional role of some decomposit...

  8. Nanostructured palladium tailored via carbonyl chemical route towards oxygen reduction reaction

    International Nuclear Information System (INIS)

    Graphical Abstract: Mass-depending morphologies of nanostructured Palladium obtained via the carbonyl chemical route. Display Omitted -- Highlights: •Mass-depending morphology was observed in nanostructured palladium supported on carbon prepared by the carbonyl chemical route. •The Morphological effect of carbon supported Pd was investigated towards ORR. -- Abstract: Carbon supported palladium nanostructures were synthesized via the carbonyl chemical route. Compared with nanostructured platinum, prepared via carbonyl chemical route, Pd nanomaterials showed mass-loading morphology, whereas particle size and morphology of Pt nanostructures was constant. The oxygen reduction reaction (ORR) on nanostructured Pd, with different morphology in both acid and alkaline medium was investigated. A relationship, based on X-ray diffraction structural analysis pattern, transmission electron microscope, with the Pd morphological effect on ORR activity was identified

  9. 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.

  10. 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.

  11. Simulations of isoprene: Ozone reactions for a general circulation/chemical transport model

    Science.gov (United States)

    Makar, P. A.; Mcconnell, J. C.

    1994-01-01

    A parameterized reaction mechanism has been created to examine the interactions between isoprene and other tropospheric gas-phase chemicals. Tests of the parameterization have shown that its results match those of a more complex reaction set to a high degree of accuracy. Comparisons between test runs have shown that the presence of isoprene at the start of a six day interval can enhance later ozone concentrations by as much as twenty-nine percent. The test cases used no input fluxes beyond the initial time, implying that a single input of a biogenic hydrocarbon to an airmass can alter its ozone chemistry over a time scale on the order of a week.

  12. 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.

  13. 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

  14. Challenge for real-time and real-space resolved spectroscopy of surface chemical reactions. Aiming at trace of irreversible and inhomogeneous reactions

    International Nuclear Information System (INIS)

    A novel experimental technique, time-resolved wavelength-dispersive soft X-ray imaging spectroscopy, is proposed in order to achieve real-time and real-space resolved spectroscopy for the observation of irreversible and inhomogeneous surface chemical reactions. By combining the wavelength-dispersed soft X rays, in which the X-ray wavelength (photon energy) changes as a function of position on the sample, with the photoelectron emission microscope, the soft X-ray absorption spectra are separately obtained at different positions on the sample without scanning the X-ray monochromator. Therefore, the real-time resolved measurement of site-selective soft X-ray absorption spectroscopy is realized in one event without repeating the chemical reaction. It is expected that the spatial distribution of different chemical species is traced during the surface chemical reaction, which is essential to understand the reaction mechanism. (author)

  15. Numerical simulation of the interaction of transport, diffusion and chemical reactions in an urban plume

    Science.gov (United States)

    Vogel, Bernhard; Vogel, Heike; Fiedler, Franz

    1994-01-01

    A model system is presented that takes into account the main physical and chemical processes on the regional scale here in an area of 100x100 sq km. The horizontal gridsize used is 2x2 sq km. For a case study, it is demonstrated how the model system can be used to separate the contributions of the processes advection, turbulent diffusion, and chemical reactions to the diurnal cycle of ozone. In this way, typical features which are visible in observations and are reproduced by the numerical simulations can be interpreted.

  16. Self-propelled motion of a fluid droplet under chemical reaction

    CERN Document Server

    Yabunaka, Shunsuke; Yoshinaga, Natsuhiko

    2012-01-01

    We study self-propelled dynamics of a droplet due to a Marangoni effect and chemical reactions in a binary fluid with a dilute third component of chemical product which affects the interfacial energy of a droplet. The equation for the migration velocity of the center of mass of a droplet is derived in the limit of an infinitesimally thin inter- face. We found that there is a bifurcation from a motionless state to a propagating state of droplet by changing the strength of the Marangoni effect.

  17. 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.

  18. 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.

  19. Acid-functionalized polyolefin materials and their use in acid-promoted chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Oyola, Yatsandra; Tian, Chengcheng; Bauer, John Christopher; Dai, Sheng

    2016-06-07

    An acid-functionalized polyolefin material that can be used as an acid catalyst in a wide range of acid-promoted chemical reactions, wherein the acid-functionalized polyolefin material includes a polyolefin backbone on which acid groups are appended. Also described is a method for the preparation of the acid catalyst in which a precursor polyolefin is subjected to ionizing radiation (e.g., electron beam irradiation) of sufficient power and the irradiated precursor polyolefin reacted with at least one vinyl monomer having an acid group thereon. Further described is a method for conducting an acid-promoted chemical reaction, wherein an acid-reactive organic precursor is contacted in liquid form with a solid heterogeneous acid catalyst comprising a polyolefin backbone of at least 1 micron in one dimension and having carboxylic acid groups and either sulfonic acid or phosphoric acid groups appended thereto.

  20. The study of thermodynamic properties and transport properties of multicomponent systems with chemical reactions

    Directory of Open Access Journals (Sweden)

    Samujlov E.

    2013-04-01

    Full Text Available In case of system with chemical reaction the most important properties are heat conductivity and heat capacity. In this work we have considered the equation for estimate the component of these properties caused by chemical reaction and ionization processes. We have evaluated the contribution of this part in heat conductivity and heat capacity too. At the high temperatures contribution in heat conductivity from ionization begins to play an important role. We have created a model, which describe partial and full ionization of gases and gas mixtures. In addition, in this work we present the comparison of our result with experimental data and data from numerical simulation. We was used the data about transport properties of middle composition of Russian coals and the data of thermophysical properties of natural gas for comparison.

  1. Graphene-Semiconductor Catalytic Nanodiodes for Quantitative Detection of Hot Electrons Induced by a Chemical Reaction.

    Science.gov (United States)

    Lee, Hyosun; Nedrygailov, Ievgen I; Lee, Young Keun; Lee, Changhwan; Choi, Hongkyw; Choi, Jin Sik; Choi, Choon-Gi; Park, Jeong Young

    2016-03-01

    Direct detection of hot electrons generated by exothermic surface reactions on nanocatalysts is an effective strategy to obtain insight into electronic excitation during chemical reactions. For this purpose, we fabricated a novel catalytic nanodiode based on a Schottky junction between a single layer of graphene and an n-type TiO2 layer that enables the detection of hot electron flows produced by hydrogen oxidation on Pt nanoparticles. By making a comparative analysis of data obtained from measuring the hot electron current (chemicurrent) and turnover frequency, we demonstrate that graphene's unique electronic structure and extraordinary material properties, including its atomically thin nature and ballistic electron transport, allow improved conductivity at the interface between the catalytic Pt nanoparticles and the support. Thereby, graphene-based nanodiodes offer an effective and facile way to approach the study of chemical energy conversion mechanisms in composite catalysts with carbon-based supports. PMID:26910271

  2. Metal-Catalyzed Chemical Reaction of Single Molecules Directly Probed by Vibrational Spectroscopy.

    Science.gov (United States)

    Choi, Han-Kyu; Park, Won-Hwa; Park, Chan-Gyu; Shin, Hyun-Hang; Lee, Kang Sup; Kim, Zee Hwan

    2016-04-01

    The study of heterogeneous catalytic reactions remains a major challenge because it involves a complex network of reaction steps with various intermediates. If the vibrational spectra of individual molecules could be monitored in real time, one could characterize the structures of the intermediates and the time scales of reaction steps without ensemble averaging. Surface-enhanced Raman scattering (SERS) spectroscopy does provide vibrational spectra with single-molecule sensitivity, but typical single-molecule SERS signals exhibit spatial heterogeneities and temporal fluctuations, making them difficult to be used in single-molecule kinetics studies. Here we show that SERS can monitor the single-molecule catalytic reactions in real time. The surface-immobilized reactants placed at the junctions of well-defined nanoparticle-thin film structures produce time-resolved SERS spectra with discrete, step-transitions of photoproducts. We interpret that such SERS-steps correspond to the reaction events of individual molecules occurring at the SERS hotspot. The analyses of the yield, dynamics, and the magnitude of such SERS steps, along with the associated spectral characteristics, fully support our claim. In addition, a model that is based on plasmonic field enhancement and surface photochemistry reproduces the key features of experimental observation. Overall, the result demonstrates that it is possible, under well-controlled conditions, to differentiate the chemical and physical processes contributing to the single-molecule SERS signals, and thus shows the use of single-molecule SERS as a tool for studying the metal-catalyzed organic reactions. PMID:26964567

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

    OpenAIRE

    Srinivasacharya D.; Mendu Upendar

    2014-01-01

    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 sol...

  5. Faradiac Impedance of a Heterogeneous Chemical Reaction and an Adsorption Process

    OpenAIRE

    Qudah MMA

    2015-01-01

    The electrochemical behaviour of stainless steel 302 has been investigated in 0.10 M K2SO4 solution using the impedance technique at several anodic potentials. Stainless steel 302 is passive up to 1300 mV, due to the main formation of Cr2O3. Above this potential stainless steel became active. Faradiac impedances of a heterogeneous chemical reaction and an adsorption process were discussed.

  6. Ultrafast electron diffraction and direct observation of transient structures in a chemical reaction

    OpenAIRE

    Cao, Jianming; Ihee, Hyotcherl; Zewail, Ahmed H.

    1999-01-01

    Ultrafast electron diffraction is a unique method for the studies of structural changes of complex molecular systems. In this contribution, we report direct ultrafast electron diffraction study of the evolution of short-lived intermediates in the course of a chemical change. Specifically, we observe the transient intermediate in the elimination reaction of 1,2-diiodotetrafluoroethane (C2F4I2) to produce the corresponding ethylene derivative by the breakage of two carbon-iodine, C---I, bonds. ...

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

    OpenAIRE

    2009-01-01

    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 ...

  8. Automated Discovery of Elementary Chemical Reaction Steps Using Freezing String and Berny Optimization Methods

    OpenAIRE

    Suleimanov, Yury V.; Green, William H.

    2015-01-01

    We present a simple protocol which allows fully automated discovery of elementary chemical reaction steps using in cooperation single- and double-ended transition-state optimization algorithms - the freezing string and Berny optimization methods, respectively. To demonstrate the utility of the proposed approach, the reactivity of several systems of combustion and atmospheric chemistry importance is investigated. The proposed algorithm allowed us to detect without any human intervention not on...

  9. Magnetohydrodynamic (MHD) stretched flow of nanofluid with power-law velocity and chemical reaction

    OpenAIRE

    Tasawar Hayat; Madiha Rashid; Maria Imtiaz; Ahmed Alsaedi

    2015-01-01

    This paper deals with the boundary layer flow of nanofluid over power-law stretched surface. Analysis has been carried out in the presence of applied magnetic field and chemical reaction. Heat and mass transfer characteristics are studied using heat and mass convective conditions. The governing partial differential equations are transferred to the nonlinear ordinary differential equations. Convergent series solutions are obtained for fluid velocity, temperature and concentrations fields. Infl...

  10. On the graph and systems analysis of reversible chemical reaction networks with mass action kinetics

    OpenAIRE

    Rao, Shodhan; Jayawardhana, Bayu; der Schaft, Arjan van

    2012-01-01

    Motivated by the recent progresses on the interplay between the graph theory and systems theory, we revisit the analysis of reversible chemical reaction networks described by mass action kinetics by reformulating it using the graph knowledge of the underlying networks. Based on this formulation, we can characterize the space of equilibrium points and provide simple dynamical analysis on the state space modulo the space of equilibrium points.

  11. 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…

  12. 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…

  13. Drop-by-drop chemical reaction and sample introduction for capillary electrophoresis.

    Science.gov (United States)

    Chen, Fengming; Rang, Ying; Weng, Ying; Lin, Luyao; Zeng, Hulie; Nakajim, Hizuru; Lin, Jin-Ming; Uchiyama, Katsumi

    2015-06-21

    In this paper, we report a novel sample introduction and chemical reaction strategy by drop-by-drop inkjet injection for an electrophoretically mediated microanalysis (EMMA). This method makes it possible to achieve an on-line introduction of reactant solutions by alternately ejecting small plugs, with an overlapping region of the plugs for mixing the reactants by electrophoresis, supporting chemical reactions, followed by electrophoretic separation of the final compounds. As a proof-of-concept of the method, the EMMA of an inkjetted mixture of 4-fluoro-7-nitrobenzofurazan (NBD-F) and amino acids was carried out as a model chemical reaction. The product NBD-amino acids were quantified by detection with laser induced fluorescence. The optimal conditions for the procedure were: inkjet driving voltage: +40-44 V; pulse width: 20-24 μs; drop-by-drop injection of reactant solutions: alternately 2 drops × 25 times for the amino acid solution and the NBD-F solution; zone overlapping voltage and time: 3 kV and 2 s; incubation time after overlapping: 5 min; separation voltage: 18 kV. Under the optimized conditions, a significant enhancement in sensitivity and a sensitive quantitative analysis were realized. The results obtained were comparable with those using the off-line labeling method. This method is rapid, cost-effective, and readily automated for EMMA. PMID:25728632

  14. Production of cold formaldehyde molecules for study and control of chemical reaction dynamics with hydroxyl radicals

    CERN Document Server

    Hudson, E R; Sawyer, B C; Taatjes, C A; Lewandowski, H J; Bochinski, J R; Bohn, J L; Ye, J; Hudson, Eric R.; Ticknor, Christopher; Sawyer, Brian C.; Taatjes, Craig A.; Bohn, John L.; Ye, Jun

    2005-01-01

    We propose a method for controlling a class of low temperature chemical reactions. Specifically, we show the hydrogen abstraction channel in the reaction of formaldehyde (H$_{2}$CO) and the hydroxyl radical (OH) can be controlled through either the molecular state or an external electric field. We also outline experiments for investigating and demonstrating control over this important reaction. To this end, we report the first Stark deceleration of the H$_{2}$CO molecule. We have decelerated a molecular beam of H$_{2}$CO essentially to rest, producing cold molecule packets at a temperature of 100 mK with a few million molecules in the packet at a density of $\\sim10^{6}$ cm$^{-3}$.

  15. Nobel Prize 1992: Rudolph A. Marcus: theory of electron transfer reactions in chemical systems

    International Nuclear Information System (INIS)

    A review of the theory developed by Rudolph A. Marcus is presented, who for his rating to the theory of electron transfer in chemical systems was awarded the Nobel Prize in Chemistry in 1992. Marcus theory has constituted not only a good extension of the use of a spectroscopic principle, but also has provided an energy balance and the application of energy conservation for electron transfer reactions. A better understanding of the reaction coordinate is exposed in terms energetic and establishing the principles that govern the transfer of electrons, protons and some labile small molecular groups as studied at present. Also, the postulates and equations described have established predictive models of reaction time, very useful for industrial environments, biological, metabolic, and others that involve redox processes. Marcus theory itself has also constituted a large contribution to the theory of complex transition

  16. FEARCF a multidimensional free energy method for investigating conformational landscapes and chemical reaction mechanisms

    Institute of Scientific and Technical Information of China (English)

    NAIDOO Kevin J.

    2012-01-01

    The development and implementation of a computational method able to produce free energies in multiple dimensions,descriptively named the free energies from adaptive reaction coordinate forces (FEARCF) method is described in this paper.While the method can be used to calculate free energies of association,conformation and reactivity here it is shown in the context of chemical reaction landscapes.A reaction free energy surface for the Claisen rearrangement of chorismate to prephenate is used as an illustration of the method's efficient convergence.FEARCF simulations are shown to achieve fiat histograms for complex multidimensional free energy volumes.The sampling efficiency by which it produces multidimensional free energies is demonstrated on the complex puckering of a pyranose ring,that is described by a three dimensional W(θ1,θ2,θ3) potential of mean force.

  17. Chemically Accurate Simulation of a Polyatomic Molecule-Metal Surface Reaction.

    Science.gov (United States)

    Nattino, Francesco; Migliorini, Davide; Kroes, Geert-Jan; Dombrowski, Eric; High, Eric A; Killelea, Daniel R; Utz, Arthur L

    2016-07-01

    Although important to heterogeneous catalysis, the ability to accurately model reactions of polyatomic molecules with metal surfaces has not kept pace with developments in gas phase dynamics. Partnering the specific reaction parameter (SRP) approach to density functional theory with ab initio molecular dynamics (AIMD) extends our ability to model reactions with metals with quantitative accuracy from only the lightest reactant, H2, to essentially all molecules. This is demonstrated with AIMD calculations on CHD3 + Ni(111) in which the SRP functional is fitted to supersonic beam experiments, and validated by showing that AIMD with the resulting functional reproduces initial-state selected sticking measurements with chemical accuracy (4.2 kJ/mol ≈ 1 kcal/mol). The need for only semilocal exchange makes our scheme computationally tractable for dissociation on transition metals. PMID:27284787

  18. Chemically Accurate Simulation of a Polyatomic Molecule-Metal Surface Reaction

    Science.gov (United States)

    2016-01-01

    Although important to heterogeneous catalysis, the ability to accurately model reactions of polyatomic molecules with metal surfaces has not kept pace with developments in gas phase dynamics. Partnering the specific reaction parameter (SRP) approach to density functional theory with ab initio molecular dynamics (AIMD) extends our ability to model reactions with metals with quantitative accuracy from only the lightest reactant, H2, to essentially all molecules. This is demonstrated with AIMD calculations on CHD3 + Ni(111) in which the SRP functional is fitted to supersonic beam experiments, and validated by showing that AIMD with the resulting functional reproduces initial-state selected sticking measurements with chemical accuracy (4.2 kJ/mol ≈ 1 kcal/mol). The need for only semilocal exchange makes our scheme computationally tractable for dissociation on transition metals. PMID:27284787

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

    International Nuclear Information System (INIS)

    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−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

  20. 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. PMID:22512717

  1. Nuclear quantum effects in chemical reactions via higher-order path-integral calculations

    International Nuclear Information System (INIS)

    Highlights: • The study presents path-integral calculations for chemical reactions. • The path-integrals use higher-order factorizations of the density matrix. • The Eckart potential and the H2 + H reaction are used as test cases for the methods. • The Chin higher order factorization enhances QM transmission convergence. • The higher order factorizations enhance eigenvalue and partition function convergence. - Abstract: A practical approach to treat nuclear quantum mechanical effects in simulations of condensed phases, such as enzymes, is via Feynman path integral (PI) formulations. Typically, the standard primitive approximation (PA) is employed in enzymatic PI simulations. Nonetheless, these PI simulations are computationally demanding due to the large number of beads required to obtain converged results. The efficiency of PI simulations may be greatly improved if higher-order factorizations of the density matrix operator are employed. Herein, we compare the results of model calculations obtained employing the standard PA, the improved operator of Takahashi and Imada (TI), and a gradient-based forward corrector algorithm due to Chin (CH). The quantum transmission coefficient is computed for the Eckart potential while the partition functions and rate constant are computed for the H2 + H hydrogen transfer reaction. These potentials are simple models for chemical reactions. The study of the different factorization methods reveals that in most cases the higher-order action converges faster than the PA and TI approaches, at a moderate computational cost

  2. TREATABILITY STUDIES USED TO TEST FOR EXOTHERMIC REACTIONS OF PLUTONIUM DECONTAMINATION CHEMICALS

    International Nuclear Information System (INIS)

    Fluor Hanford is decommissioning the Plutonium Finishing Plant (PFP) at the Hanford site in Eastern Washington. Aggressive chemicals are commonly used to remove transuranic contaminants from process equipment to allow disposal as low level waste. Chemicals being considered for decontamination of gloveboxes in PFP include cerium(IV) nitrate in a nitric acid solution, and proprietary commercial solutions that include acids, degreasers, and sequestering agents. Fluor's decontamination procedure involves application of chemical solutions as a spray on the contaminated surfaces, followed by a wipe-down with rags. This process effectively transfers the transuranic materials to the decontamination liquids, which are then absorbed by rags and packaged for disposal as TRU waste. Concerns regarding the safety of this procedure developed following a fire at Rocky Flats in 2003. The fire occurred in a glovebox that had been treated with cerium nitrate, which is one of the decontamination chemicals that Fluor Hanford has proposed to use. The investigation of the event was hampered by the copious use of chemicals and water to extinguish the fire, and was not conclusive regarding the cause. However, the reviewers noted that rags were found in the glovebox, suggesting that the combination of rags and chemicals may have contributed to the fire. With that uncertainty, Fluor began an investigation into the potential for fire when using the chemicals and materials in the decontamination process. The focus of this work has been to develop a disposal strategy that will provide a chemically stable waste form at expected Hanford waste storage temperatures. Treatability tests under CERCLA were used to assess the use of certain chemicals and wipes during the decontamination process. Chemicals being considered for decontamination of gloveboxes at PFP include cerium (IV) nitrate in a nitric acid solution, and proprietary commercial solutions as RadPro(trademark) that include acids, degreasers

  3. 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.

  4. Laser induced and controlled chemical reaction of carbon monoxide and hydrogen

    Science.gov (United States)

    du Plessis, Anton; Strydom, Christien A.; Uys, Hermann; Botha, Lourens R.

    2011-11-01

    Bimolecular chemical reaction control of gaseous CO and H2 at room temperature and atmospheric pressure, without any catalyst, using shaped femtosecond laser pulses is presented. High intensity laser radiation applied to a reaction cell facilitates non-resonant bond breakage and the formation of a range of ions, which can then react to form new products. Stable reaction products are measured after irradiation of a reaction cell, using time of flight mass spectroscopy. Bond formation of C-O, C-C, and C-H bonds is demonstrated as CO2+, C2H2+, CH+, and CH3+ were observed in the time of flight mass spectrum of the product gas, analyzed after irradiation. The formation of CO2 is shown to be dependent on laser intensity, irradiation time, and on the presence of H2 in the reaction cell. Using negatively chirped laser pulses more C-O bond formation takes place as compared to more C-C bond formation for unchirped pulses.

  5. Surftherm: A program to analyze thermochemical and kinetic data in gas-phase and surface chemical reaction mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Coltrin, M.E.; Moffat, H.K.

    1994-06-01

    This report documents the Surftherm program that analyzes transport coefficient, thermochemical- and kinetic rate information in complex gas-phase and surface chemical reaction mechanisms. The program is designed for use with the Chemkin (gas-phase chemistry) and Surface Chemkin (heterogeneous chemistry) programs. It was developed as a ``chemist`s companion`` in using the Chemkin packages with complex chemical reaction mechanisms. It presents in tabular form detailed information about the temperature and pressure dependence of chemical reaction rate constants and their reverse rate constants, reaction equilibrium constants, reaction thermochemistry, chemical species thermochemistry and transport properties. This report serves as a user`s manual for use of the program, explaining the required input and the output.

  6. A coupled mechanical and chemical damage model for concrete affected by alkali–silica reaction

    International Nuclear Information System (INIS)

    To model the complex degradation phenomena occurring in concrete affected by alkali–silica reaction (ASR), we formulate a poro-mechanical model with two isotropic internal variables: the chemical and the mechanical damage. The chemical damage, related to the evolution of the reaction, is caused by the pressure generated by the expanding ASR gel on the solid concrete skeleton. The mechanical damage describes the strength and stiffness degradation induced by the external loads. As suggested by experimental results, degradation due to ASR is considered to be localized around reactive sites. The effect of the degree of saturation and of the temperature on the reaction development is also modeled. The chemical damage evolution is calibrated using the value of the gel pressure estimated by applying the electrical diffuse double-layer theory to experimental values of the surface charge density in ASR gel specimens reported in the literature. The chemo-damage model is first validated by simulating expansion tests on reactive specimens and beams; the coupled chemo-mechanical damage model is then employed to simulate compression and flexure tests results also taken from the literature. -- Highlights: •Concrete degradation due to ASR in variable environmental conditions is modeled. •Two isotropic internal variables – chemical and mechanical damage – are introduced. •The value of the swelling pressure is estimated by the diffuse double layer theory. •A simplified scheme is proposed to relate macro- and microscopic properties. •The chemo-mechanical damage model is validated by simulating tests in literature

  7. 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

  8. 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.

  9. 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. PMID:16866359

  10. 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.

  11. Chemical Reaction Effects on MHD Flow Past an Impulsively Started Isothermal Vertical Plate with Uniform Mass Diffusion

    Directory of Open Access Journals (Sweden)

    Chandrakala P.

    2014-05-01

    Full Text Available A numerical technique is employed to derive a solution to the transient natural convection flow of an incompressible viscous fluid past an impulsively started infinite isothermal vertical plate with uniform mass diffusion in the presence of a magnetic field and homogeneous chemical reaction of first order. The governing equations are solved using implicit finite-difference method. The effects of velocity, temperature and concentration for different parameters such as the magnetic field parameter, chemical reaction parameter, Prandtl number, Schmidt number, thermal Grashof number and mass Grashof number are studied. It is observed that the fluid velocity decreases with increasing the chemical reaction parameter and the magnetic field parameter.

  12. 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.

  13. 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.

  14. Two-scale large deviations for chemical reaction kinetics through second quantization path integral

    International Nuclear Information System (INIS)

    Motivated by the study of rare events for a typical genetic switching model in systems biology, in this paper we aim to establish the general two-scale large deviations for chemical reaction systems. We build a formal approach to explicitly obtain the large deviation rate functionals for the considered two-scale processes based upon the second quantization path integral technique. We get three important types of large deviation results when the underlying two timescales are in three different regimes. This is realized by singular perturbation analysis to the rate functionals obtained by the path integral. We find that the three regimes possess the same deterministic mean-field limit but completely different chemical Langevin approximations. The obtained results are natural extensions of the classical large volume limit for chemical reactions. We also discuss its implication on the single-molecule Michaelis–Menten kinetics. Our framework and results can be applied to understand general multi-scale systems including diffusion processes. (paper)

  15. On the use of chemical reaction rates with discrete internal energies in the direct simulation Monte Carlo method

    Science.gov (United States)

    Gimelshein, S. F.; Gimelshein, N. E.; Levin, D. A.; Ivanov, M. S.; Wysong, I. J.

    2004-07-01

    The conventional chemical reaction models of the direct simulation Monte Carlo method developed with the assumption of continuous rotational or vibrational modes that are shown to exhibit systematic errors when used with discrete energy modes. A reaction model is proposed that is consistent with the use of discrete energy distributions of rotational and vibrational modes, and is equally applicable to diatomic and polyatomic systems. The sensitivity of the model to variations of different reaction rate parameters is examined. The revised chemical reaction model is then applied to the modeling of hypersonic flows over spacecraft in the Martian and Earth atmospheres.

  16. 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

  17. Collisions of polyatomic ions with surfaces: incident energy partitioning and chemical reactions

    International Nuclear Information System (INIS)

    Collision of polyatomic ions with surfaces were investigated in ion-surface scattering experiments to obtain more information on energy partitioning in ion-surface collision and on chemical reactions at surfaces. Mass spectra, translation energy and angular distributions of product ions were measured in dependence on the incident energy and the incident angle of polyatomic projectiles. From these data distributions of energy fractions resulting in internal excitation of the projectile, translation energy of the product ions, and energy absorbed by the surface were determined. The surface investigated were a standard stainless steel surface, covered by hydrocarbons, carbon surfaces at room and elevated temperatures, and several surfaces covered by a self-assembled monolayers (C12-hydrocarbon SAM, C11-perfluorohydrocarbon SAM, and C11 hydrocarbon with terminal -COOH group SAM). The main processes observed at collision energies of 10 - 50 eV were: neutralization of the ions at surfaces, inelastic scattering and dissociations of the projectile ions, quasi elastic scattering of the projectile ions, and chemical reactions with the surface material (usually hydrogen-atom transfer reactions). The ion survival factor was estimated to be a few percent for even-electron ions (like protonated ethanol ion, C2H5O+, CD5+) and about 10 - 102 times lower for radical ions (like ethanol and benzene molecular ions, CD4+). In the polyatomic ion -surface energy transfer experiments, the ethanol molecular ion was used as a well-characterized projectile ion. The results with most of the surfaces studied showed in the collision energy range of 13 - 32 eV that most collisions were strongly inelastic with about 6 - 8 % of the incident projectile energy transformed into internal excitation of the projectile (independent of the incident angle) and led partially to its further dissociation in a unimolecular way after the interaction with the surface. The incident energy transformed into the

  18. Rate constants of chemical reactions from semiclassical transition state theory in full and one dimension

    Science.gov (United States)

    Greene, Samuel M.; Shan, Xiao; Clary, David C.

    2016-06-01

    Semiclassical Transition State Theory (SCTST), a method for calculating rate constants of chemical reactions, offers gains in computational efficiency relative to more accurate quantum scattering methods. In full-dimensional (FD) SCTST, reaction probabilities are calculated from third and fourth potential derivatives along all vibrational degrees of freedom. However, the computational cost of FD SCTST scales unfavorably with system size, which prohibits its application to larger systems. In this study, the accuracy and efficiency of 1-D SCTST, in which only third and fourth derivatives along the reaction mode are used, are investigated in comparison to those of FD SCTST. Potential derivatives are obtained from numerical ab initio Hessian matrix calculations at the MP2/cc-pVTZ level of theory, and Richardson extrapolation is applied to improve the accuracy of these derivatives. Reaction barriers are calculated at the CCSD(T)/cc-pVTZ level. Results from FD SCTST agree with results from previous theoretical and experimental studies when Richardson extrapolation is applied. Results from our implementation of 1-D SCTST, which uses only 4 single-point MP2/cc-pVTZ energy calculations in addition to those for conventional TST, agree with FD results to within a factor of 5 at 250 K. This degree of agreement and the efficiency of the 1-D method suggest its potential as a means of approximating rate constants for systems too large for existing quantum scattering methods.

  19. Rate constants of chemical reactions from semiclassical transition state theory in full and one dimension.

    Science.gov (United States)

    Greene, Samuel M; Shan, Xiao; Clary, David C

    2016-06-28

    Semiclassical Transition State Theory (SCTST), a method for calculating rate constants of chemical reactions, offers gains in computational efficiency relative to more accurate quantum scattering methods. In full-dimensional (FD) SCTST, reaction probabilities are calculated from third and fourth potential derivatives along all vibrational degrees of freedom. However, the computational cost of FD SCTST scales unfavorably with system size, which prohibits its application to larger systems. In this study, the accuracy and efficiency of 1-D SCTST, in which only third and fourth derivatives along the reaction mode are used, are investigated in comparison to those of FD SCTST. Potential derivatives are obtained from numerical ab initio Hessian matrix calculations at the MP2/cc-pVTZ level of theory, and Richardson extrapolation is applied to improve the accuracy of these derivatives. Reaction barriers are calculated at the CCSD(T)/cc-pVTZ level. Results from FD SCTST agree with results from previous theoretical and experimental studies when Richardson extrapolation is applied. Results from our implementation of 1-D SCTST, which uses only 4 single-point MP2/cc-pVTZ energy calculations in addition to those for conventional TST, agree with FD results to within a factor of 5 at 250 K. This degree of agreement and the efficiency of the 1-D method suggest its potential as a means of approximating rate constants for systems too large for existing quantum scattering methods. PMID:27369506

  20. Chemical reactions induced by oscillating external fields in weak thermal environments

    CERN Document Server

    Craven, Galen T; Hernandez, Rigoberto

    2015-01-01

    Chemical reaction rates must increasingly be determined in systems that evolve under the control of external stimuli. In these systems, when a reactant population is induced to cross an energy barrier through forcing from a temporally varying external field, the transition state that the reaction must pass through during the transformation from reactant to product is no longer a fixed geometric structure, but is instead time-dependent. For a periodically forced model reaction, we develop a recrossing-free dividing surface that is attached to a transition state trajectory [T. Bartsch, R. Hernandez, and T. Uzer, Phys. Rev. Lett. 95, 058301 (2005)]. We have previously shown that for single-mode sinusoidal driving, the stability of the time-varying transition state directly determines the reaction rate [G. T. Craven, T. Bartsch, and R. Hernandez, J. Chem. Phys. 141, 041106 (2014)]. Here, we extend our previous work to the case of multi-mode driving waveforms. Excellent agreement is observed between the rates pred...

  1. Simple Chemical Solution Deposition of Co₃O₄ Thin Film Electrocatalyst for Oxygen Evolution Reaction.

    Science.gov (United States)

    Jeon, Hyo Sang; Jee, Michael Shincheon; Kim, Haeri; Ahn, Su Jin; Hwang, Yun Jeong; Min, Byoung Koun

    2015-11-11

    Oxygen evolution reaction (OER) is the key reaction in electrochemical processes, such as water splitting, metal-air batteries, and solar fuel production. Herein, we developed a facile chemical solution deposition method to prepare a highly active Co3O4 thin film electrode for OER, showing a low overpotential of 377 mV at 10 mA/cm(2) with good stability. An optimal loading of ethyl cellulose additive in a precursor solution was found to be essential for the morphology control and thus its electrocatalytic activity. Our results also show that the distribution of Co3O4 nanoparticle catalysts on the substrate is crucial in enhancing the inherent OER catalytic performance. PMID:26489005

  2. Coupling sample paths to the partial thermodynamic limit in stochastic chemical reaction networks

    CERN Document Server

    Levien, Ethan

    2016-01-01

    We present a new technique for reducing the variance in Monte Carlo estimators of stochastic chemical reaction networks. Our method makes use of the fact that many stochastic reaction networks converge to piecewise deterministic Markov processes in the large system-size limit. The statistics of the piecewise deterministic process can be obtained much more efficiently than those of the exact process. By coupling sample paths of the exact model to the piecewise deterministic process we are able to reduce the variance, and hence the computational complexity of the Monte Carlo estimator. In addition to rigorous results concerning the asymptotic behavior of our method, numerical simulations are performed on some simple biological models suggesting that significant computational gains are made for even moderate system-sizes.

  3. Regularities of development of unspecific reaction of cells, and modification of chemical protection

    International Nuclear Information System (INIS)

    Regularities of development of a unspecific reaction of cells under the effect of different substances belonging to weak electrolytes have been studied. It was demonstrated that the rate of the unspecific reaction development under the effect of cysteamine and caffeine-benzoate depends on the agent concentration, temperature and pH of a medium. It was established that the response of a cell is determined by the overall intracellular concentration of the agent rather than by its specific character. The total concentration of the substance inside the cell depends on its physico-chemical characteristics and, with a pH gradient between cell and medium, can markedly vary from that in the medium. With similar intracellular content, both substances proved to be virtually equally effective. This suggests that it is possible to assess the effectiveness of some other biologically active substances many of which are weak electrolytes

  4. A "partitioned leaping" approach for multiscale modeling of chemical reaction dynamics

    CERN Document Server

    Harris, L A; Clancy, Paulette; Harris, Leonard A.

    2006-01-01

    We present a novel multiscale simulation approach for modeling stochasticity in chemical reaction networks. The approach seamlessly integrates exact-stochastic and "leaping" methodologies into a single *partitioned leaping* algorithmic framework. Distinguishing characteristics of the method include automatic, dynamic and theoretically justifiable time step determination and timescale separation procedures that utilize concepts underlying the tau-leap approach [D.T. Gillespie, J. Chem. Phys. 115, 1716 (2001); D.T. Gillespie and L.R. Petzold, J. Chem. Phys. 119, 8229 (2003)] and require the definition of only three model-independent parameters. Both procedures are based on an individual (but not independent) consideration of reactions, a subtle yet significant ideological concept used in the development of previous exact-stochastic simulation methods [D.T. Gillespie, J. Comput. Phys. 22, 403 (1976); M.A. Gibson and J. Bruck, J. Phys. Chem. A 104, 1876 (2000)]. The result is a method that correctly accounts for ...

  5. Single-collision studies of hot atom energy transfer and chemical reaction

    International Nuclear Information System (INIS)

    This report discusses research in the collision dynamics of translationally hot atoms, with funding with DOE for the project ''Single-Collision Studies of Hot Atom Energy Transfer and Chemical Reaction,'' Grant Number DE-FG03-85ER13453. The work reported here was done during the period September 9, 1988 through October 31, 1991. During this period this DOE-funded work has been focused on several different efforts: (1) experimental studies of the state-to-state dynamics of the H + RH → H2 R reactions where RH is CH4, C2H6, or C3H8, (2) theoretical (quasiclassical trajectory) studies of hot hydrogen atom collision dynamics, (3) the development of photochemical sources of translationally hot molecular free radicals and characterization of the high resolution CARS spectroscopy of molecular free radicals, (4) the implementation of stimulated Raman excitation (SRE) techniques for the preparation of vibrationally state-selected molecular reactants

  6. Radiation, Chemical reaction, Double dispersion effects on Heat and mass transfer in Non-Newtonian fluids

    Directory of Open Access Journals (Sweden)

    Dr. A.S.N. Murti

    2010-03-01

    Full Text Available Radiation and chemical reaction effects on heat and mass transfer in non-Darcynon-Newtonian fluid over a vertical surface is considered. In this article we havemaintained the constant temperature. A mathematical model is developed takinginto the account the new elements introduced. Numerical solutions for thegoverning nonlinear momemtum, energy and concentration are obtained.Thegoverning boundary layer equations and boundary conditions are simplified byusing similarity transformations. The governing equations are solved numericallyby means of Fourth-order Runge-Kutta method coupled with double-shootingtechnique. The influence of viscosity index n , thermal and solute dispersion,velocity, temperature, concentration, Heat and mass transfer rates arediscussed.

  7. Processing of Biomorphic Porous Ceramics by Chemical Vapor Infiltration and Reaction Technique (CVI-R)

    OpenAIRE

    Ghanem, Hanadi

    2008-01-01

    Biomorphic ceramics are a new class of materials derived from natural biopolymers that can be fabricated by different ceramization routes in order to produce carbides, nitrides and oxides, depending on the processing conditions. A wide variety of non-oxide ceramics such as SiC, Si3N4 and SiC-Si3N4 in addition to oxide-based ceramics like TiO2 have been produced in this study from carbonized paper preforms using Chemical Vapor Infiltration and Reaction (CVI-R) technique. For production of non-...

  8. Etching rate control by MeV O+ implantation for laser-chemical reaction of ferrite

    International Nuclear Information System (INIS)

    The control of etching rate in laser-induced chemical reaction of Mn-Zn ferrite in H3PO4 solution by MeV O+ implantation has been investigated. The etching induced by Ar+-ion laser irradiation in a H3PO4 solution was suppressed by implantating 3 MeV O+ to a dose of 1 x 1017 cm-2 when the laser power was low. The etching suppression disappeared when the O+-implanted sample was thermally annealed at 850degC for 30 min. The suppression is found to be related to the crystallinity change induced by ion implantation instead of surface reflectivity change. (author)

  9. Uses and abuses of the Langevin equation for chemical reactions in condensed phases

    International Nuclear Information System (INIS)

    The Langevin and Fokker-Planck equations are useful in the description of many classical and quantum mechanical systems. However, these equations are justifiable from molecular considerations under very restricted conditions. These conditions include weak coupling. Brownian motion, and systems with special Hamiltonians. The application of these equations to chemical reactions in condensed phases is fraught with peril, particularly for fluid systems. The authors examine the molecular derivations of these equations and describe the conditions under which they are justifiable. It is, of course, possible that the equations are useful under other conditions

  10. Introduction to dynamic spin chemistry magnetic field effects on chemical and biochemical reactions

    CERN Document Server

    Hayashi, Hisaharu

    2004-01-01

    This book presents a detailed account of one of the most mysterious problems in science - whether ordinary magnetic fields can exert an appreciable influence on chemical and biochemical reactions. The first aim of the book is to introduce this research, through theoretical and dynamic spin chemistry, to graduate students and researchers, by means of detailed theoretical and experimental descriptions. The second aim is to review typical recent investigations, which will stimulate new interest and applications in the 21st century. Because dynamic spin chemistry is based on established science, i

  11. A ``partitioned leaping'' approach for multiscale modeling of chemical reaction dynamics

    Science.gov (United States)

    Harris, Leonard A.; Clancy, Paulette

    2006-10-01

    We present a novel multiscale simulation approach for modeling stochasticity in chemical reaction networks. The approach seamlessly integrates exact-stochastic and "leaping" methodologies into a single partitioned leaping algorithmic framework. The technique correctly accounts for stochastic noise at significantly reduced computational cost, requires the definition of only three model-independent parameters, and is particularly well suited for simulating systems containing widely disparate species populations. We present the theoretical foundations of partitioned leaping, discuss various options for its practical implementation, and demonstrate the utility of the method via illustrative examples.

  12. Radiation and chemical reaction effects on MHD flow along a moving vertical porous plate

    Science.gov (United States)

    Ramana Reddy, G. V.; Bhaskar Reddy, N.; Gorla, R. S. R.

    2016-02-01

    This paper presents an analysis of the effects of magnetohydrodynamic force and buoyancy on convective heat and mass transfer flow past a moving vertical porous plate in the presence of thermal radiation and chemical reaction. The governing partial differential equations are reduced to a system of self-similar equations using the similarity transformations. The resultant equations are then solved numerically using the fourth order Runge-Kutta method along with the shooting technique. The results are obtained for the velocity, temperature, concentration, skin-friction, Nusselt number and Sherwood number. The effects of various parameters on flow variables are illustrated graphically, and the physical aspects of the problem are discussed.

  13. On participation of unsolvated electron in chemical reactions in alcohol solutions

    International Nuclear Information System (INIS)

    The probabilities, I2, of positronium formation in ethyl alcohol to which effective solvated electron acceptors have been added, such as nitrobenzene, nitric and chloric acid, have been determined. Nitrobenzene and nitrate ions have a strongly reducing effect on I2, while the presence of chloric acid does not apparently affect the I2 value. The effect of additive concentration on the probability of positronium formation is correlative with that of the same factor on the radiation-and chemically stipulated chlorine atoms yield under γ-radiolysis of 0.4 M chlorobenzene solution in ethanol. This is indicative of the possible participation in the reactions of unsolvated electron

  14. 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.

  15. Chemical reaction path modeling of hydrothermal processes on Mars: Preliminary results

    Science.gov (United States)

    Plumlee, Geoffrey S.; Ridley, W. Ian

    1992-01-01

    Hydrothermal processes are thought to have had significant roles in the development of surficial mineralogies and morphological features on Mars. For example, a significant proportion of the Martian soil could consist of the erosional products of hydrothermally altered impact melt sheets. In this model, impact-driven, vapor-dominated hydrothermal systems hydrothermally altered the surrounding rocks and transported volatiles such as S and Cl to the surface. Further support for impact-driven hydrothermal alteration on Mars was provided by studies of the Ries crater, Germany, where suevite deposits were extensively altered to montmorillonite clays by inferred low-temperature (100-130 C) hydrothermal fluids. It was also suggested that surface outflow from both impact-driven and volcano-driven hydrothermal systems could generate the valley networks, thereby eliminating the need for an early warm wet climate. We use computer-driven chemical reaction path calculation to model chemical processes which were likely associated with postulated Martian hydrothermal systems.

  16. A Gas-Kinetic Scheme for Multimaterial Flows and Its Application in Chemical Reaction

    Science.gov (United States)

    Lian, Yongsheng; Xu, Kun

    1999-01-01

    This paper concerns the extension of the multicomponent gas-kinetic BGK-type scheme to multidimensional chemical reactive flow calculations. In the kinetic model, each component satisfies its individual gas-kinetic BGK equation and the equilibrium states of both components are coupled in space and time due to the momentum and energy exchange in the course of particle collisions. At the same time, according to the chemical reaction rule one component can be changed into another component with the release of energy, where the reactant and product could have different gamma. Many numerical test cases are included in this paper, which show the robustness and accuracy of kinetic approach in the description of multicomponent reactive flows.

  17. 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.

  18. A multi target approach to control chemical reactions in their inhomogeneous solvent environment

    Science.gov (United States)

    Keefer, Daniel; Thallmair, Sebastian; Zauleck, Julius P. P.; de Vivie-Riedle, Regina

    2015-12-01

    Shaped laser pulses offer a powerful tool to manipulate molecular quantum systems. Their application to chemical reactions in solution is a promising concept to redesign chemical synthesis. Along this road, theoretical developments to include the solvent surrounding are necessary. An appropriate theoretical treatment is helpful to understand the underlying mechanisms. In our approach we simulate the solvent by randomly selected snapshots from molecular dynamics trajectories. We use multi target optimal control theory to optimize pulses for the various arrangements of explicit solvent molecules simultaneously. This constitutes a major challenge for the control algorithm, as the solvent configurations introduce a large inhomogeneity to the potential surfaces. We investigate how the algorithm handles the new challenges and how well the controllability of the system is preserved with increasing complexity. Additionally, we introduce a way to statistically estimate the efficiency of the optimized laser pulses in the complete thermodynamical ensemble.

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

    International Nuclear Information System (INIS)

    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 298.150K and one atmosphere

  20. [Studies of chemical reactions in solid matrices]. Final report, December 1,, 1979-November 30, 1984

    International Nuclear Information System (INIS)

    This program, which has been supported for 35 years by the Atomic Energy Commission and its successor agencies, has produced significant advances in the understanding of the mechanisms of: (1) chemical activation by nuclear processes; (2) radiation chemistry; and (3) photochemistry. It has advanced knowledge of the reactions of electrons, hydrogen atoms and small free radicals, particularly in solids at cryogenic temperatures. It has applied radioisotopes as a tool in the solution of a number of chemical problems, has developed useful new techniques, and has contributed to the training of approximately 150 scientists at various levels. This final report includes a review of the evolution of areas of research emphasized, tabulations of the publications (chronologically and by research area) and Ph.D. theses resulting from the program, and tabulations of the research personnel (by academic category, by dates in the program and by subsequent employment)

  1. 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

  2. Chemical reaction rates and non-equilibrium pressure of reacting gas mixtures in the state-to-state approach

    International Nuclear Information System (INIS)

    Highlights: • State-to-state approach for coupled vibrational relaxation and chemical reactions. • Self-consistent model for rates of non-equilibrium reactions and energy transitions. • In viscous flows mass action law is violated. • Cross coupling between reaction rates and non-equilibrium pressure in viscous flow. • Results allow implementing the state-to-state approach for viscous flow simulations. - Abstract: Viscous gas flows with vibrational relaxation and chemical reactions in the state-to-state approach are analyzed. A modified Chapman–Enskog method is used for the determination of chemical reaction and vibrational transition rates and non-equilibrium pressure. Constitutive equations depend on the thermodynamic forces: velocity divergence and chemical reaction/transition affinity. As an application, N2 flow with vibrational relaxation across a shock wave is investigated. Two distinct processes occur behind the shock: for small values of the distance the affinity is large and vibrational relaxation is in its initial stage; for large distances the affinity is small and the chemical reaction is in its final stage. The affinity contributes more to the transition rate than the velocity divergence and the effect of these two contributions are more important for small distances from the shock front. For the non-equilibrium pressure, the term associated with the bulk viscosity increases by a small amount the hydrostatic pressure

  3. Control of a chemical reaction (photodegradation of the p3ht polymer) with nonlocal dielectric environments

    Science.gov (United States)

    Peters, V. N.; Tumkur, T. U.; Zhu, G.; Noginov, M. A.

    2015-10-01

    Proximity to metallic surfaces, plasmonic structures, cavities and other inhomogeneous dielectric environments is known to control spontaneous emission, energy transfer, scattering, and many other phenomena of practical importance. The aim of the present study was to demonstrate that, in spirit of the Marcus theory, the rates of chemical reactions can, too, be influenced by nonlocal dielectric environments, such as metallic films and metal/dielectric bilayer or multilayer structures. We have experimentally shown that metallic, composite metal/dielectric substrates can, indeed, control ordering as well as photodegradation of thin poly-3-hexylthiophene (p3ht) films. In many particular experiments, p3ht films were separated from metal by a dielectric spacer, excluding conventional catalysis facilitated by metals and making modification of the nonlocal dielectric environment a plausible explanation for the observed phenomena. This first step toward understanding of a complex relationship between chemical reactions and nonlocal dielectric environments is to be followed by the theory development and a broader scope of thorough experimental studies.

  4. Methods and systems for carrying out a pH-influenced chemical and/or biological reaction

    Science.gov (United States)

    Stern, Michael C.; Simeon, Fritz; Hatton, Trevor Alan

    2016-04-05

    The present invention generally relates to methods and systems for carrying out a pH-influenced chemical and/or biological reaction. In some embodiments, the pH-influenced reaction involves the conversion of CO.sub.2 to a dissolved species.

  5. Influence of Chemical Kinetics on Postcolumn Reaction in a Capillary Taylor Reactor with Catechol Analytes and Photoluminescence Following Electron Transfer

    OpenAIRE

    Jung, Moon Chul; Weber, Stephen G.

    2005-01-01

    Postcolumn derivatization reactions can enhance detector sensitivity and selectivity, but their successful combination with capillary liquid chromatography has been limited because of the small peak volumes in capillary chromatography. A capillary Taylor reactor (CTR), developed in our laboratory, provides simple and effective mixing and reaction in a 25-μm-radius postcolumn capillary. Homogenization of reactant streams occurs by radial diffusion, and a chemical reaction follows. Three charac...

  6. Polarization of molecular angular momentum in the chemical reactions Li + HF and F + HD

    Science.gov (United States)

    Krasilnikov, Mikhail B.; Popov, Ruslan S.; Roncero, Octavio; De Fazio, Dario; Cavalli, Simonetta; Aquilanti, Vincenzo; Vasyutinskii, Oleg S.

    2013-06-01

    The quantum mechanical approach to vector correlation of angular momentum orientation and alignment in chemical reactions [G. Balint-Kurti and O. S. Vasyutinskii, J. Phys. Chem. A 113, 14281 (2009)], 10.1021/jp902796v is applied to the molecular reagents and products of the Li + HF [L. Gonzalez-Sanchez, O. S. Vasyutinskii, A. Zanchet, C. Sanz-Sanz, and O. Roncero, Phys. Chem. Chem. Phys. 13, 13656 (2011)], 10.1039/c0cp02452j and F + HD [D. De Fazio, J. Lucas, V. Aquilanti, and S. Cavalli, Phys. Chem. Chem. Phys. 13, 8571 (2011)], 10.1039/c0cp02738c reactions for which accurate scattering information has become recently available through time-dependent and time-independent approaches. Application of the theory to two important particular cases of the reactive collisions has been considered: (i) the influence of the angular momentum polarization of reactants in the entrance channel on the spatial distribution of the products in the exit channel and (ii) angular momentum polarization of the products of the reaction between unpolarized reactants. In the former case, the role of the angular momentum alignment of the reactants is shown to be large, particularly when the angular momentum is perpendicular to the reaction scattering plane. In the latter case, the orientation and alignment of the product angular momentum was found to be significant and strongly dependent on the scattering angle. The calculation also reveals significant differences between the vector correlation properties of the two reactions under study which are due to difference in the reaction mechanisms. In the case of F + HD reaction, the branching ratio between HF and DF production points out interest in the insight gained into the detailed dynamics, when information is available either from exact quantum mechanical calculations or from especially designed experiments. Also, the geometrical arrangement for the experimental determination of the product angular momentum orientation and alignment based

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

    International Nuclear Information System (INIS)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Menzeleev, Artur R.; Bell, Franziska; Miller, Thomas F., E-mail: tfm@caltech.edu [Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125 (United States)

    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.

  9. Performance and cost of energy transport and storage systems for dish applications using reversible chemical reactions

    Science.gov (United States)

    Schredder, J. M.; Fujita, T.

    1984-01-01

    The use of reversible chemical reactions for energy transport and storage for parabolic dish networks is considered. Performance and cost characteristics are estimated for systems using three reactions (sulfur-trioxide decomposition, steam reforming of methane, and carbon-dioxide reforming of methane). Systems are considered with and without storage, and in several energy-delivery configurations that give different profiles of energy delivered versus temperature. Cost estimates are derived assuming the use of metal components and of advanced ceramics. (The latter reduces the costs by three- to five-fold). The process that led to the selection of the three reactions is described, and the effects of varying temperatures, pressures, and heat exchanger sizes are addressed. A state-of-the-art survey was performed as part of this study. As a result of this survey, it appears that formidable technical risks exist for any attempt to implement the systems analyzed in this study, especially in the area of reactor design and performance. The behavior of all components and complete systems under thermal energy transients is very poorly understood. This study indicates that thermochemical storage systems that store reactants as liquids have efficiencies below 60%, which is in agreement with the findings of earlier investigators.

  10. A study of the chemical effects of metal hydroxides upon cement hydration reactions

    Energy Technology Data Exchange (ETDEWEB)

    Fowler, G.D.; Asavapisit, S.; Cheeseman, C.R.; Perry, R. [Centre for Environmental Control and Waste Management, Civil Engineering Building, Imperial College GB, London (United Kingdom)

    1997-12-31

    By the addition of individual metal hydroxides (Pb(II), Zn(II), Cr(III) and Fe(III)) to ordinary Portland cement in an inert atmosphere, the chemical interactions which occur have been studied by examining changes in the solution chemistry through IC and ICP-AES. The extent of the cement hydration reactions were also studied by following the production of Ca(OH)2 using DTA and the rate of heat evolution as hydration proceeded by isothermal conduction calorimetry. These results showed that the effects of each metal are different. With respect to the effects upon the hydration reactions, Fe(OH){sub 3} accelerates whilst Cr(OH){sub 3} slightly retarded them. The Zn(OH){sub 2} completely suppressed hydration whilst Pb(OH){sub 2} retarded the reaction by about 8 days. With regard to solution effects, reduced levels of Ca{sup 2+} and SO{sub 4}{sup 2-} were released compared to an OPC control and re-solubilization of the metals in the cement system was noted, partially as a result of oxidation effects. By using Ca Cl{sub 2}, it was shown to be possible to partially overcoming the retarding effects of Pb(OH){sub 2}

  11. Ab Initio Studies of Shock-Induced Chemical Reactions of Inter-Metallics

    Science.gov (United States)

    Zaharieva, Roussislava; Hanagud, Sathya

    2009-06-01

    Shock-induced and shock assisted chemical reactions of intermetallic mixtures are studied by many researchers, using both experimental and theoretical techniques. The theoretical studies are primarily at continuum scales. The model frameworks include mixture theories and meso-scale models of grains of porous mixtures. The reaction models vary from equilibrium thermodynamic model to several non-equilibrium thermodynamic models. The shock-effects are primarily studied using appropriate conservation equations and numerical techniques to integrate the equations. All these models require material constants from experiments and estimates of transition states. Thus, the objective of this paper is to present studies based on ab initio techniques. The ab inito studies, to date, use ab inito molecular dynamics. This paper presents a study that uses shock pressures, and associated temperatures as starting variables. Then intermetallic mixtures are modeled as slabs. The required shock stresses are created by straining the lattice. Then, ab initio binding energy calculations are used to examine the stability of the reactions. Binding energies are obtained for different strain components super imposed on uniform compression and finite temperatures. Then, vibrational frequencies and nudge elastic band techniques are used to study reactivity and transition states. Examples include Ni and Al.

  12. 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

    2012-08-01

    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. PMID:23919126

  13. Comparative Studies of Chemical Effects following Nuclear Reactions and Transformations on Metal Organic Phenyl Compounds

    International Nuclear Information System (INIS)

    A study of the chemical effects created by the energetic recoil atoms of nuclear reactions in solids and liquids was made on the basis of a broad comparison of the products formed by (n, γ) and (n, 2n) processes in the metalphenyl compounds of germanium, tin, lead, arsenic and antimony. In addition, the radioactive recoil products formed after the K-capture process on Ge68 - tetraphenyl are compared with the results from the (n, γ) -process on Ga-triphenyl and the (n,p) process on Ge-tetra phenyl. Finally, the studies include the β- transition on Ge77-tetraphenyl to As77. Applying different separation methods, e.g. adsorption chromatography on alumina, ion exchange and electrophoresis, the various radioactive recoil products were separated and the individual yields determined. It was found that in nuclear reactions the compounds of the mentioned metals having identical ligands formed practically the same classes of recoil products. The yield distribution however reveals characteristic alterations between the (n, γ) and (n, 2n) reaction. Only a small influence on the yields is perceptible when irradiations are performed in liquids and solutions. The large differences found for the new compounds formed by nuclear transformations are striking, not only in the kind of typical products but also in their percentage yields. Thus, several recoil products of Ge and Ga with metalorganic character were found by nuclear reactions on Ge-tetraphenyl that could not be detected at all by the K-capture process on Ge68-tetraphenyl. The β- decay on Ge77-tetraphenyl produces practically the same chemical compounds as were observed by nuclear reactions. However, a remarkable increase in the portion of the labelled parent molecules (retention) is typical for the β- transition. The results are discussed on the basis of theoretical considerations of the amount of kinetic energy transferred to the reacting molecule by the nuclear recoil and the resulting excitation. The hypothesis is

  14. 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.

  15. 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

  16. 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.

  17. Numerical analysis of supersonic gas jets into liquid pools with or without chemical reaction using the SERAPHIM program

    International Nuclear Information System (INIS)

    Highlights: ► We perform numerical analysis on gas jet into liquid with or without reaction. ► We apply multi-fluid model and surface reaction model. ► Proposed model can reproduce behaviors of gas jet into liquid with reaction. - Abstract: A computer program called SERAPHIM has been developed to calculate multicomponent multiphase flow involving sodium-water chemical reaction in a steam generator of sodium cooled fast reactors. In this study, numerical analyses of supersonic gas jets into liquid pools with or without chemical reaction were performed to validate proposed numerical methods. The SERAPHIM program uses a multi-fluid model and a HSMAC method modified for compressible multiphase flows. An interfacial drag force was calculated from a newly constructed model. A surface reaction model, which has been developed by the authors, was applied to evaluate a mass generation rate by chemical reaction between a gas and liquid phase. As validation for a non-reaction problem, the experiment on horizontal supersonic air jet into water was analyzed. Numerical results showed that velocity of the injected air decreased by the effect of a interfacial drag force, and then the air went upward because of buoyancy. A horizontal penetration length of the air jet agreed with experimental results very well. On the other hand, we analyzed the experiment on vertical supersonic chlorine jet into Na–NaCl mixture. In this analysis, the injected gas disappeared at a certain height from chemical reaction. An estimated plume length showed good agreement with experimental data. The proposed numerical methods were found to be applicable to multiphase flow with supersonic gas jet and chemical reaction.

  18. Remote and in situ sensing products in chemical reaction using a flexible terahertz pipe waveguide.

    Science.gov (United States)

    You, Borwen; Lu, Ja-Yu

    2016-08-01

    The feasibility of remote chemical detection is experimentally demonstrated by using a Teflon pipe as a scanning arm in a continuous-terahertz wave sensing and imaging system. Different tablets with distinct mixed ratios of aluminum and polyethylene powders are well distinguished by measuring the power reflectivities of 0.4 THz wave associated with their distinct terahertz refractive indices. Given its refractive index sensitivity and fast response, the reflective terahertz sensing system can be used to real-time trace and quantitatively analyze the ammonium-chloride aerosols produced by the chemical reaction between hydrochloric acid and ammonia vapors. With a tightly focusing terahertz beam spot, the spatial and concentration distributions of the generated chemical product are successfully mapped out by the 1D scan of the flexible pipe probe. In consideration of the responsitivity, power stability, and focused spot size of the system, its detection limit for the ammonium-chloride aerosol is estimated to be approximately 165 nmol/mm2. The reliable and compact terahertz pipe scan system is potentially suitable for practical applications, such as biomedical or industrial fiber endoscopy. PMID:27505768

  19. The chemical kinetics of the reactions of lithium with steam-air mixtures

    International Nuclear Information System (INIS)

    This work involved the experimental and analytical determination of the consequences of lithium fires in the presence of steam. Experiments were performed to characterize the chemical reactions of lithium with steam-nitrogen and steam-air mixtures. Models were introduced in the LITFIRE code to describe lithium fires in the presence of steam inside the containment building and plasma chamber of a hypothetical fusion reactor. The code was also equipped with the capability to determine the effects of decay heat and lithium fire on the temperature response of the reactor first wall in the event of a coolant disturbance. Forty-two kinetics experiments were performed in which a stream of steam-nitrogen or steam-air was passed over and reacted with approximately three grams of lithium heated to a predetermined temperature. The lithium reaction rates with the constituent gases were measured and characterized for a wide range of lithium temperatures and gas compositions. Experiments were performed with steam molar concentrations of 5, 15 and 30% and lithium temperatures ranging from 400 to 1100 degree C, inclusive. The LITFIRE code was modified to enable it to model the interactions of lithium with steam-air atmospheres. Results of the reaction kinetics experiments were used in the reaction model, and the heat transfer model was expanded to allow it to handle condensible atmospheres. Three groups of accidents were investigated: a spill on the containment building floor, a spill inside the reactor plasma chamber, and a spill inside the plasma chamber with steam injection to the containment building simulating a steam line break. The results were compared to dry air cases under the same conditions. 23 refs., 66 figs., 18 tabs

  20. Mixing and non-equilibrium chemical reaction in a compressible mixing layer. M.S. Thesis Final Report

    Science.gov (United States)

    Steinberger, Craig J.

    1991-01-01

    The effects of compressibility, chemical reaction exothermicity, and non-equilibrium chemical modeling in a reacting plane mixing layer were investigated by means of two dimensional direct numerical simulations. The chemical reaction was irreversible and second order of the type A + B yields Products + Heat. The general governing fluid equations of a compressible reacting flow field were solved by means of high order finite difference methods. Physical effects were then determined by examining the response of the mixing layer to variation of the relevant non-dimensionalized parameters. The simulations show that increased compressibility generally results in a suppressed mixing, and consequently a reduced chemical reaction conversion rate. Reaction heat release was found to enhance mixing at the initial stages of the layer growth, but had a stabilizing effect at later times. The increased stability manifested itself in the suppression or delay of the formation of large coherent structures within the flow. Calculations were performed for a constant rate chemical kinetics model and an Arrhenius type kinetic prototype. The choice of the model was shown to have an effect on the development of the flow. The Arrhenius model caused a greater temperature increase due to reaction than the constant kinetic model. This had the same effect as increasing the exothermicity of the reaction. Localized flame quenching was also observed when the Zeldovich number was relatively large.

  1. Chemical reactions in a scramjet combustor and two-dimensional nozzles

    Science.gov (United States)

    Yeung, Moon-Tai

    Finite-rate chemistry of hydrogen-air combustion is to be investigated numerically in a one-dimensional constant pressure SCRAMJET combustor and two-dimensional nozzles. Detailed reaction mechanisms and temperature dependent thermodynamics are to be used in the models. The aspects of interest include the combustion characteristics at different fuel-air ratios, pressures and initial temperatures in the combustor. Methods for enhancing the combustion rate in the combustor is to be studied also. The effect of expansion rate on the hydrogen-air reactions is the prime focus of the nozzle calculation. The results from different inlet conditions and wall geometries are to be analyzed. A computer model for a one-dimensional (channel-flow) combustor is constructed based on the chemical kinetics subroutine library CHEMKIN. Subsequent calculations show that the initial temperature is the most important parameter in the combustor. It is further discovered that certain reaction steps are responsible for the initial delay exhibited in all hydrogen-air combustion processes. Low temperature behavior is studied extensively and augmentation methods are developed. The introduction of a small percentage of the hydrogen radical into the initial mixture is found to be the most effective in reducing the reaction delay. The combustor pressure enters the overall reaction process in a linear manner. The calculations over five combustor pressures show that the initial delay in hydrogen-air reaction and the following period of explosion are proportional to the combustor pressure raised to certain powers. The nozzle model is two-dimensional, steady and inviscid with no conductivity and diffusivity. Two schemes are developed to handle the boundary conditions. One is based on pure numerical interpolation/extrapolation methods while the other imposes analytical supersonic characteristic equations. The former scheme is found to be more efficient while the latter is more accurate. In analysing the

  2. 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

  3. Chemical Characterization and Reactivity Testing of Fuel-Oxidizer Reaction Product (Test Report)

    Science.gov (United States)

    1996-01-01

    The product of incomplete reaction of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants, or fuel-oxidizer reaction product (FORP), has been hypothesized as a contributory cause of an anomaly which occurred in the chamber pressure (PC) transducer tube on the Reaction Control Subsystem (RCS) aft thruster 467 on flight STS-51. A small hole was found in the titanium-alloy PC tube at the first bend below the pressure transducer. It was surmised that the hole may have been caused by heat and pressure resulting from ignition of FORP. The NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) was requested to define the chemical characteristics of FORP, characterize its reactivity, and simulate the events in a controlled environment which may have lead to the Pc-tube failure. Samples of FORP were obtained from the gas-phase reaction of MMH with NTO under laboratory conditions, the pulsed firings of RCS thrusters with modified PC tubes using varied oxidizer or fuel lead times, and the nominal RCS thruster firings at WSTF and Kaiser-Marquardt. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), ion chromatography (IC), inductively coupled plasma (ICP) spectrometry, thermogravimetric analysis (TGA) coupled to FTIR (TGA/FTIR), and mechanical impact testing were used to qualitatively and quantitatively characterize the chemical, thermal, and ignition properties of FORP. These studies showed that the composition of FORP is variable but falls within a limited range of compositions that depends on the fuel loxidizer ratio at the time of formation, composition of the post-formation atmosphere (reducing or oxidizing), and reaction or postreaction temperature. A typical composition contains methylhydrazinium nitrate (MMHN), ammonium nitrate (AN), methylammonium nitrate (MAN), and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. The thermal decomposition

  4. Propensity approach to nonequilibrium thermodynamics of a chemical reaction network: Controlling single E-coli β-galactosidase enzyme catalysis through the elementary reaction steps

    Energy Technology Data Exchange (ETDEWEB)

    Das, Biswajit; Gangopadhyay, Gautam, E-mail: gautam@bose.res.in [S. N. Bose National Centre For Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700 098 (India); Banerjee, Kinshuk [Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Kolkata 700 009 (India)

    2013-12-28

    In this work, we develop an approach to nonequilibrium thermodynamics of an open chemical reaction network in terms of the elementary reaction propensities. The method is akin to the microscopic formulation of the dissipation function in terms of the Kullback-Leibler distance of phase space trajectories in Hamiltonian system. The formalism is applied to a single oligomeric enzyme kinetics at chemiostatic condition that leads the reaction system to a nonequilibrium steady state, characterized by a positive total entropy production rate. Analytical expressions are derived, relating the individual reaction contributions towards the total entropy production rate with experimentally measurable reaction velocity. Taking a real case of Escherichia coli β-galactosidase enzyme obeying Michaelis-Menten kinetics, we thoroughly analyze the temporal as well as the steady state behavior of various thermodynamic quantities for each elementary reaction. This gives a useful insight in the relative magnitudes of various energy terms and the dissipated heat to sustain a steady state of the reaction system operating far-from-equilibrium. It is also observed that, the reaction is entropy-driven at low substrate concentration and becomes energy-driven as the substrate concentration rises.

  5. Transport phenomena in solid oxide fuel cell electrodes focusing on heat transfer related to chemical reactions

    Science.gov (United States)

    Navasa, M.; Andersson, M.; Yuan, J.; Sundén, B.

    2012-11-01

    Solid oxide fuel cells (SOFCs) are widely studied for their advantages especially at high temperatures. However, operating at high temperatures represents a high cost due to the strict requirements the materials are expected to fulfill. Thus, the main goal in SOFC research has been to decrease the operating temperature so that the range of available materials is widened and hence, the operating cost can be reduced. In this paper, the different heat sources that contribute to the cell energy balance are presented with strong emphasis on the chemical reactions that take place in SOFCs. The knowledge of which heat sources or sinks taking place and their locations within the SOFC can provide useful information for further design and efficiency improvements.

  6. Synthesis and chemical reactions of the steroidal hormone 17α-methyltestosterone.

    Science.gov (United States)

    El-Desoky, El-Sayed Ibrahim; Reyad, Mahmoud; Afsah, Elsayed Mohammed; Dawidar, Abdel-Aziz Mahmoud

    2016-01-01

    Structural modifications of natural products with complex structures like steroids require great synthetic effort. A review of literature is presented on the chemistry of the steroidal hormone 17α-methyltestosterone that is approved by Food and Drug Administration (FDA) in the United States as an androgen for estrogen-androgen hormone replacement therapy treatment. The analog also offers special possibilities for the prevention/treatment of hormone-sensitive cancers. The testosterone skeleton has important functionalities in the molecule that can act as a carbonyl component, an active methylene compound, α,β-unsaturated enone and tertiary hydroxyl group in various chemical reactions to access stereoisomeric steroidal compounds with potent activity. In addition, microbiological methods of synthesis and transformation of this hormone are presented. PMID:26639430

  7. The quantum instanton (QI) model for chemical reaction rates: The 'Simplest' QI with one dividing surface

    International Nuclear Information System (INIS)

    A new version of the quantum instanton (QI) approach to thermal rate constants of chemical reactions is presented, namely, the simplest QI (SQI) approximation with one dividing surface (DS), referred to here as SQI1. (The SQI approximation presented originally was applicable only with two DSs.) As with all versions of the QI approach, the rate is expressed wholly in terms of the (quantum) Boltzmann operator (which, for complex systems, can be evaluated by Monte Carlo path integral methods). Test calculations on some simple model problems show the SQI1 model to be slightly less accurate than the original version of the QI approach, but it is the easiest version to implement; it requires only a constrained free-energy calculation, location of the (transition-state) DS so as to maximize this free energy, and the curvature (second derivative) of the free energy at this maximum

  8. 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.

  9. Axisymmetric mixed convective MHD flow over a slender cylinder in the presence of chemically reaction

    Directory of Open Access Journals (Sweden)

    Prasad K.V.

    2016-02-01

    Full Text Available The present analysis is focused on the study of the magnetic effect on coupled heat and mass transfer by mixed convection boundary layer flow over a slender cylinder in the presence of a chemical reaction. The buoyancy effect due to thermal diffusion and species diffusion is investigated. Employing suitable similarity transformations, the governing equations are transformed into a system of coupled non-linear ordinary differential equations and are solved numerically via the implicit, iterative, second order finite difference method. The numerical results obtained are compared with the available results in the literature for some special cases and the results are found to be in excellent agreement. The velocity, temperature, and the concentration profiles are presented graphically and analyzed for several sets of the pertinent parameters. The pooled effect of the thermal and mass Grashof number is to enhance the velocity and is quite the opposite for temperature and the concentration fields.

  10. Shock-induced hotspot formation and chemical reaction initiation in PETN containing a spherical void

    International Nuclear Information System (INIS)

    We present results of reactive molecular dynamics simulations of hotspot formation and chemical reaction initiation in shock-induced compression of pentaerythritol tetranitrate (PETN) with the ReaxFF reactive force field. A supported shockwave is driven through a PETN crystal containing a 20 nm spherical void at a sub-threshold impact velocity of 2 km/s. Formation of a hotspot due to shock-induced void collapse is observed. During void collapse, NO2 is the dominant species ejected from the upstream void surface. Once the ejecta collide with the downstream void surface and the hotspot develops, formation of final products such as N2 and H2O is observed. The simulation provides a detailed picture of how void collapse and hotspot formation leads to initiation at sub-threshold impact velocities.

  11. Evolution of Autocatalytic Sets in Computational Models of Chemical Reaction Networks

    Science.gov (United States)

    Hordijk, Wim

    2016-06-01

    Several computational models of chemical reaction networks have been presented in the literature in the past, showing the appearance and (potential) evolution of autocatalytic sets. However, the notion of autocatalytic sets has been defined differently in different modeling contexts, each one having some shortcoming or limitation. Here, we review four such models and definitions, and then formally describe and analyze them in the context of a mathematical framework for studying autocatalytic sets known as RAF theory. The main results are that: (1) RAF theory can capture the various previous definitions of autocatalytic sets and is therefore more complete and general, (2) the formal framework can be used to efficiently detect and analyze autocatalytic sets in all of these different computational models, (3) autocatalytic (RAF) sets are indeed likely to appear and evolve in such models, and (4) this could have important implications for a possible metabolism-first scenario for the origin of life.

  12. Evolution of Autocatalytic Sets in Computational Models of Chemical Reaction Networks.

    Science.gov (United States)

    Hordijk, Wim

    2016-06-01

    Several computational models of chemical reaction networks have been presented in the literature in the past, showing the appearance and (potential) evolution of autocatalytic sets. However, the notion of autocatalytic sets has been defined differently in different modeling contexts, each one having some shortcoming or limitation. Here, we review four such models and definitions, and then formally describe and analyze them in the context of a mathematical framework for studying autocatalytic sets known as RAF theory. The main results are that: (1) RAF theory can capture the various previous definitions of autocatalytic sets and is therefore more complete and general, (2) the formal framework can be used to efficiently detect and analyze autocatalytic sets in all of these different computational models, (3) autocatalytic (RAF) sets are indeed likely to appear and evolve in such models, and (4) this could have important implications for a possible metabolism-first scenario for the origin of life. PMID:26499126

  13. Development of catalysts for chemical reactions driven by concentrated solar energy

    International Nuclear Information System (INIS)

    The aim of this phase of the work is to study commercially available low priced catalysts, for the methanation and reforming processes in the closed-loop solar chemical heat pipe. This report summarized some long term tests of commercially available methanation catalysts and the measurement of their active surface before and after reaction. It was found that the 1%Ru on alumina stars catalysts (prepared by Englehard Company according to our request) is very active and stable at 350-750 C. The catalyst 'A' produced in Russia, is less active, however, did not lose the mechanical strength. The 50% Ni/SiO2 catalyst is active as the 'A' catalyst but loses its activity after treatment at temperature > 600 C, its geometrical size shrinked. (authors). 25 refs., 25 figs., 36 tabs

  14. 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.

  15. Chemical Effects of the (n, p) Reaction in Gaseous Systems: Simple Alkanes and their Chloroderivatives

    International Nuclear Information System (INIS)

    The chemical effects accompanying the reaction Cl35(n, p)S35 in organic system, have been studied in this paper. Chemical species in which the hot S35 atoms are stabilized were studied in the first part of this article. Methyl chloride, ethyl chloride and methane-hydrogen chloride mixture in gaseous state were used as target materials. All samples were prepared by vacuum technique and irradiated in a horizontal channel of the VVR-S reactor. The irradiated samples were analysed by radio-gas chromatography. The pressure dependence of yields of individual species has been also investigated in methyl chloride and ethyl chloride with no additives. Only a slight effect of pressure (in the range of 200-500 mm Hg) was found for irradiated methyl chloride, while the apparent increase of the yield of some simple S35-labelled compounds appeared in ethyl chloride under the same conditions. The reactions of recoil S35 atoms with gaseous methane have been examined in detail. For this purpose, the methane-hydrogen chloride mixture with additives were irradiated under constant conditions. Argon and nitric oxide were used as moderator and scavenger respectively. The composition of irradiated samples varied in the range of 20-260 mm Hg of methane and argon, 0.02-12 mm Hg of nitric oxide, the partial pressure of hydrogen chloride keeping constant (100 mm Hg). The S35-labelled hydrogen sulphide and methyl mercaptane were found as main products in irradiated samples. The results obtained show that the yield of hydrogen sulphide is mostly affected by the concentration of nitric oxide. On the other hand the amount of methyl mercaptane formed is determined mainly by the concentration of argon. (author)

  16. 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.

  17. Spectroscopy and dynamics of chemical reactions in van der Waals complexes

    International Nuclear Information System (INIS)

    Transition metal elements have d valence electrons and are characterized by a great variety of electronic configurations responsible for their specific reactivity. The elements of the second row in particular have 4d and 5s atomic orbitals of similar size and energy which can be both involved in chemical processes. We have been interested in the reactivity of a transition metal element, zirconium, combined with a simple organic functionalized molecule in a van der Waals complex formed in a supersonic molecular beam in the model reaction Zr + CH3F. In this context, one of the chemicals reactions that we are interested in leads to the formation of ZrF. The electronic spectroscopy of ZrF in the spectral domain 400 - 470 nm is extremely rich and surprising for a diatomic molecule. With this study, we have been able to identify the ground state of ZrF (X2Δ) by simulating the observed rotational structures and obtain essential information on the electronic structure. These experimental results are in agreement with ab initio calculations. The excited states of the complex Zr...F-CH3 have been studied with a depopulation method. The spectral domain 615 - 700 nm is particularly interesting because it reveals a group of diffuse bands red-shifted and broadened with respect to the transition a3F → z3F in the metal. This transition is forbidden from the ground state a3F2 of zirconium but allowed from the a3F4 state. Complexation of the metal atom with a CH3F molecule allows coupling of these two states to occur which ensures the optical transition from the ground state of the complex. (author)

  18. 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.

  19. Elucidation of Mechanisms and Selectivities of Metal-Catalyzed Reactions using Quantum Chemical Methodology.

    Science.gov (United States)

    Santoro, Stefano; Kalek, Marcin; Huang, Genping; Himo, Fahmi

    2016-05-17

    Quantum chemical techniques today are indispensable for the detailed mechanistic understanding of catalytic reactions. The development of modern density functional theory approaches combined with the enormous growth in computer power have made it possible to treat quite large systems at a reasonable level of accuracy. Accordingly, quantum chemistry has been applied extensively to a wide variety of catalytic systems. A huge number of problems have been solved successfully, and vast amounts of chemical insights have been gained. In this Account, we summarize some of our recent work in this field. A number of examples concerned with transition metal-catalyzed reactions are selected, with emphasis on reactions with various kinds of selectivities. The discussed cases are (1) copper-catalyzed C-H bond amidation of indoles, (2) iridium-catalyzed C(sp(3))-H borylation of chlorosilanes, (3) vanadium-catalyzed Meyer-Schuster rearrangement and its combination with aldol- and Mannich-type additions, (4) palladium-catalyzed propargylic substitution with phosphorus nucleophiles, (5) rhodium-catalyzed 1:2 coupling of aldehydes and allenes, and finally (6) copper-catalyzed coupling of nitrones and alkynes to produce β-lactams (Kinugasa reaction). First, the methodology adopted in these studies is presented briefly. The electronic structure method in the great majority of these kinds of mechanistic investigations has for the last two decades been based on density functional theory. In the cases discussed here, mainly the B3LYP functional has been employed in conjunction with Grimme's empirical dispersion correction, which has been shown to improve the calculated energies significantly. The effect of the surrounding solvent is described by implicit solvation techniques, and the thermochemical corrections are included using the rigid-rotor harmonic oscillator approximation. The reviewed examples are chosen to illustrate the usefulness and versatility of the adopted methodology in

  20. 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. PMID:26129639

  1. 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.

  2. Chemo-selective high yield microwave assisted reaction turns cellulose to green chemicals.

    Science.gov (United States)

    Hassanzadeh, Salman; Aminlashgari, Nina; Hakkarainen, Minna

    2014-11-01

    Exceptionally high cellulose liquefaction yields, up to 87% as calculated from the amount of solid residue, were obtained under mild conditions by utilizing the synergistic effect of microwave radiation and acid catalysis. The effect of processing conditions on degradation products was fingerprinted by rapid laser desorption ionization-mass spectrometry (LDI-MS) method. The reaction was chemo-tunable, enabling production of glucose (Glc) or levulinic acid (LeA) at significantly high selectivity and yields, the relative molar yields being up to 50 and 69%, respectively. A turning point from pure depolymerization to glucose to further degradation to levulinic acid and formic acid was observed at approximately 50% liquefaction or above 140 °C. This was accompanied by the formation of small amounts of solid spherical carbonized residues. The reaction was monitored by multiple analytical techniques. The high yields were connected to the ability of the process to break the strong secondary interactions in cellulose. The developed method has great potential for future production of green platform chemicals. PMID:25129766

  3. Chemical looping coal gasification with calcium ferrite and barium ferrite via solid--solid reactions

    Energy Technology Data Exchange (ETDEWEB)

    Siriwardane, Ranjani [U.S. Department of Energy/NETL; Riley, Jarrett [Oak Ridge Inst. for Science and Education (ORISE), Oak Ridge, TN (United States); Tian, Hanjing [West Virginia Univ., Morgantown, WV (United States); Richards, George [U.S. Department of Energy/NETL

    2016-01-01

    Coal gasification to produce synthesis gas by chemical looping was investigated with two oxygen carriers, barium ferrite (BaFe2O4) and calcium ferrite (CaFe2O4). Thermo-gravimetric analysis (TGA) and fixed-bed flow reactor data indicated that a solid–solid interaction occurred between oxygen carriers and coal to produce synthesis gas. Both thermodynamic analysis and experimental data indicated that BaFe2O4 and CaFe2O4 have high reactivity with coal but have a low reactivity with synthesis gas, which makes them very attractive for the coal gasification process. Adding steam increased the production of hydrogen (H2) and carbon monoxide (CO), but carbon dioxide (CO2) remained low because these oxygen carriers have minimal reactivity with H2 and CO. Therefore, the combined steam–oxygen carrier produced the highest quantity of synthesis gas. It appeared that neither the water–gas shift reaction nor the water splitting reaction promoted additional H2 formation with the oxygen carriers when steam was present. Wyodak coal, which is a sub-bituminous coal, had the best gasification yield with oxygen carrier–steam while Illinois #6 coal had the lowest. The rate of gasification and selectivity for synthesis gas production was significantly higher when these oxygen carriers were present during steam gasification of coal. The rates and synthesis gas yields during the temperature ramps of coal–steam with oxygen carriers were better than with gaseous oxygen.

  4. Computer model for the transport and chemical reaction of debris in direct containment heating experiments

    International Nuclear Information System (INIS)

    The transport and chemical reaction of debris is a problem of current interest in the study of certain nuclear reactor accident scenarios. In some situations, debris from the core of a reactor could be expelled into the atmosphere inside a reactor containment building. The debris would then heat the gas, resulting in an increase in the pressure in the containment. Furthermore, the exothermic reaction of the debris with the oxygen in the air would cause additional heating of the atmosphere. The present work is part of a study being carried out to determine whether this heating will be sufficient to place the integrity of the containment building at risk due to overpressurization. The authors have developed methods for computer simulation of some of the physical processes involved in such direct containment heating (DCH) configurations. In this paper, these numerical algorithms are used to model experiments pertinent to the reactor debris dispersal problem. The resulting computer code, referred to as Kiva-DCH, has been applied to the simulation of experiments performed in the Surtsey facility at Sandia National Laboratories in Albuquerque, New Mexico. It is found that the computational results agree well with those obtained from an experiment conducted at modest debris mass

  5. Sensitivity of polar stratospheric ozone loss to uncertainties in chemical reaction kinetics

    Directory of Open Access Journals (Sweden)

    S. R. Kawa

    2009-06-01

    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

  6. Direct spatiotemporal analysis of femtosecond laser-induced plasma-mediated chemical reactions

    International Nuclear Information System (INIS)

    Localized, micron to millimetre-scale plasmas resulting from the fleeting interaction between ultrashort laser pulses and matter have been studied extensively in inert atmospheres. In spite of recent interest in reactive plasmas as a nanofabrication tool, ultrashort pulsed laser ablation in reactive gas atmospheres has undergone little study. In this study, we develop a methodology combining time-resolved optical emission spectroscopy and spectrally filtered time-gated fast photography to directly observe and analyse plasma-mediated chemical reactions that occur when laser ablation is performed in reactive gases. Specifically, we compare the ablation of silicon dioxide in an atmosphere of xenon difluoride gas to its ablation in nitrogen and xenon atmospheres. We show that when xenon difluoride molecules are collisionally driven into an excited state by the silicon plasma produced during laser-induced decomposition of the solid substrate, the gas undergoes dissociation. The resulting fluorine radicals react spontaneously with the silicon plasma to produce volatile fluorinated silicon compounds. In particular, mass spectroscopy shows that the primary reaction byproduct is SiF2 with small amounts of SiF and SiF4. The high spatial and temporal resolution of our methodology reveals a slowly expanding plume having an atomic silicon core with a XeF∗ shell that persists for less than 300 ns. As the silicon is fluorinated, the optical emission due to excited silicon is quenched. The absence of a silicon signal after 300 ns establishes this as the upper limit of the reaction lifetime given the conditions of the experiment. (letter)

  7. 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).

  8. Chemical reactions involved in 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; Cr203 + 2 Na2S04(1) + 3/2 02 yields 2 Na2Cr04(1) + 2 S03(g)n TiO2 + Na2S04(1) yields Na20(T102)n + 503(g)n T102 + Na2Cro4(1) yields Na2(T102)n + Cr03(g).

  9. Synthesis of high surface area nanometer magnesia by solid-state chemical reaction

    Institute of Scientific and Technical Information of China (English)

    GUAN Hongbo; WANG Pei; ZHAO Biying; ZHU Yuexiang; XIE Youchang

    2007-01-01

    Nanometer MgO samples with high surface area,small crystal size and mesoporous texture were synthesized tion process accelerated the sintering of MgO,and MgO with calcining its precursor in flowing dry nitrogen at 520℃ for 4 h.The samples were characterized by X-ray diffraction,N2 adsorption,transmission electron microscopy,thermogravimetry,and differential thermal analysis.The as-prepared MgO was composed of nanocrystals with a size of about 4-5 nm and formed a wormhole-like porous structure.The MgO also had good thermal stability,and its surface areas remained at 357 and 153 m2.g-1 after calcination at 600 and 800℃ for 2 h,respectively.Compared with the MgO sample prepared by the precipitation method,MgO prepared by solid-state chemical reaction has uniform pore size distribution,surface area,and crystal size.The solid-state chemical method has the advantages of low cost,low pollution,and high yield,therefore it appears to be a promising method in the industrial manufacture of nanometer MgO.

  10. Modeling reaction histories to study chemical pathways in condensed phase detonation

    Science.gov (United States)

    Scott Stewart, D.; Hernández, Alberto; Lee, Kibaek

    2016-03-01

    The estimation of pressure and temperature histories, which are required to understand chemical pathways in condensed phase explosives during detonation, is discussed. We argue that estimates made from continuum models, calibrated by macroscopic experiments, are essential to inform modern, atomistic-based reactive chemistry simulations at detonation pressures and temperatures. We present easy to implement methods for general equation of state and arbitrarily complex chemical reaction schemes that can be used to compute reactive flow histories for the constant volume, the energy process, and the expansion process on the Rayleigh line of a steady Chapman-Jouguet detonation. A brief review of state-of-the-art of two-component reactive flow models is given that highlights the Ignition and Growth model of Lee and Tarver [Phys. Fluids 23, 2362 (1980)] and the Wide-Ranging Equation of State model of Wescott, Stewart, and Davis [J. Appl. Phys. 98, 053514 (2005)]. We discuss evidence from experiments and reactive molecular dynamic simulations that motivate models that have several components, instead of the two that have traditionally been used to describe the results of macroscopic detonation experiments. We present simplified examples of a formulation for a hypothetical explosive that uses simple (ideal) equation of state forms and detailed comparisons. Then, we estimate pathways computed from two-component models of real explosive materials that have been calibrated with macroscopic experiments.

  11. 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...

  12. The influence of the “cage effect” on the mechanism of reversible bimolecular multistage chemical reactions in solutions

    International Nuclear Information System (INIS)

    Manifestations of the “cage effect” at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a “cage complex.” Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the “cage effect” leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants

  13. A method for incorporating equilibrium chemical reactions into multiphase flow models for CO2 storage

    Science.gov (United States)

    Saaltink, Maarten W.; Vilarrasa, Victor; De Gaspari, Francesca; Silva, Orlando; Carrera, Jesús; Rötting, Tobias S.

    2013-12-01

    CO2 injection and storage in deep saline aquifers involves many coupled processes, including multiphase flow, heat and mass transport, rock deformation and mineral precipitation and dissolution. Coupling is especially critical in carbonate aquifers, where minerals will tend to dissolve in response to the dissolution of CO2 into the brine. The resulting neutralization will drive further dissolution of both CO2 and calcite. This suggests that large cavities may be formed and that proper simulation may require full coupling of reactive transport and multiphase flow. We show that solving the latter may suffice whenever two requirements are met: (1) all reactions can be assumed to occur in equilibrium and (2) the chemical system can be calculated as a function of the state variables of the multiphase flow model (i.e., liquid and gas pressure, and temperature). We redefine the components of multiphase flow codes (traditionally, water and CO2), so that they are conservative for all reactions of the chemical system. This requires modifying the traditional constitutive relationships of the multiphase flow codes, but yields the concentrations of all species and all reaction rates by simply performing speciation and mass balance calculations at the end of each time step. We applied this method to the H2O-CO2-Na-Cl-CaCO3 system, so as to model CO2 injection into a carbonate aquifer containing brine. Results were very similar to those obtained with traditional formulations, which implies that full coupling of reactive transport and multi-phase flow is not really needed for this kind of systems, but the resulting simplifications may make it advisable even for cases where the above requirements are not met. Regarding the behavior of carbonate rocks, we find that porosity development near the injection well is small because of the low solubility of calcite. Moreover, dissolution concentrates at the front of the advancing CO2 plume because the brine below the plume tends to reach

  14. Change of the chemical barrier performance of cement materials altered by hydrothermal reaction

    International Nuclear Information System (INIS)

    Cement has been considered to be a useful material because its chemical property is potentially suitable for immobilization of radioactive waste. In particular, the sorption of radionuclides onto cement material is very important parameter in the TRU waste disposal system containing long-life radionuclides. For the long term, in the disposal environment, cement materials must be altered by dissolution, chemical reaction with ions dissolved in the ground water, and hydrothermal reaction etc. Once the composition or crystallinity of minerals in cement is changed, the chemical properties, especially sorption, might be changed. However, the mechanism of the process of cement alteration and mechanism of radionuclide sorption onto cement are not yet fully understood. In this paper, the hydrothermal alteration process was studied experimentally, and the effect of alteration on the sorption properties of cement was investigated by the bath sorption test for Sr and Se. The results follow: 1) OPC and OPC/BFS-blended cement (hereafter BFS cement) were heated at temperatures up to 70degC in the synthetic cement equilibrated groundwater or distilled water for 1 month. Changes of crystallinity of the minerals were observed. For example, it was observed that the crystallinity of CSH-gel might increase. Ettringite decomposed on heating. For treatment in distilled water, monosulphate was formed only in the case of BFS cement. 2) In the case of Sr (as a representative cation) sorption, the distribution coefficient for hydrothermally altered OPC and BFS cement decreased as the alteration temperature increased. This is mainly caused by the decrease of distribution coefficient for the CSH-gel phase in cement accompanying the change of its crystallinity. In the case of Se(as a model anion, selenite) sorption, the distribution coefficient decreased as the alteration temperature increased for OPC in both distilled water and synthetic ground water, and also for BFS in groundwater. This is

  15. Surface reactivity and layer analysis of chemisorbed reaction films in the surface-chemical environment of alkyl octadecenoates

    Indian Academy of Sciences (India)

    R B Choudhary; O N Anand; O S Tyagi

    2009-05-01

    Studies on surface reactivity of substrate iron (Fe-particles) were made in the tribo-chemical environment of alkyl octadecenoates. Two alkyl octadecenoates namely ethyl octadecenoate and methyl 12-hydroxy octadecenoate, slightly different in their chemical nature, were taken for preparing the chemisorbed reaction films (CRF) at the temperature 100 ± 5°C. The reaction products collected in the composite (amorphous) phase were isolated into three different solvent-soluble fractions (sub-layer films) using polar solvents of increasing polar strength. The FTIR analysis of these films showed that these were primarily organic in nature and were composed of alkyl and/or aryl hydroxy ethers, unsaturated hydroxy ketones, and aromatic structures chemically linked with iron surface. These reaction films also contained large amount of iron (Fe). Further, these film fractions also showed varying thermal behaviour during thermal decomposition in the temperature range of 50-800°C when thermally evaluated in the nitrogen environment.

  16. Chemical reaction calculation simulation of redox behavior of metal ions and the like in the nitric acid solution

    International Nuclear Information System (INIS)

    It is known that corrosion rate of stainless steel in nitric acid solution is affected by the valence change of oxidizing metallic ions. In this study, we conducted redox reaction analyses using chemical reaction calculation model to clarify the mechanism of valence change. We obtained that the oxidization of metallic ions in the solution is not only caused by nitric acid but also nitrogen oxides. (author)

  17. Influence of chemical kinetics on postcolumn reaction in a capillary Taylor reactor with catechol analytes and photoluminescence following electron transfer.

    Science.gov (United States)

    Jung, Moon Chul; Weber, Stephen G

    2005-02-15

    Postcolumn derivatization reactions can enhance detector sensitivity and selectivity, but their successful combination with capillary liquid chromatography has been limited because of the small peak volumes in capillary chromatography. A capillary Taylor reactor (CTR), developed in our laboratory, provides simple and effective mixing and reaction in a 25-microm-radius postcolumn capillary. Homogenization of reactant streams occurs by radial diffusion, and a chemical reaction follows. Three characteristic times for a given reaction process can be predicted using simple physical and chemical parameters. Two of these times are the homogenization time, which governs how long it takes the molecules in the analyte and reagent streams to mix, and the reaction time, which governs how long the molecules in a homogeneous solution take to react. The third characteristic time is an adjustment to the reaction time called the start time, which represents an estimate of the average time the analyte stream spends without exposure to reagent. In this study, laser-induced fluorescence monitored the extent of the postcolumn reaction (reduction of Os(bpy)3(3+) by analyte to the photoluminescent Os(bpy)3(2+)) in a CTR. The reaction time depends on the reaction rates. Analysis of product versus time data yielded second-order reaction rate constants between the PFET reagent, tris(2,2'-bipyridine)osmium, and standards ((ferrocenylmethyl)trimethylammonium cation and p-hydroquinone) or catechols (dopamine, epinephrine, norepinephrine, 3, 4-dihydroxyphenylacetic acid. The extent of the reactions in a CTR were then predicted from initial reaction conditions and compared to experimental results. Both the theory and experimental results suggested the reactions of catechols were generally kinetically controlled, while those of the standards were controlled by mixing time (1-2 s). Thus, the extent of homogenization can be monitored in a CTR using the relatively fast reaction of the reagent and p

  18. 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. PMID:21425793

  19. 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.

  20. Effects of Radiation and Chemical Reaction on MHD Convective Flow over a Permeable Stretching Surface with Suction and Heat Generation

    Directory of Open Access Journals (Sweden)

    Penem Mohan KRISNA

    2014-03-01

    Full Text Available In this study, we analyze the effects of thermal radiation and chemical reaction on the steady 2 dimensional stagnation point flow of a viscous incompressible electrically conducting fluid over a stretching surface, with suction and heat generation. The partial differential equations governing the flow are solved numerically by using the shooting technique. The effects of various parameters on velocity, temperature, and concentration profiles, as well as Nusselt number, Skin friction coefficient, and Sherwood number, are examined, and presented graphically and through tables. It is found that velocity, temperature, and rate of heat transfer of the fluid are influenced more by radiation and chemical reaction parameters, along with applied magnetic field.

  1. 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

    ’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...... general description of chemical reactions among constituents is described. The Petrov – Galerkin approach are used in favour of the standard Galerkin weighting in order to improve the solution when the convective part of the problem is dominant. A modified type of Newton – Raphson scheme is derived for...

  2. The behaviour of chemically altered coals in ZnCl{sub 2}-catalysed reaction with hydrogen and methanol

    Energy Technology Data Exchange (ETDEWEB)

    Kuznetsov, P.N.; Bimer, J.; Salbut, P.D.; Gruber, R.; Djega-Mariadassou, G.; Brodzki, D.; Korniyets, E.; Kuznetsova, L.; Krzton, A. [Institute of Chemistry and Chemico-Metallurgical Processes, Krasnoyarsk (Russian Federation)

    1996-08-01

    A series of chemically altered coals was investigated in the reaction with methanol and hydrogen in the presence of ZnCl{sub 2} as a catalyst. Significant beneficial effects were observed when high-rank coals were altered by reductive and radioactively methylating pretreatments. The behaviour of altered low-rank brown and subbituminous coals was affected by both the mode of chemical pretreatment and the reaction conditions. The benefit can be explained by partial depolymerization of the coal matter through the disruption of cross-links and the passivation of hydroxyl groups by methylation. 33 refs., 7 figs., 3 tabs.

  3. Chromatographic elution profile of an analyte involved in reversible chemical reaction of the type A + B AB.

    Science.gov (United States)

    Kanatyeva, A Yu

    2007-05-25

    The chromatographic peak profile of the analyte involved in a chemical reaction of the type A + B AB is considered using method of the apparent adsorption isotherm. The apparent isotherms derived are nonlinear even under assumption of Henry isotherms of individual solutes. Nonlinearity of apparent adsorption isotherm results in peak distortion. The resulted chromatographic peak profile depends on several factors such as the equilibrium constant K(mob) and Henry constants of the solutes. Simulated peak profiles of solutes involved in the chemical reaction are presented as illustration of influence of various factors. PMID:16965781

  4. Exact solutions for the magnetohydrodynamic flow of a Jeffrey fluid with convective boundary conditions and chemical reaction

    Energy Technology Data Exchange (ETDEWEB)

    Alsaedi, Ahmed [King Abdulaziz Univ., Jeddah (Saudi Arabia). Dept. of Mathematics; Iqbal, Zahid; Hayat, Tasawar [Quaid-i-Azam Univ., Islamabad (Pakistan). Dept. of Mathematics; Mustafa, Meraj [National Univ. of Sciences and Technology (NUST), Islamabad (Pakistan). Research Centre for Modeling and Simulation (RCMS)

    2012-08-15

    The two-dimensional magnetohydrodynamic (MHD) flow of a Jeffrey fluid is investigated in this paper. The characteristics of heat and mass transfer with chemical reaction have also been analyzed. Convective boundary conditions have been invoked for the thermal boundary layer problem. Exact similarity solutions for flow, temperature, and concentration are derived. Interpretation to the embedded parameters is assigned through graphical results for dimensionless velocity, temperature, concentration, skin friction coefficient, and surface heat and mass transfer. The results indicate an increase in the velocity and the boundary layer thickness by increasing the rheological parameter of the Jeffrey fluid. An intensification in the chemical reaction leads to a thinner concentration boundary layer. (orig.)

  5. Numerical modelling of shock-induced chemical reactions (SICR) in reactive powder mixtures using smoothed particle hydrodynamics (SPH)

    Science.gov (United States)

    S, Siva Prasad A. V.; Basu, Sumit

    2015-10-01

    Shock compaction of reactive powder mixtures to synthesize new materials is one of the oldest material processing techniques and has been studied extensively by several researchers over the past few decades. The quantitative connection between the shock energy imparted and the extent of reaction that can be completed in the small time window associated with the passage of the shock wave is complicated and depends on a large variety of parameters. In particular, our understanding of the complex interplay between the thermo-elasto-viscoplastic behaviour of the granular constituents and their temperature dependent, diffusion-limited reaction mechanism may be enriched through careful numerical simulations. A robust numerical model should be able to handle extremely large deformations coupled with diffusion mediated fast reaction kinetics. In this work, a meshfree discrete particle numerical method based on smoothed particle hydrodynamics (SPH) to simulate shock-induced chemical reactions (SICR) in reactive powder mixtures is proposed. We present a numerical strategy to carry out reactions between reactant powder particles and partition the obtained products between the particles in a manner that accounts for the requirement that the total mass of the entire system remains constant as the reactions occur. Instead of solving the reaction-diffusion problem, we propose a ‘pseudo-diffusion’ model in which a distance dependent reaction rate constant is defined to carry out chemical reaction kinetics. This approach mimics the actual reaction-diffusion process at short times. Our numerical model is demonstrated for the well-studied reaction system Nb  +  2Si \\rightleftharpoons NbSi 2 . The predicted mass fractions of the product obtained from the simulations are in agreement with experimental observations. Finally, the effects of impact speed, particle arrangement and mixing ratio on the predicted product mass fractions are discussed.

  6. 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.

  7. Combined treatment with antioxidants and immunosuppressants on cytokine release by human peripheral blood mononuclear cells - chemically injured keratocyte reaction

    OpenAIRE

    Yi, Kayoung; Chung, Tae Young; Hyon, Joon Young; Koh, Jae Woong; Wee, Won Ryang; Shin, Young Joo

    2011-01-01

    Purpose To investigate the effect of antioxidants and immunosuppresants on mixed peripheral blood mononuclear cells (PBMC) - chemically injured keratocytes reaction (MLKR). Methods The PBMC stimulation assay was performed using chemically injured keratocytes treated with 0.05 N NaOH for 90 s (MLKR). MLKR were treated with various drugs including rapamycin, dexamethasone, mycophenoleic acid (MPA), alpha lipoic acid (ALA), and N-acetyl cysteine (NAC). Matrix metalloprotease-9 (MMP-9), transform...

  8. The kinetics of the photo-induced solid-state chemical reaction in Ag/As33S67 bilayers and its reaction products

    Science.gov (United States)

    Wagner, T.; Marquez, E.; Fernandez-Pena, J.; Gonzalez-Leal, J. M.; Ewen, P. J. S.; Kasap, S. O.

    1999-02-01

    The kinetics of the photo-induced solid-state chemical reaction of silver with amorphous As33S67 films in a conventional sandwich structure was measured by monitoring the change in thickness of the undoped chalcogenide using a modified computer-controlled reflection technique. The reaction between silver and the chalcogenide layer was induced by an Ar-ion laser. The Ag As33S67 sample was illuminated by the laser beam coming from the chalcogenide side of the sample. The consumption of the elemental silver source in the course of the reaction was monitored by the simultaneous measurement of the electrical resistance of the silver layer. The kinetic data obtained show that there are two stages in the photoreaction process, with the second stage having a sublinear dependence. The exhaustion of the elemental silver source in the course of the reaction does not significantly influence the reaction rate. The reaction rates characterizing each stage have been measured, and a comparison of the composition and structure has been made. All the structure-sensitive parameters, Tg, Cp and Delta Cp, measured by the temperature modulated differential scanning calorimetry (MDSC) technique, show a change in the structure of As33S67 as silver is introduced by photodoping or in melt-quenched Ag-As-S glasses. Further, by using far-infrared spectroscopy it was possible to correlate the MDSC results to the structure of As33S67 and Ag-As-S glasses.

  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. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization

    Science.gov (United States)

    Vaikkinen, Anu; Kauppila, Tiina J.; Kostiainen, Risto

    2016-04-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M+. decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques.

  11. Surface modification of poly(ethylene terephthalate) fabric via photo-chemical reaction of dimethylaminopropyl methacrylamide

    International Nuclear Information System (INIS)

    Highlights: ► PET fibers were UV-grafted with dimethylaminopropyl methacrylamide (DMAPMA). ► The graft yield could be controlled by irradiation time and monomer concentration. ► The tertiary amino groups of the grafted PDMAPMA were quaternized with alkyl bromides. ► The quaternization reaction had a high yield, when bromides with shorter alkyl chain were employed. ► The antimicrobial effect was highest, when samples were quaternized with 1-bromohexane and 1-bromooctane. - Abstract: Photo-chemical reactions and surface modifications of poly(ethylene terephthalate) (PET) fabrics with the monomer dimethylaminopropyl methacrylamide (DMAPMA) and benzophenone (BP) as photo-initiator using a broad-band UV lamp source were investigated. The tertiary amino groups of the grafted poly(DMAPMA) chains were subsequently quaternized with alkyl bromides of different chain lengths to establish antibacterial activity. The surface composition, structure and morphology of modified PET fabrics were characterized by Fourier transform infrared spectroscopy (FTIR/ATR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). To evaluate the amount of quaternary and tertiary ammonium groups on the modified surface, PET was dyed with an acid dye which binds to the ammonium groups. Therefore, the color depth is a direct indicator of the amount of ammonium groups. The resulting antibacterial activity of the modified PET fabrics was tested with Escherichia coli. The results of all experiments show that a photochemical modification of PET is possible using DMAPMA, benzophenone and UV light. Also, the quaternization of tertiary amino groups as well as the increase in antibacterial activity of the modified PET by the established quaternary ammonium groups were successful.

  12. Modelling chemical and biological reactions during unsaturated flow in silty arable soils

    Science.gov (United States)

    Michel, Kerstin; Herrmann, Sandra; Ludwig, Bernard

    2010-05-01

    Ion dynamics in arable soils are strongly affected by the chemical and biological transformations triggered by fertilizer input. Hydrogeochemical models may improve our understanding of underlying processes. Our objective was to test the ability of the hydrogeochemical model PHREEQC2 in combination with the parameter optimization programme PEST to describe and predict chemical and biological processes in silty soils triggered by fertilizer application or acidification and to investigate the usefulness of different parameterization approaches. Three different experiments were carried out using undisturbed columns of two topsoils (0-25 cm) from Germany (Göttingen, GO) and from the Oman (Qasha', QA). The columns were irrigated at 10 oC with 3 mm day-1 for one year using 1 mM HCl (HCl experiment) and two fertilizer solutions with low (0.1 to 0.9 mmol L-1) and high concentrations (1.3 to 14.7 mmol L-1) of N (as NH4NO3), K, Ca and Mg. In the fertilization experiments (Fert1, Fert2), the columns were alternately irrigated with the two different solutions for variable time periods. One-dimensional transport and homogenous and heterogenous reactions were calculated using PHREEQC2. The Fert1 experiment was used for calibration. The models were validated using the Fert2 and HCl experiments. The models tested were model variant m1 with no adjustable parameters, model variant m2 in which nitrate concentrations in input solutions and cation exchange capacity were optimized for Fert1, and m3 in which additionally all cation exchange coefficients and ion concentrations in the initial solution were optimized. Model variant m1 failed to predict the concentrations of several cations for both soils (modelling efficiencies (EF) ≤ 0), since N dynamics were not considered adequately. Model variants m2 and m3 described (Fert1 treatment) and predicted (Fert2 and HCl treatment) pH, cation and NO3- concentrations generally more accurately for both soils. For nutrient cations, EF values

  13. Evidence for the occurrence of electrochemical reactions and their interaction with chemical reactions during the corrosion of pure Fe with solid NaCl deposit in water vapor at 600 C

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Yanbing; Liu, Li; Li, Ying; Wang, Fuhui [State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, Wencui Road 62, Shenyang 110016 (China)

    2010-02-15

    The results of this work prove that electrochemical reactions are involved in the whole corrosion process of pure Fe with a solid NaCl deposit in water vapor at 600 C. The interaction of chemical and electrochemical reactions accelerates the corrosion rate of pure Fe significantly. The electrochemical reaction is coupled with a preceding chemical reaction process (ce), in which Fe first reacts chemically with NaCl and water vapor to generate HCl{sub (g)}. And then, the electrochemical reaction proceeds via a one-electron electrochemical reduction to form H{sub 2}. (author)

  14. 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.

  15. Modelling transport of water and ions and chemical reactions in compacted bentonite - Two flexible modelling platforms

    International Nuclear Information System (INIS)

    ; - solution of the models in the selected approach; - presentation of the results by flexible support of chosen platforms. In order to bind our results to earlier models and carry out verification, we apply in parallel with our tools also the TOUGH2 or TOUGHREACT codes. We are planning to present a new version of our transport and chemical reaction model (RFT, Reactions, Fluxes, Temperature). One new feature will be a saturation model based on tomographical measurements

  16. Molecular-Level Simulations of Chemical Reaction Equilibrium and Diffusion in Slit and Cylindrical Nanopores: Model Dimerisation Reactions

    Czech Academy of Sciences Publication Activity Database

    Lísal, Martin; Předota, Milan; Brennan, J.K.

    2013-01-01

    Roč. 39, č. 13 (2013), s. 1103-1120. ISSN 0892-7022 R&D Projects: GA ČR GA13-09914S Grant ostatní: GA ČR(CZ) GA13-08651S Institutional support: RVO:67985858 Keywords : molecular dynamics * reaction ensemble Monte Carlo * slit and cylindrical nanopores Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.119, year: 2013

  17. The swelling behavior of ionic polymers in the presence of diffusion and chemical reactions

    Science.gov (United States)

    Baek, Seungik

    During the past few decades, ionic polymers have attracted much attention due to their unique properties, i.e., a stimulus-sensitive swelling behavior. The use of ionic polymers in biotechnology and medicine is increasingly attractive for applications such as controlled drug delivery, biomimetic actuators, and chemical valves. The ability to model and predict the swelling behavior of polymers and mass flux with respect to external environmental conditions is very important in such applications. The focus of this dissertation is on developing a continuum model for the behavior of a swollen solid and diffusion of a fluid through it in the presence of chemical reactions. To model diffusion through an ionic/nonionic polymer in the presence of mechanical deformation, we develop a variational procedure based on a thermodynamic framework for a swollen solid subject to constraints. This thermodynamic framework was mainly developed by Rajagopal and Srinivasa as a general thermodynamic framework for inelastic behavior of materials. First, a model for the mechanical behavior of a rubber-like solid in the presence of mass diffusion is developed using the variational procedure. By assuming a specific form for the Helmholtz potential function, we obtain an equilibrium equation that is identical to the equation suggested by Flory, Huggins, and Rehner. For the non-equilibrium problem, we assume a specific form for the rate of dissipation function and obtain the relation between pressure difference and mass flux. The numerical results show very good agreement with experimental data for the diffusion of organic solvents through a rubber slab. Hysteresis response of the swollen solid due to time-dependent loads is also simulated by the model. The variational procedure is also applied to pH-sensitive ionic polymers, which not only yields the equations for the deformation of a swollen solid and mass flux, but also the equations for chemical equilibrium. As a specific example, an

  18. 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)

  19. Infrared emission associated with chemical reactions on Shuttle and SIRTF surfaces

    Science.gov (United States)

    Hollenbach, D. J.; Tielens, Alexander G. G. M.

    1984-01-01

    The infrared intensities which would be observed by the Shuttle Infrared Telescope Facility (SIRTF), and which are produced by surface chemistry following atmospheric impact on SIRTF and the shuttle are estimated. Three possible sources of reactants are analyzed: (1) direct atmospheric and scattered contaminant fluxes onto the shuttle's surface; (2) direct atmospheric and scattered contaminant fluxes onto the SIRTF sunshade; and (3) scattered fluxes onto the cold SIRTF mirror. The chemical reactions are primarily initiated by the dominent flux of reactive atomic oxygen on the surfaces. Using observations of the optical glow to constrain theoretical parameters, it is estimated for source (1) that the infrared glow on the SIRTF mirror will be comparable to the zodiacal background between 1 and 10 micron wavelengths. It is speculated that oxygen reacts with the atoms and the radicals bound in the organic molecules that reside on the shuttle and the Explorer surfaces. It is concluded that for source (2) that with suitable construction, a warm sunshade will produce insignificant infrared glow. It is noted that the atomic oxygen flux on the cold SIRTF mirror (3) is insufficient to produce significant infrared glow. Infrared absorption by the ice buildup on the mirror is also small.

  20. Exchange repulsive potential adaptable for electronic structure changes during chemical reactions

    International Nuclear Information System (INIS)

    Hybrid methods combining quantum mechanical (QM) and classical calculations are becoming important tools in chemistry. The popular approach to calculate the interaction between QM and classical calculations employs interatomic potentials. In most cases, the interatomic potential is constructed of an electrostatic (ES) potential and a non-ES potential. Because QM treatment is employed in the calculation of the ES potential, the electronic change can be considered in this ES potential. However, QM treatment of the non-ES potential is difficult because of high computational cost. To overcome this difficulty of evaluating the non-ES potential, we proposed an exchange repulsive potential as the main part of the non-ES potential on the basis of a QM approach. This potential is independent of empirical parameters and adaptable for electronic structure. We combined this potential with the reference interaction site model self-consistent field explicitly including spatial electron density distribution and successfully applied it to the chemical reactions in aqueous phase

  1. Performing chemical reactions in virtual capillary of surface tension-confined microfluidic devices

    Indian Academy of Sciences (India)

    Angshuman Nag; Biswa Ranjan Panda; Arun Chattopadhyay

    2005-10-01

    In this paper we report a new method of fabrication of surface tension-confined microfluidic devices on glass. 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 were fabricated by making parallel lines using permanent marker pen ink or other polymer on glass surfaces. Two mirror image patterned glass plates were then sandwiched one on top of the other, separated by a thin gap - created using a spacer. The aqueous liquid moves between the surfaces by capillary forces, confined to the hydrophilic areas without wetting the hydrophobic lines, achieving liquid confinement without physical side-walls. We have shown that the microfluidic devices designed in such a way can be very useful due to their simplicity and low fabrication cost. More importantly, we have also demonstrated that the minimum requirement of such a working device is a hydrophilic line surrounded by hydrophobic environment, two walls of which are constituted of air and the rest is made of a hydrophobic surface.

  2. The physical and chemical properties of polymerization reaction for contact lens irradiated by electron beam

    International Nuclear Information System (INIS)

    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 → 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

  3. 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.

  4. Effect of different chemical modification of carbon nanotubes for the oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    The electrochemical reduction of oxygen on chemically modified multi-walled carbon nanotubes (CNTs) electrodes in 1 M KOH solution has been studied using the rotating ring disc electrode (RDE). The surface modification of CNTs has been estimated by XPS and Raman spectroscopy. The effect of different oxygen functionalities on the surface of carbon nanotube for the oxygen reduction reaction (ORR) is considered in terms of the number of electrons (n) involved. Electrochemical studies indicate that in the case of the modification of CNTs with citric acid and diazonium salts the n values were close to two in the measured potential range, and the electrochemical reduction is limited to the production of peroxide as the final product. In the case of the modification of carbon nanotubes with peroxymonosulphuric acid, in the measured potential range, the n value is close to 4 indicating the four-electron pathway for the ORR. By correlating ORR measurements with the XPS analysis, we propose that the increase in electrocatalytic activity towards the ORR, for CNT can be attributed to the increase in C-O groups on the surface of CNTs after modification with peroxymonosulphuric acid

  5. A priori modeling of chemical reactions on computational grid platforms: Workflows and data models

    International Nuclear Information System (INIS)

    Graphical abstract: The quantum framework of the Grid Empowered Molecular Simulator GEMS assembled on the European Grid allows the ab initio evaluation of the dynamics of small systems starting from the calculation of the electronic properties. Highlights: ► The grid based GEMS simulator accurately models small chemical systems. ► Q5Cost and D5Cost file formats provide interoperability in the workflow. ► Benchmark runs on H + H2 highlight the Grid empowering. ► O + O2 and N + N2 calculated k (T)’s fall within the error bars of the experiment. - Abstract: The quantum framework of the Grid Empowered Molecular Simulator GEMS has been assembled on the segment of the European Grid devoted to the Computational Chemistry Virtual Organization. The related grid based workflow allows the ab initio evaluation of the dynamics of small systems starting from the calculation of the electronic properties. Interoperability between computational codes across the different stages of the workflow was made possible by the use of the common data formats Q5Cost and D5Cost. Illustrative benchmark runs have been performed on the prototype H + H2, N + N2 and O + O2 gas phase exchange reactions and thermal rate coefficients have been calculated for the last two. Results are discussed in terms of the modeling of the interaction and advantages of using the Grid is highlighted.

  6. Ion beam irradiation effect on polymers. LET dependence on the chemical reactions and change of mechanical properties

    International Nuclear Information System (INIS)

    High-energy ions of H, He, C, O, Ne, Ar with 10-460 MeV from an AVF cyclotron accelerator were used to irradiate polymer films of 100x100 mm2 area by beam scanning. The changes of mechanical properties and also the chemical reactions such as chain scission or double bond formation were investigated. The linear energy transfer (LET) dependence of the changes of polymer properties was found to be very small when compared with adsorbed dose and was the same as that under gamma ray or electron beam irradiation. It means that the probability and also the mechanisms of chemical reaction should be almost the same even if LET was different. The ion energy would be dispersed widely in the polymer material, where the chemical reaction proceeds rather homogeneously. The chemical reaction sites are not so concentrated in a local area under high LET radiation, and the concentration in the local area might be the same as under low LET radiation. If the track model along the ion path is applied, the diameter may be a few 100 nm for C5+ (220 MeV) ion irradiation and is proportional to the square root of LET

  7. The initiation temperature of chemical reaction in the wave of filtration combustion of gases in the presence of heat sink

    International Nuclear Information System (INIS)

    We consider a single-temperature model of filtration combustion of gases in an inert porous medium in a non-adiabatic formulation. The condition of the initiation of the chemical reaction is obtained by solving the problem of incomplete expending of insufficient component of the gas mixture at zero temperature gradient. (author)

  8. Chemical reaction of sputtered Cu film with PI modified by low energy reactive atomic beam

    International Nuclear Information System (INIS)

    Polyimide (PMDA-ODA) surface was irradiated by low energy reactive atomic beam with energy 160-180 eV to enhance the adhesion with metal Cu film. O2+ and N2+ ions were irradiated at the fluence from 5 x 1015 to 1 x 1018 cm-2. Wetting angle 78o of distilled deionized (DI) water for bare PI was greatly reduced down to 2-4o after critical ion flounce, and the surface energy was increased from 37 to 81.2 erg/cm. From the analysis of O 1s core-level XPS spectra, such improvement seemed to result from the increment of hydrophilic carbonyl oxygen content on modified PI surface. To see more carefully correlation of the peel strength with interfacial reaction between Cu and PI, flexible copper clad laminate with Cu (9 μm)/Cu (200 nm) on modified PI substrate (25 μm) was fabricated by successive sputtering and electroplating. Firstly, peel strength was measured by using t-test and it was largely increased from 0.2 to 0.5 kgf/cm for Ar+ only irradiated PI to 0.72-0.8 kgf/cm for O2+ or N2O+ irradiated PI. Chemical reaction at the interface was reasoned by analyzing C 1s, O 1s, N 1s, and Cu 2p core-level X-ray photoelectron spectroscopy over the as-cleaved Cu-side and PI side surface through depth profiling. From the C 1s spectra of cleaved Cu-side, by the electron transfer from Cu to carbonyl oxygen, carbonyl carbon atom became less positive and as a result shifted to lower binding energy not reaching the binding energy of C2 and C3. The binding energy shift of the peak C4 as small as 1.7 eV indicates that carbonyl oxygen atoms were not completely broken. From the analysis of the O 1s spectra, it was found that new peak at 530.5 eV (O3) was occurred and the increased area of the peak O3 was almost the same with reduced area of the peak carbonyl oxygen peak O1. Since there was no change in the relative intensity of ether oxygen (O2) to carbonyl oxygen (O1), and thus O3 was believed to result from Cu oxide formation via a local bonding of Cu with carbonyl oxygen atoms

  9. A Study on the Role of Reaction Modeling in Multi-phase CFD-based Simulations of Chemical Looping Combustion

    International Nuclear Information System (INIS)

    Chemical Looping Combustion is an energy efficient combustion technology for the inherent separation of carbon dioxide for both gaseous and solid fuels. For scale up and further development of this process multi-phase CFD-based simulations have a strong potential which rely on kinetic models for the solid/gaseous reactions. Reaction models are usually simple in structure in order to keep the computational cost low. They are commonly derived from thermogravimetric experiments. With only few CFD-based simulations performed on chemical looping combustion, there is a lack in understanding of the role and of the sensitivity of the applied chemical reaction model on the outcome of a simulation. The aim of this investigation is therefore the study of three different carrier materials CaSO4, Mn3O4 and NiO with the gaseous fuels H2 and CH4 in a batch type reaction vessel. Four reaction models namely the linear shrinking core, the spherical shrinking core, the Avrami-Erofeev and a recently proposed multi parameter model are applied and compared on a case by case basis. (authors)

  10. Two Optimization Methods to Determine the Rate Constants of a Complex Chemical Reaction Using FORTRAN and MATLAB

    Directory of Open Access Journals (Sweden)

    Abdel-Latif A. Seoud

    2010-01-01

    Full Text Available Problem statement: For chemical reactions, the determination of the rate constants is both very difficult and a time consuming process. The aim of this research was to develop computer programs for determining the rate constants for the general form of any complex reaction at a certain temperature. The development of such program can be very helpful in the control of industrial processes as well as in the study of the reaction mechanisms. Determination of the accurate values of the rate constants would help in establishing the optimum conditions of reactor design including pressure, temperature and other parameters of the chemical reaction. Approach: From the experimental concentration-time data, initial values of rate constants were calculated. Experimental data encountered several types of errors, including temperature variation, impurities in the reactants and human errors. Simulations of a second order consecutive irreversible chemical reaction of the saponification of diethyl ester were presented as an example of the complex reactions. The rate equations (system of simultaneous differential equations of the reaction were solved to get the analytical concentration versus time profiles. The simulation results were compared with experimental results at each measured point. All deviations between experimental and calculated values were squared and summed up to form a new function. This function was fed into a minimizer routine that gave the optimal rate constants. Two optimization techniques were developed using FORTRAN and MATLAB for accurately determining the rate constants of the reaction at certain temperature from the experimental data. Results: Results showed that the two proposed programs were very efficient, fast and accurate tools to determine the true rate constants of the reaction with less 1% error. The use of the MATLAB embedded subroutines for simultaneously solving the differential equations and minimization of the error function

  11. A Detailed Chemical Kinetic Reaction Mechanism for Oxidation of Four Small Alkyl Esters in Laminar Premixed Flames

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Westmoreland, P R; Dryer, F L; Chaos, M; Osswald, P; Kohse-Hoinghaus, K; Cool, T A; Wang, J; Yang, B; Hansen, N; Kasper, T

    2008-02-08

    A detailed chemical kinetic reaction mechanism has been developed for a group of four small alkyl ester fuels, consisting of methyl formate, methyl acetate, ethyl formate and ethyl acetate. This mechanism is validated by comparisons between computed results and recently measured intermediate species mole fractions in fuel-rich, low pressure, premixed laminar flames. The model development employs a principle of similarity of functional groups in constraining the H atom abstraction and unimolecular decomposition reactions in each of these fuels. As a result, the reaction mechanism and formalism for mechanism development are suitable for extension to larger oxygenated hydrocarbon fuels, together with an improved kinetic understanding of the structure and chemical kinetics of alkyl ester fuels that can be extended to biodiesel fuels. Variations in concentrations of intermediate species levels in these flames are traced to differences in the molecular structure of the fuel molecules.

  12. Highly vibrationally excited CO generated in a low-temperature chemical reaction between carbon vapor and molecular oxygen

    Science.gov (United States)

    Jans, E.; Frederickson, K.; Yurkovich, M.; Musci, B.; Rich, J. W.; Adamovich, I. V.

    2016-08-01

    A chemical flow reactor is used to study the vibrational population distribution of CO produced by a reaction between carbon vapor generated in an arc discharge and molecular oxygen. The results demonstrate formation of highly vibrationally excited CO, up to vibrational level v = 14, at low temperatures, T = 400-450 K, with population inversion at v = 4-7, in a collision-dominated environment, 15-20 Torr. The average vibrational energy per CO molecule formed by the reaction is 0.6-1.2 eV/molecule, which corresponds to 10-20% of reaction enthalpy. The results show feasibility of development of a new CO chemical laser using carbon vapor and oxygen as reactants.

  13. Direct measurements of the energy flux due to chemical reactions at the surface of a silicon sample interacting with a SF6 plasma

    CERN Document Server

    Dussart, Remi; Pichon, Laurianne E; Bedra, Larbi; Semmar, Nadjib; Lefaucheux, Philippe; Mathias, Jacky; Tessier, Yves; 10.1063/1.2995988

    2008-01-01

    Energy exchanges due to chemical reactions between a silicon surface and a SF6 plasma were directly measured using a heat flux microsensor (HFM). The energy flux evolution was compared with those obtained when only few reactions occur at the surface to show the part of chemical reactions. At 800 W, the measured energy flux due to chemical reactions is estimated at about 7 W.cm\\^{-2} against 0.4 W.cm\\^{-2} for ion bombardment and other contributions. Time evolution of the HFM signal is also studied. The molar enthalpy of the reaction giving SiF4 molecules was evaluated and is consistent with values given in literature.

  14. 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

  15. Purification of hydrogen under a free or combined form in a gaseous mixture, by chemical reactions with uranium

    International Nuclear Information System (INIS)

    Within the framework of the european fusion program, we are dealing with the purification of hydrogen (tritium) under a free or combined form, from a H2, N2, NH3, CH4, O2, gaseous mixture. The process consists in cracking the hydrogenated molecules and absorbing the impurities by chemical reactions with uranium, without holding back hydrogen. In the temperature range: 950 K < T < 1200 K hydrides are indeed fully decomposed for hydrogen partial pressures lower than ten atmospheres while uranium oxides, nitrides and carbides formation reactions are promoted. The experiments are carried out with massive uranium heated at 973 K in a closed reactor. They confirm that such a process may satisfy our goals, but they point out the importance of interactions occurring between the gaseous and solids systems and interfere with the conversion rates. Gaseous pressure decreases with time according to two successive phases: the first one is governed by a surface kinetic law, while after a short transition time, gas diffusion in the solid products arises and becomes the limiting step of the reactions. Experimental results with pure gases and mixtures, prove that solid products have different structures. An illustrative example is given by nitrogen and methane reactions with uranium: the solid layers are compactely formed with each pure gas and they slow down the chemical kinetic rates; on the contrary the chemical kinetic rates of the mixed gases reactions are clearly increased and the diffusional rates are postponed. Then, the compacity of the solid products merely depends on the operating conditions and the influence of the reactional surface state on the chemical kinetic rates is here pointed out

  16. Evaluation of 237Np reaction amount by chemical analysis of neptunium sample irradiated at experiment fast reactor 'JOYO'

    International Nuclear Information System (INIS)

    The chemical analysis technique was established to determine the nuclide generated in Neptunium (Np) sample with a high accuracy, to contribute to evaluation of transmutation characteristics of 237Np in the fast reactor. (1) Establishment of Chemical Analysis Technique. The chemical analysis technique containing determination technique of fission amount of 237Np, which was consist of Vanadium (V) of capsule material removal and Neodymium (Nd) recovery at high efficiency, was established with optimization of experimental conditions. Four Np samples irradiated in 'JOYO' were analyzed using this technique. Results were as follows. 237Np were determined with high accuracy (relative error was 2.2% at maximum). Errors of fission amount monitoring nuclides 148Nd were half less than that of 137Cs. Small amount of 236Pu was able to determined. (2) Evaluation of 237Np Reaction Amount. The reaction amount of capture, fission and (n, 2n) reactions were evaluated using analyzed values. Transmutation characteristics of 237Np were evaluated using reaction amount. Evaluated results were as follows. The ratio of capture or fission amount to unirradiated 237Np amount were 6.1 - 25.5 at%, 0.7 - 3.6 at%, respectively. The 237Np (n, 2n) 236mNp reaction amount was 7.0 x 10-6 times of 237Np amount at maximum. The dependences of 237Np reaction amount to neutron energy spectrum were revealed from the fact such as linearity of fission to capture reaction amount ratio against fast neutron ratio in same fuel assembly. (author)

  17. 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 coefficien

  18. 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.

  19. 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

  20. 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.

  1. Induction of primary mixed leukocyte reactions with ultraviolet B or chemically modified stimulator cells

    International Nuclear Information System (INIS)

    Treatment of stimulator cells with paraformaldehyde for 60 sec or ultraviolet-B (UV-B) irradiation eliminates their ability to elicit T cell proliferation in a primary mixed leukocyte reaction. However, a T cell response equal to 20-40% of control value could be elicited by paraformaldehyde fixed or UV-B irradiated cells providing the latter are incubated at 37 degrees C for 18 hr prior to treatment. The incubation also induces a one-log increase in the density of fluorescence when the cells are stained with monoclonal antibodies against class II molecules DR and DP as well as the intercellular adhesion molecule -1. We interpret this as an increase in the membrane expression of these structures following incubation. Chloroquine and cerulenin, known to inhibit protein degradation and antigen processing and presentation do not influence the upregulation in membrane expression of these class II and adhesion molecules, but do prevent incubation from overriding the effect of paraformaldehyde treatment. Colchicine, which reduces the traffic through tubular lysosomes, also has no effect on the upregulation but enhances allopresentation. We propose that incubation of stimulator cells in the presence of chloroquine and cerulenin results in the membrane expression of class II molecules without associated peptides. The inability of stimulator cells expressing such nude MHC molecules to elicit T cell proliferation after chemical modification could be due to easier crosslinking of the allodeterminants by paraformaldehyde when the binding site is empty but could also mean that nude MHC molecules are not per se immunogenic and become so only after acquisition of a peptide. It is also possible that chloroquine, NH4Cl, and cerulenin block the expression of signals other than the class II and cell adhesion molecules that are essential for induction of T cell proliferation

  2. Chemical reactions of fission product deposits and iodine transport in primary circuit conditions

    International Nuclear Information System (INIS)

    Highlights: • With CsI precursor, 20% of released iodine was in gaseous form in steam flow at 650 °C. • In similar conditions with Mo, gaseous iodine fraction was increased to 38–79%. • Boron trapped most of the caesium and iodine was almost completely released as gas. - Abstract: The objective of this work was to examine the chemical reactions taking place on primary circuit surfaces and their effect on fission product transport in a severe nuclear reactor accident. Especially transport of gaseous and aerosol phase iodine was studied. Caesium iodide (CsI) was used as precursor material for iodine species. Also, effects of molybdenum and boron on transport of iodine were investigated. The experimental work showed that when CsI alone was used as a precursor, as much as 20% of the released iodine was in gaseous form and the rest as aerosol particles. Aerosol particles were most likely CsI. When the amount of hydrogen in the carrier gas was increased, the fraction of gaseous iodine decreased. When Boron was added to the precursor, a glassy caesium borate surface was formed on the crucible. Boron trapped most of the caesium and also a fraction of iodine, causing almost all released iodine to be in gaseous form. When Mo was introduced in the precursor, most of the iodine was again released in gaseous form. Oxidised Mo reacted with caesium releasing iodine from CsI. The effect of Mo on iodine transport depended much on H2 concentration and was observed to be substantially greater on stainless steel surface. When stainless steel crucible was used, Mo was found in small amounts from aerosol particles, indicating that it was probably released as caesium molybdate or as molybdenum oxide

  3. Sensitivity of chemical reaction networks: a structural approach 3. Regular multimolecular systems

    CERN Document Server

    Brehm, Bernhard

    2016-01-01

    We present a systematic mathematical analysis of the qualitative steady-state response to rate perturbations in large classes of reaction networks. This includes multimolecular reactions and allows for catalysis, enzymatic reactions, multiple reaction products, nonmonotone rate functions, and non-closed autonomous systems. Our structural sensitivity analysis is based on the stoichiometry of the reaction network, only. It does not require numerical data on reaction rates. Instead, we impose mild and generic nondegeneracy conditions of algebraic type. From the structural data, only, we derive which steady-state concentrations are sensitive to, and hence influenced by, changes of any particular reaction rate - and which are not. We also establish transitivity properties for influences involving rate perturbations. This allows us to derive an influence graph which globally summarizes the influence pattern of the given network. The influence graph allows the computational, but meaningful, automatic identification ...

  4. 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

  5. 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/. PMID:26807911

  6. Power optimization of chemically driven heat engine based on first and second order reaction kinetic theory and probability theory

    Science.gov (United States)

    Zhang, Lei; Chen, Lingen; Sun, Fengrui

    2016-03-01

    The finite-time thermodynamic method based on probability analysis can more accurately describe various performance parameters of thermodynamic systems. Based on the relation between optimal efficiency and power output of a generalized Carnot heat engine with a finite high-temperature heat reservoir (heat source) and an infinite low-temperature heat reservoir (heat sink) and with the only irreversibility of heat transfer, this paper studies the problem of power optimization of chemically driven heat engine based on first and second order reaction kinetic theory, puts forward a model of the coupling heat engine which can be run periodically and obtains the effects of the finite-time thermodynamic characteristics of the coupling relation between chemical reaction and heat engine on the power optimization. The results show that the first order reaction kinetics model can use fuel more effectively, and can provide heat engine with higher temperature heat source to increase the power output of the heat engine. Moreover, the power fluctuation bounds of the chemically driven heat engine are obtained by using the probability analysis method. The results may provide some guidelines for the character analysis and power optimization of the chemically driven heat engines.

  7. Quantum chemical study on insertion and abstraction reaction of dichlorocarbene with methyl alcohol and methyl mercaptan

    Institute of Scientific and Technical Information of China (English)

    LI Zhi-Feng; ZHU Yuan-Cheng; LI Hui-Xue; LIU Xin-Wen; LU Xiao-Quan

    2009-01-01

    The Insertion and abstraction reaction mechanisms of singlet and triplet CCl2 with CH3MH (M=O, S) have been studied by using the DFT, NBO and AIM methods. The geometries of reactions, the transition state and products were completely optimized by B3LYP/6-311G(d, p). All the energy of the species was obtained at the CCSD(T)/6-311G(d, p) level. The calculated results indicated that the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl2 can not only trigger the insertion reaction with C-H and M-H in four pathways, by which the products P1 [CH3OCHCl2, reaction I (1)], P3[Cl2HCCH2OH, reaction Ⅰ(2)], PS[CH3SCHCl2, reaction Ⅱ(1)] and P7[Cl2HCCH2SH, reac-tion Ⅱ(2)] are produced respectively, but also abstract M-H, resulting P4 [CH2O+CH2Cl2, reaction Ⅰ(3)] and PS[CH2S+CH2Cl2, reaction Ⅱ (3)]. In addition, the important geometries in domain pathways have been studied by AIM and NBO theories.

  8. Delayed response of interfacial tension in propagating chemical waves of the Belousov-Zhabotinsky reaction without stirring.

    Science.gov (United States)

    Tanaka, Ryo; Nomoto, Tomonori; Toyota, Taro; Kitahata, Hiroyuki; Fujinami, Masanori

    2013-11-01

    Time-resolved measurements of the interfacial tension of propagating chemical waves of the Belousov-Zhabotinsky reaction based on the iron complex catalysts were carried out without stirring by monitoring the frequency of capillary waves with the quasi-elastic laser scattering method. A delayed response of the interfacial tension with respect to absorption was found with the delay being ligand-dependent when the reaction was conducted at a liquid/liquid interface. This behavior is attributed to differences in adsorption activity of the hydrophobic metal catalyst. The delay time and the increase in interfacial tension were also reproduced by a model considering the rate constants of equilibrium adsorption. PMID:24107133

  9. Electronic processes in fast thermite chemical reactions: A first-principles molecular dynamics study

    Science.gov (United States)

    Shimojo, Fuyuki; Nakano, Aiichiro; Kalia, Rajiv K.; Vashishta, Priya

    2008-06-01

    Rapid reaction of a molten metal with an oxide is the key to understanding recently discovered fast reactions in nanothermite composites. We have investigated the thermite reaction of Fe2O3 with aluminum by molecular dynamics simulations with interatomic forces calculated quantum mechanically in the framework of the density functional theory. A redox reaction to form iron metal and Al2O3 initiates with the rapid formation of Al-O bonds at the interface within 1 ps, followed by the propagation of the combustion front with a velocity of 70 m/s for at least 5 ps at 2000 K. The reaction time for an oxygen atom to change character from Fe2O3 type to Al2O3 type at the interface is estimated to be 1.7±0.9ps , and bond-overlap population analysis has been used to calculate reaction rates.

  10. Quantum chemical investigation of the reaction of O(32) with certain hydrocarbon radicals

    Indian Academy of Sciences (India)

    Ashutosh Gupta; R P Singh; V B Singh; Brijesh Kumar Mishra; N Sathyamurthy

    2007-09-01

    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 been computed. The possible product channels and the reaction pathways are identified in each case. In the case of methyl radical the minimum energy reaction pathway leads to the products CO + H2 + H. In the case of ethyl radical the most facile pathway leads to the products, methanal + CH3 radical. For propyl radical (- and iso-), the minimum energy reaction pathway would lead to the channel containing ethanal + methyl radical.

  11. Arrhenius' law in turbulent media and an equivalent tunnel effect. [in binary exchange chemical reactions

    Science.gov (United States)

    Tsuge, S.; Sagara, K.

    1978-01-01

    The indeterminacy inherent to the formal extension of Arrhenius' law to reactions in turbulent flows is shown to be surmountable in the case of a binary exchange reaction with a sufficiently high activation energy. A preliminary calculation predicts that the turbulent reaction rate is invariant in the Arrhenius form except for an equivalently lowered activation energy. This is a reflection of turbulence-augmented molecular vigor, and causes an appreciable increase in the reaction rate. A similarity to the tunnel effect in quantum mechanics is indicated. The anomaly associated with the mild ignition of oxy-hydrogen mixtures is discussed in this light.

  12. 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....

  13. Analysis of gas absorption to a thin liquid film in the presence of a zero-order chemical reaction

    Science.gov (United States)

    Rajagopalan, S.; Rahman, M. M.

    1995-01-01

    The paper presents a detailed theoretical analysis of the process of gas absorption to a thin liquid film adjacent to a horizontal rotating disk. The film is formed by the impingement of a controlled liquid jet at the center of the disk and subsequent radial spreading of liquid along the disk. The chemical reaction between the gas and the liquid film can be expressed as a zero-order homogeneous reaction. The process was modeled by establishing equations for the conservation of mass, momentum, and species concentration and solving them analytically. A scaling analysis was used to determine dominant transport processes. Appropriate boundary conditions were used to solve these equations to develop expressions for the local concentration of gas across the thickness of the film and distributions of film height, bulk concentration, and Sherwood number along the radius of the disk. The partial differential equation for species concentration was solved using the separation of variables technique along with the Duhamel's theorem and the final analytical solution was expressed using confluent hypergeometric functions. Tables for eigenvalues and eigenfunctions are presented for a number of reaction rate constants. A parametric study was performed using Reynolds number, Ekman number, and dimensionless reaction rate as parameters. At all radial locations, Sherwood number increased with Reynolds number (flow rate) as well as Ekman number (rate of rotation). The enhancement of mass transfer due to chemical reaction was found to be small when compared to the case of no reaction (pure absorption), but the enhancement factor was very significant when compared to pure absorption in a stagnant liquid film. The zero-order reaction processes considered in the present investigation included the absorption of oxygen in aqueous alkaline solutions of sodiumdithionite and rhodium complex catalyzed carbonylation of methanol. Present analytical results were compared to previous theoretical

  14. Stochastic Modeling of CO2 Migrations and Chemical Reactions in Deep Saline Formations

    Science.gov (United States)

    Ni, C.; Lee, I.; Lin, C.

    2013-12-01

    Carbon capture and storage (CCS) has been recognized the feasible technology that can significant reduce the anthropogenic CO2 emissions from large point sources. The CO2 injection in geological formations is one of the options to permanently store the captured CO2. Based on this concept a large number of target formations have been identified and intensively investigated with different types of techniques such as the hydrogeophysical experiments or numerical simulations. The numerical simulations of CO2 migrations in saline formations recently gather much attention because a number of models are available for this purpose and there are potential sites existing in many countries. The lower part of Cholan Formation (CF) near Changhua Coastal Industrial Park (CCIP) in west central Taiwan was identified the largest potential site for CO2 sequestration. The top elevations of the KF in this area varies from 1300 to 1700m below the sea level. Laboratory experiment showed that the permeability of CF is 10-14 to 10-12 m2. Over the years the offshore seismic survey and limited onshore borehole logs have provided information for the simulation of CO2 migration in the CF although the original investigations might not focus on the purpose of CO2 sequestration. In this study we modify the TOUGHREACT model to consider the small-scale heterogeneity in target formation and the cap rock of upper CF. A Monte Carlo Simulation (MCS) approach based on the TOUGHREACT model is employed to quantify the effect of small-scale heterogeneity on the CO2 migrations and hydrochemical reactions in the CF. We assume that the small-scale variability of permeability in KF can be described with a known Gaussian distribution. Therefore, the Gaussian type random field generator such as Sequential Gaussian Simulation (SGSIM) in Geostatistical Software Library (GSLIB) can be used to provide the random permeability realizations for the MCS. A variety of statistical parameters such as the variances and

  15. Identification of Maillard reaction induced chemical modifications on Ara h 1

    Science.gov (United States)

    The Maillard reaction is a non-enzymatic glycation reaction between proteins and reducing sugars that can modify nut allergens during thermal processing. These modifications can alter the structural and immunological properties of these allergens, and may result in increased IgE binding. Here, we ...

  16. Iterative approach to the characteristic time for chemical reactions of type A + B ! C + D

    CERN Document Server

    Aldrovandi, R

    2013-01-01

    The analytic solution for the kinetic description of binary reactions can be seen as the continuum version of a basic discrete iterate mapping. This fact allows a clear definition of the reaction characteristic time which takes the backward effect into account.

  17. Encapsulated nano-heat-sinks for thermal management of heterogeneous chemical reactions.

    Science.gov (United States)

    Zhang, Minghui; Hong, Yan; Ding, Shujiang; Hu, Jianjun; Fan, Yunxiao; Voevodin, Andrey A; Su, Ming

    2010-12-01

    This paper describes a new way to control temperatures of heterogeneous exothermic reactions such as heterogeneous catalytic reaction and polymerization by using encapsulated nanoparticles of phase change materials as thermally functional additives. Silica-encapsulated indium nanoparticles and silica encapsulated paraffin nanoparticles are used to absorb heat released in catalytic reaction and to mitigate gel effect of polymerization, respectively. The local hot spots that are induced by non-homogenous catalyst packing, reactant concentration fluctuation, and abrupt change of polymerization rate lead to solid to liquid phase change of nanoparticle cores so as to avoid thermal runaway by converting energies from exothermic reactions to latent heat of fusion. By quenching local hot spots at initial stage, reaction rates do not rise significantly because the thermal energy produced in reaction is isothermally removed. Nanoparticles of phase change materials will open a new dimension for thermal management of exothermic reactions to quench local hot spots, prevent thermal runaway of reaction, and change product distribution. PMID:20967399

  18. Detailed Chemical Kinetic Reaction Mechanisms for Primary Reference Fuels for Diesel Cetane Number and Spark-Ignition Octane Number

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-03-03

    For the first time, a detailed chemical kinetic reaction mechanism is developed for primary reference fuel mixtures of n-hexadecane and 2,2,4,4,6,8,8-heptamethyl nonane for diesel cetane ratings. The mechanisms are constructed using existing rules for reaction pathways and rate expressions developed previously for the primary reference fuels for gasoline octane ratings, n-heptane and iso-octane. These reaction mechanisms are validated by comparisons between computed and experimental results for shock tube ignition and for oxidation under jet-stirred reactor conditions. The combined kinetic reaction mechanism contains the submechanisms for the primary reference fuels for diesel cetane ratings and submechanisms for the primary reference fuels for gasoline octane ratings, all in one integrated large kinetic reaction mechanism. Representative applications of this mechanism to two test problems are presented, one describing fuel/air autoignition variations with changes in fuel cetane numbers, and the other describing fuel combustion in a jet-stirred reactor environment with the fuel varying from pure 2,2,4,4,6,8,8-heptamethyl nonane (Cetane number of 15) to pure n-hexadecane (Cetane number of 100). The final reaction mechanism for the primary reference fuels for diesel fuel and gasoline is available on the web.

  19. A Coupled Dynamical Model of Redox Flow Battery Based on Chemical Reaction, Fluid Flow, and Electrical Circuit

    OpenAIRE

    Li, Minghua; Hikihara, Takashi

    2008-01-01

    The redox (Reduction-Oxidation) flow battery is one of the most promising rechargeable batteries due to its ability to average loads and output of power sources. The transient characteristics are well known as the remarkable feature of the battery. Then it can also compensate for a sudden voltage drop. The dynamics are governed by the chemical reactions, fluid flow, and electrical circuit of its structure. This causes the difficulty of the analysis at transient state. This paper discusses the...

  20. Influence of reaction parameters on synthesis of high-quality single-layer graphene on Cu using chemical vapor deposition

    International Nuclear Information System (INIS)

    Large-area monolayer graphene samples grown on polycrystalline copper foil by thermal chemical vapor deposition with differing CH4 flux and growth time are investigated by Raman spectra, scanning electron microscopy, atomic force microscopy, and scanning tunneling microscopy. The defects, number of layers, and quality of graphene are shown to be controllable through tuning the reaction conditions: ideally to 2–3 sccm CH4 for 30 minutes. (rapid communication)