WorldWideScience

Sample records for chemical reaction yield

  1. RADIOCHEMICAL YIELDS OF GRAFT POLYMERIZATION REACTIONS OF CELLULOSE

    Energy Technology Data Exchange (ETDEWEB)

    Arthur, Jr, J C; Blouin, F A

    1963-12-15

    The preparation of radioinduced graft polymers of cotton cellulose, while retaining the fibrous nature and high molecular weight of the cellulose, depended primarily on the radiochemical yields of cellulose reactions and of graft polymerization reactions. Yields of the initial major molecular changes in cellulosic polymer indicated that, in the case of scission of the molecule and carboxyl group formation, chain reactions were not initiated by radiation; however, in the case of carbonyl group formation chain reactions were initiated but quickly terminated. Generally, experimental procedures, used in graft polymerization reactions, were: simultaneous irradiation reactions, that is, application of monomers or solutions of monomers to cellulose or chemically modified celluloses, then irradiation; and post-irradiation reactions, that is, irradiation of cellulose or chemically modified celluloses, then after removal from the field of radiation, contacting the irradiated cellulose with monomer. Some of the most important factors influencing the radiochemical yields of graft polymerization reactions, of styrene and acrylonitrile onto cellulose were: concentration of monomer in treating solution; solvent; ratio of monomer solution to cellulose; prior chemical modification of cellulose; and absence of oxygen, particularly in post-irradiation reactions. Experimental data are presented, and the direct and indirect effects of Co/sup 60/ gamma radiation on these reactions are discussed. (auth)

  2. Infrared laser-induced chemical reactions

    International Nuclear Information System (INIS)

    Katayama, Mikio

    1978-01-01

    The experimental means which clearly distinguishes between infrared ray-induced reactions and thermal reactions has been furnished for the first time when an intense monochromatic light source has been obtained by the development of infrared laser. Consequently, infrared laser-induced chemical reactions have started to develop as one field of chemical reaction researches. Researches of laser-induced chemical reactions have become new means for the researches of chemical reactions since they were highlighted as a new promising technique for isotope separation. Specifically, since the success has been reported in 235 U separation using laser in 1974, comparison of this method with conventional separation techniques from the economic point of view has been conducted, and it was estimated by some people that the laser isotope separation is cheaper. This report briefly describes on the excitation of oscillation and reaction rate, and introduces the chemical reactions induced by CW laser and TEA CO 2 laser. Dependence of reaction yield on laser power, measurement of the absorbed quantity of infrared ray and excitation mechanism are explained. Next, isomerizing reactions are reported, and finally, isotope separation is explained. It was found that infrared laser-induced chemical reactions have the selectivity for isotopes. Since it is evident that there are many examples different from thermal and photo-chemical reactions, future collection of the data is expected. (Wakatsuki, Y.)

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

    Science.gov (United States)

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

    2014-03-11

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

  4. Chemical reactions confined within carbon nanotubes.

    Science.gov (United States)

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

    2016-08-22

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

  5. Predicting oil and gas compositional yields via chemical structure-chemical yield modeling (CS-CYM): Part 1 - Concepts and implementation

    Energy Technology Data Exchange (ETDEWEB)

    Freund, H.; Walters, C.C.; Kelemen, S.R.; Siskin, M.; Gorbaty, M.L.; Curry, D.J.; Bence, A.E. [ExxonMobil Research & Engineering Co., Annandale, NJ (United States)

    2007-07-01

    We have developed a method to calculate the amounts and composition of products resulting from the thermal decomposition of a solid complex carbonaceous material. This procedure provides a means of using laboratory measurements of complex carbonaceous solids to construct a representative model of its chemical structure (CS) that is then coupled with elementary reaction pathways to predict the chemical yield (CY) upon thermal decomposition. Data from elemental analysis, H, N, O, S, solid state {sup 13}C NMR, X-ray photoelectron spectroscopy (XPS), sulfur X-ray absorption structure spectroscopy (XANES), and pyrolysis-gas chromatography (GC) are used to constrain the construction of core molecular structures representative of the complex carbonaceous material. These core structures are expanded stochastically to describe large macromolecules ({gt} 10{sup 6} cores with similar to 10{sup 6} atoms) with bulk properties that match the experimental results. Gas, liquid and solid product yields, resulting from thermal decomposition, are calculated by identifying reactive functional groups within the CS stochastic ensemble and imposing a reaction network constrained by fundamental thermodynamics and kinetics. An expulsion model is added to the decomposition model to calculate the chemical products in open and closed systems. Product yields may then be predicted under a wide range of time-temperature conditions used in rapid laboratory pyrolysis experiments, refinery processes, or geologic maturation.

  6. Kinetics of chemical reactions initiated by hot atoms

    International Nuclear Information System (INIS)

    Firsova, L.P.

    1977-01-01

    Modern ideas about kinetics of chemical reactions of hot atoms are generalized. The main points of the phenomenological theories (''kinetic theory'' of Wolfgang-Estrup hot reactions and the theory of ''reactions integral probability'' of Porter) are given. Physico-chemical models of elastic and non-elastic collisions are considered which are used in solving Boltzmann integro-differential equations and stochastic equations in the Porter theory. The principal formulas are given describing probabilities or yields of chemical reactions, initiated with hot atoms, depending on the distribution functions of hot particles with respect to energy. Briefly described are the techniques and the results of applying the phenomenological theories for interpretation of the experimental data obtained during nuclear reactions with hot atoms, photochemical investigations, etc. 96 references are given

  7. Yield of 73Se for various reactions and its chemical processing

    International Nuclear Information System (INIS)

    Nozaki, T.; Itoh, Y.; Ogawa, K.

    1979-01-01

    Excitation curves for the formation of 73 Se by the following reactions were measured up to proton energy of 50 MeV and 3 He- and α-particle energies of 40 MeV, together with those for byproduct formation reactions: (1) 75 As(p, 3n) 73 Se, (2) Ge + 3 He → 73 Se, and (3) Ge + α → 73 Se. The proton reaction has proved to be much superior to the other reactions both in yield and product purity. Volatilization of 73 Se from a solution of condensed polyphosphoric acid was found to give an excellent method of 73 Se separation from various arsenic targets without carrier. Also, solvent extraction of red selenium 73 Se with a minute amount of carrier was shown to be a useful separation method. (author)

  8. Insights into the mechanisms on chemical reactions: reaction paths for chemical reactions

    International Nuclear Information System (INIS)

    Dunning, T.H. Jr.; Rosen, E.; Eades, R.A.

    1987-01-01

    We report reaction paths for two prototypical chemical reactions: Li + HF, an electron transfer reaction, and OH + H 2 , an abstraction reaction. In the first reaction we consider the connection between the energetic terms in the reaction path Hamiltonian and the electronic changes which occur upon reaction. In the second reaction we consider the treatment of vibrational effects in chemical reactions in the reaction path formalism. 30 refs., 9 figs

  9. Track models and radiation chemical yields

    International Nuclear Information System (INIS)

    Chatterjee, A.; Magee, J.L.

    1987-01-01

    The authors are concerned only with systems in which single track effects dominate and radiation chemical yields are sums of yields for individual tracks. The authors know that the energy deposits of heavy particle tracks are composed of spurs along the particle trajectory (about one-half of the energy) and a more diffuse pattern composed of the tracks of knock-on electrons, called the penumbra (about one-half of the energy). The simplest way to introduce the concept of a unified track model for heavy particles is to consider the special case of the track of a heavy particle with an LET below 0.2-0.3eV/A, which in practice limits us to protons, deuterons, or particles with energy above 100 MeV per nucleon. At these LET values, to a good approximation, spurs formed by the main particle track can be considered to remain isolated throughout the radiation chemical reactions

  10. 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...

  11. 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...... as well as the possibility for establishing a renewable chemical industry is discussed. The development of a procedure for using unsaturated aldehydes as olefin synthons in the Diels- Alder reaction is described in chapter three. This procedure affords good yields of the desired Diels- Alder adducts...... 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...

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

    Science.gov (United States)

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

    2014-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Diogo A R S Latino

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

  14. 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

  15. Global Controllability of Chemical Reactions

    OpenAIRE

    Drexler, Dániel András; Tóth, János

    2015-01-01

    Controllability of chemical reactions is an important problem in chemical engineering science. In control theory, analysis of the controllability of linear systems is well-founded, however the dynamics of chemical reactions is usually nonlinear. Global controllability properties of chemical reactions are analyzed here based on the Lie-algebra of the vector fields associated to elementary reactions. A chemical reaction is controllable almost everywhere if all the reaction rate coefficients can...

  16. Systematic trends in photonic reagent induced reactions in a homologous chemical family.

    Science.gov (United States)

    Tibbetts, Katharine Moore; Xing, Xi; Rabitz, Herschel

    2013-08-29

    The growing use of ultrafast laser pulses to induce chemical reactions prompts consideration of these pulses as "photonic reagents" in analogy to chemical reagents. This work explores the prospect that photonic reagents may affect systematic trends in dissociative ionization reactions of a homologous family of halomethanes, much as systematic outcomes are often observed for reactions between homologous families of chemical reagents and chemical substrates. The experiments in this work with photonic reagents of varying pulse energy and linear spectral chirp reveal systematic correlations between observable ion yields and the following set of natural variables describing the substrate molecules: the ionization energy of the parent molecule, the appearance energy of each fragment ion, and the relative strength of carbon-halogen bonds in molecules containing two different halogens. The results suggest that reactions induced by photonic reagents exhibit systematic behavior analogous to that observed in reactions driven by chemical reagents, which provides a basis to consider empirical "rules" for predicting the outcomes of photonic reagent induced reactions.

  17. Sintering with a chemical reaction as applied to uranium monocarbide

    International Nuclear Information System (INIS)

    Accary, A.; Caillat, R.

    1960-01-01

    The present paper provides a survey of different investigations whose aim was the preparation and fabrication of uranium monocarbide for nuclear use. If a chemical reaction takes place in the sample during the sintering operation, it may be expected that the atom rearrangements involved in this reaction should favour the sintering process and thereby lower the temperature needed to yield a body of a given density. With this hypothesis in mind, the following methods have been studied: - Sintering of U-C mixtures; - Sintering of UO 2 -C mixtures; - Hot pressing of U-C mixtures; - Extrusion of U-C mixtures. To generalize our result, it could be said that a chemical reaction does not lead to high densification, if one depends on a simple contact between discrete particles. On the contrary, a chemical reaction can help sintering if, as our hot pressing experiments shows, the densification can be achieved prior to the reaction. (author) [fr

  18. Microfluidic chemical reaction circuits

    Science.gov (United States)

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

    2012-06-26

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

  19. Reformulation and solution of the master equation for multiple-well chemical reactions.

    Science.gov (United States)

    Georgievskii, Yuri; Miller, James A; Burke, Michael P; Klippenstein, Stephen J

    2013-11-21

    We consider an alternative formulation of the master equation for complex-forming chemical reactions with multiple wells and bimolecular products. Within this formulation the dynamical phase space consists of only the microscopic populations of the various isomers making up the reactive complex, while the bimolecular reactants and products are treated equally as sources and sinks. This reformulation yields compact expressions for the phenomenological rate coefficients describing all chemical processes, i.e., internal isomerization reactions, bimolecular-to-bimolecular reactions, isomer-to-bimolecular reactions, and bimolecular-to-isomer reactions. The applicability of the detailed balance condition is discussed and confirmed. We also consider the situation where some of the chemical eigenvalues approach the energy relaxation time scale and show how to modify the phenomenological rate coefficients so that they retain their validity.

  20. Introduction to chemical reaction engineering

    International Nuclear Information System (INIS)

    Kim, Yeong Geol

    1990-10-01

    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.

  1. 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.

  2. Reaction Decoder Tool (RDT): extracting features from chemical reactions.

    Science.gov (United States)

    Rahman, Syed Asad; Torrance, Gilliean; Baldacci, Lorenzo; Martínez Cuesta, Sergio; Fenninger, Franz; Gopal, Nimish; Choudhary, Saket; May, John W; Holliday, Gemma L; Steinbeck, Christoph; Thornton, Janet M

    2016-07-01

    Extracting chemical features like Atom-Atom Mapping (AAM), Bond Changes (BCs) and Reaction Centres from biochemical reactions helps us understand the chemical composition of enzymatic reactions. Reaction Decoder is a robust command line tool, which performs this task with high accuracy. It supports standard chemical input/output exchange formats i.e. RXN/SMILES, computes AAM, highlights BCs and creates images of the mapped reaction. This aids in the analysis of metabolic pathways and the ability to perform comparative studies of chemical reactions based on these features. This software is implemented in Java, supported on Windows, Linux and Mac OSX, and freely available at https://github.com/asad/ReactionDecoder : asad@ebi.ac.uk or s9asad@gmail.com. © The Author 2016. Published by Oxford University Press.

  3. Chemical burn or reaction

    Science.gov (United States)

    Chemicals that touch skin can lead to a reaction on the skin, throughout the body, or both. ... leave the person alone and watch carefully for reactions affecting the entire body. Note: If a chemical gets into the eyes, the eyes should be ...

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

    International Nuclear Information System (INIS)

    Sugimoto, Shun-ichi; Nishii, Masanobu

    1985-01-01

    Previous studies of radiation induced chemical reactions of CO-H 2 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-H 2 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-H 2 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 (NH 3 ) and radical scavenger (O 2 ) on the products yields were also carried out on the CO-H 2 -CH 4 mixture. (author)

  5. Calculation of total free energy yield as an alternative approach for predicting the importance of potential chemolithotrophic reactions in geothermal springs.

    Science.gov (United States)

    Dodsworth, Jeremy A; McDonald, Austin I; Hedlund, Brian P

    2012-08-01

    To inform hypotheses regarding the relative importance of chemolithotrophic metabolisms in geothermal environments, we calculated free energy yields of 26 chemical reactions potentially supporting chemolithotrophy in two US Great Basin hot springs, taking into account the effects of changing reactant and product activities on the Gibbs free energy as each reaction progressed. Results ranged from 1.2 × 10(-5) to 3.6 J kg(-1) spring water, or 3.7 × 10(-5) to 11.5 J s(-1) based on measured flow rates, with aerobic oxidation of CH(4) or NH4 + giving the highest average yields. Energy yields calculated without constraining pH were similar to those at constant pH except for reactions where H(+) was consumed, which often had significantly lower yields when pH was unconstrained. In contrast to the commonly used normalization of reaction chemical affinities per mole of electrons transferred, reaction energy yields for a given oxidant varied by several orders of magnitude and were more sensitive to differences in the activities of products and reactants. The high energy yield of aerobic ammonia oxidation is consistent with previous observations of significant ammonia oxidation rates and abundant ammonia-oxidizing archaea in sediments of these springs. This approach offers an additional lens through which to view the thermodynamic landscape of geothermal springs. © 2012 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

  6. 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.

  7. Study of pp{yields}pp{eta} reaction at threshold; Etude de la reaction pp{yields}pp{eta} au seuil

    Energy Technology Data Exchange (ETDEWEB)

    Taleb, A

    1994-11-01

    The {eta} production has been studied through the pp {yields} pp{eta} reaction at threshold. Data were taken at the Synchrotron of the ``Laboratoire National Saturne``. The detection in coincidence of the two protons scattered near 0 deg and analysed with the magnetic spectrometer SPES3 allows the reconstruction of missing mass spectra for the {eta} signature. A simulation program which takes into account all the experimental set up characteristics has been realized and tested through the pp {yields} d{pi}{sup +} reaction detected simultaneously with pp {yields} pp{eta}. The generated proton momentum spectra for pp {yields} pp{eta} show a pronounced {eta} mass dependence. This characteristic, connected to the kinematical properties of pp {yields} pp{eta} at threshold, is used to extract the mass of the meson {eta}. The obtained value, m{sub {eta}} = 547.65 {+-} 0.18 MeV, is in good agreement with measurement done recently through the pd {yields} {sup H}e{eta} reaction. The total cross section {sigma}{sub t} of pp {yields} pp{eta} measured at 1260, 1265 and 1300 MeV presents a strong energy dependence. This cross section increases less with energy than the phase-space. The influence of p-p and {eta}-p final state interactions in our measurements is studied. Our results are compared with theoretical predictions and assess the dominant character of the baryonic resonance N{sup *}(1535) in the {eta} mechanism production at threshold. These experimental results give an energy dependence which is not well reproduced by the theoretical predictions. This discrepancy could be an incorrect description of the {eta}-p interaction in the models. (author). 48 refs., 60 figs., 15 tabs.

  8. 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

  9. Chemical kinetics and reaction mechanism

    International Nuclear Information System (INIS)

    Jung, Ou Sik; Park, Youn Yeol

    1996-12-01

    This book is about chemical kinetics and reaction mechanism. It consists of eleven chapters, which deal with reaction and reaction speed on reaction mechanism, simple reaction by rate expression, reversible reaction and simultaneous reaction, successive reaction, complicated reaction mechanism, assumption for reaction mechanism, transition state theory, successive reaction and oscillating reaction, reaction by solution, research method high except kinetics on reaction mechanism, high reaction of kinetics like pulsed radiolysis.

  10. Chemical potential and reaction electronic flux in symmetry controlled reactions.

    Science.gov (United States)

    Vogt-Geisse, Stefan; Toro-Labbé, Alejandro

    2016-07-15

    In symmetry controlled reactions, orbital degeneracies among orbitals of different symmetries can occur along a reaction coordinate. In such case Koopmans' theorem and the finite difference approximation provide a chemical potential profile with nondifferentiable points. This results in an ill-defined reaction electronic flux (REF) profile, since it is defined as the derivative of the chemical potential with respect to the reaction coordinate. To overcome this deficiency, we propose a new way for the calculation of the chemical potential based on a many orbital approach, suitable for reactions in which symmetry is preserved. This new approach gives rise to a new descriptor: symmetry adapted chemical potential (SA-CP), which is the chemical potential corresponding to a given irreducible representation of a symmetry group. A corresponding symmetry adapted reaction electronic flux (SA-REF) is also obtained. Using this approach smooth chemical potential profiles and well defined REFs are achieved. An application of SA-CP and SA-REF is presented by studying the Cs enol-keto tautomerization of thioformic acid. Two SA-REFs are obtained, JA'(ξ) and JA'' (ξ). It is found that the tautomerization proceeds via an in-plane delocalized 3-center 4-electron O-H-S hypervalent bond which is predicted to exist only in the transition state (TS) region. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

  11. Diabatic models with transferrable parameters for generalized chemical reactions

    International Nuclear Information System (INIS)

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

    2017-01-01

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

  12. Modeling chemical reactions for drug design.

    Science.gov (United States)

    Gasteiger, Johann

    2007-01-01

    Chemical reactions are involved at many stages of the drug design process. This starts with the analysis of biochemical pathways that are controlled by enzymes that might be downregulated in certain diseases. In the lead discovery and lead optimization process compounds have to be synthesized in order to test them for their biological activity. And finally, the metabolism of a drug has to be established. A better understanding of chemical reactions could strongly help in making the drug design process more efficient. We have developed methods for quantifying the concepts an organic chemist is using in rationalizing reaction mechanisms. These methods allow a comprehensive modeling of chemical reactivity and thus are applicable to a wide variety of chemical reactions, from gas phase reactions to biochemical pathways. They are empirical in nature and therefore allow the rapid processing of large sets of structures and reactions. We will show here how methods have been developed for the prediction of acidity values and of the regioselectivity in organic reactions, for designing the synthesis of organic molecules and of combinatorial libraries, and for furthering our understanding of enzyme-catalyzed reactions and of the metabolism of drugs.

  13. Amazing variational approach to chemical reactions

    OpenAIRE

    Fernández, Francisco M.

    2009-01-01

    In this letter we analyse an amazing variational approach to chemical reactions. Our results clearly show that the variational expressions are unsuitable for the analysis of empirical data obtained from chemical reactions.

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

    Science.gov (United States)

    Fooshee, David; Andronico, Alessio; Baldi, Pierre

    2013-11-25

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

  15. Learning to predict chemical reactions.

    Science.gov (United States)

    Kayala, Matthew A; Azencott, Chloé-Agathe; Chen, Jonathan H; Baldi, Pierre

    2011-09-26

    Being able to predict the course of arbitrary chemical reactions is essential to the theory and applications of organic chemistry. Approaches to the reaction prediction problems can be organized around three poles corresponding to: (1) physical laws; (2) rule-based expert systems; and (3) inductive machine learning. Previous approaches at these poles, respectively, are not high throughput, are not generalizable or scalable, and lack sufficient data and structure to be implemented. We propose a new approach to reaction prediction utilizing elements from each pole. Using a physically inspired conceptualization, we describe single mechanistic reactions as interactions between coarse approximations of molecular orbitals (MOs) and use topological and physicochemical attributes as descriptors. Using an existing rule-based system (Reaction Explorer), we derive a restricted chemistry data set consisting of 1630 full multistep reactions with 2358 distinct starting materials and intermediates, associated with 2989 productive mechanistic steps and 6.14 million unproductive mechanistic steps. And from machine learning, we pose identifying productive mechanistic steps as a statistical ranking, information retrieval problem: given a set of reactants and a description of conditions, learn a ranking model over potential filled-to-unfilled MO interactions such that the top-ranked mechanistic steps yield the major products. The machine learning implementation follows a two-stage approach, in which we first train atom level reactivity filters to prune 94.00% of nonproductive reactions with a 0.01% error rate. Then, we train an ensemble of ranking models on pairs of interacting MOs to learn a relative productivity function over mechanistic steps in a given system. Without the use of explicit transformation patterns, the ensemble perfectly ranks the productive mechanism at the top 89.05% of the time, rising to 99.86% of the time when the top four are considered. Furthermore, the system

  16. Learning to Predict Chemical Reactions

    Science.gov (United States)

    Kayala, Matthew A.; Azencott, Chloé-Agathe; Chen, Jonathan H.

    2011-01-01

    Being able to predict the course of arbitrary chemical reactions is essential to the theory and applications of organic chemistry. Approaches to the reaction prediction problems can be organized around three poles corresponding to: (1) physical laws; (2) rule-based expert systems; and (3) inductive machine learning. Previous approaches at these poles respectively are not high-throughput, are not generalizable or scalable, or lack sufficient data and structure to be implemented. We propose a new approach to reaction prediction utilizing elements from each pole. Using a physically inspired conceptualization, we describe single mechanistic reactions as interactions between coarse approximations of molecular orbitals (MOs) and use topological and physicochemical attributes as descriptors. Using an existing rule-based system (Reaction Explorer), we derive a restricted chemistry dataset consisting of 1630 full multi-step reactions with 2358 distinct starting materials and intermediates, associated with 2989 productive mechanistic steps and 6.14 million unproductive mechanistic steps. And from machine learning, we pose identifying productive mechanistic steps as a statistical ranking, information retrieval, problem: given a set of reactants and a description of conditions, learn a ranking model over potential filled-to-unfilled MO interactions such that the top ranked mechanistic steps yield the major products. The machine learning implementation follows a two-stage approach, in which we first train atom level reactivity filters to prune 94.00% of non-productive reactions with a 0.01% error rate. Then, we train an ensemble of ranking models on pairs of interacting MOs to learn a relative productivity function over mechanistic steps in a given system. Without the use of explicit transformation patterns, the ensemble perfectly ranks the productive mechanism at the top 89.05% of the time, rising to 99.86% of the time when the top four are considered. Furthermore, the system

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

    International Nuclear Information System (INIS)

    Roh, Heui-Seol

    2015-01-01

    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. Using Simulation to Increase Yields in Chemical Engineering

    Directory of Open Access Journals (Sweden)

    William C. Conley

    2003-06-01

    Full Text Available Trying to increase the yields or profit or efficiency (less pollution of chemical processes is a central goal of the chemical engineer in theory and practice. Certainly sound training in chemistry, business and pollution control help the engineer to set up optimal chemical processes. However, the ever changing demands of customers and business conditions, plus the multivariate complexity of the chemical business can make optimization challenging. Mathematical tools such as statistics and linear programming have certainly been useful to chemical engineers in their pursuit of optimal efficiency. However, some processes can be modeled linearly and some can not. Therefore, presented here will be an industrial chemical process with potentially five variables affecting the yield. Data from over one hundred runs of the process has been collected, but it is not known initially whether the yield relationship is linear or nonlinear. Therefore, the CTSP multivariate correlation coefficient will be calculated for the data to see if a relationship exists among the variables. Then once it is proven that there is a statistically significant relationship, an appropriate linear or nonlinear equation can be fitted to the data, and it can be optimized for use in the chemical plant.

  19. Mining chemical reactions using neighborhood behavior and condensed graphs of reactions approaches.

    Science.gov (United States)

    de Luca, Aurélie; Horvath, Dragos; Marcou, Gilles; Solov'ev, Vitaly; Varnek, Alexandre

    2012-09-24

    This work addresses the problem of similarity search and classification of chemical reactions using Neighborhood Behavior (NB) and Condensed Graphs of Reaction (CGR) approaches. The CGR formalism represents chemical reactions as a classical molecular graph with dynamic bonds, enabling descriptor calculations on this graph. Different types of the ISIDA fragment descriptors generated for CGRs in combination with two metrics--Tanimoto and Euclidean--were considered as chemical spaces, to serve for reaction dissimilarity scoring. The NB method has been used to select an optimal combination of descriptors which distinguish different types of chemical reactions in a database containing 8544 reactions of 9 classes. Relevance of NB analysis has been validated in generic (multiclass) similarity search and in clustering with Self-Organizing Maps (SOM). NB-compliant sets of descriptors were shown to display enhanced mapping propensities, allowing the construction of better Self-Organizing Maps and similarity searches (NB and classical similarity search criteria--AUC ROC--correlate at a level of 0.7). The analysis of the SOM clusters proved chemically meaningful CGR substructures representing specific reaction signatures.

  20. Femtosecond laser control of chemical reactions

    CSIR Research Space (South Africa)

    Du Plessis, A

    2010-08-31

    Full Text Available Femtosecond laser control of chemical reactions is made possible through the use of pulse-shaping techniques coupled to a learning algorithm feedback loop – teaching the laser pulse to control the chemical reaction. This can result in controllable...

  1. 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).

  2. Generating Converged Accurate Free Energy Surfaces for Chemical Reactions with a Force-Matched Semiempirical Model.

    Science.gov (United States)

    Kroonblawd, Matthew P; Pietrucci, Fabio; Saitta, Antonino Marco; Goldman, Nir

    2018-04-10

    We demonstrate the capability of creating robust density functional tight binding (DFTB) models for chemical reactivity in prebiotic mixtures through force matching to short time scale quantum free energy estimates. Molecular dynamics using density functional theory (DFT) is a highly accurate approach to generate free energy surfaces for chemical reactions, but the extreme computational cost often limits the time scales and range of thermodynamic states that can feasibly be studied. In contrast, DFTB is a semiempirical quantum method that affords up to a thousandfold reduction in cost and can recover DFT-level accuracy. Here, we show that a force-matched DFTB model for aqueous glycine condensation reactions yields free energy surfaces that are consistent with experimental observations of reaction energetics. Convergence analysis reveals that multiple nanoseconds of combined trajectory are needed to reach a steady-fluctuating free energy estimate for glycine condensation. Predictive accuracy of force-matched DFTB is demonstrated by direct comparison to DFT, with the two approaches yielding surfaces with large regions that differ by only a few kcal mol -1 .

  3. Time-resolved imaging of purely valence-electron dynamics during a chemical reaction

    DEFF Research Database (Denmark)

    Hockett, Paul; Bisgaard, Christer Z.; Clarkin, Owen J.

    2011-01-01

    Chemical reactions are manifestations of the dynamics of molecular valence electrons and their couplings to atomic motions. Emerging methods in attosecond science can probe purely electronic dynamics in atomic and molecular systems(1-6). By contrast, time-resolved structural-dynamics methods...... such as electron(7-10) or X-ray diffraction(11) and X-ray absorption(12) yield complementary information about the atomic motions. Time-resolved methods that are directly sensitive to both valence-electron dynamics and atomic motions include photoelectron spectroscopy(13-15) and high-harmonic generation(16......,17): in both cases, this sensitivity derives from the ionization-matrix element(18,19). Here we demonstrate a time-resolved molecular-frame photoelectron-angular-distribution (TRMFPAD) method for imaging the purely valence-electron dynamics during a chemical reaction. Specifically, the TRMFPADs measured during...

  4. Isotope yield ratios as a probe of the reaction dynamics

    International Nuclear Information System (INIS)

    Trautmann, W.; Hildenbrand, K.D.; Lynen, U.; Mueller, W.F.J.; Rabe, H.J.; Sann, H.; Stelzer, H.; Trockel, R.; Wada, R.; Brummund, N.; Glasow, R.; Kampert, K.H.; Santo, R.; Eckert, E.M.; Pochodzalla, J.; Bock, I.; Pelte, D.

    1987-04-01

    Isotopically resolved yields of particles and complex fragments from 12 C and 18 O induced reactions on 53 Ni, 54 Ni, Ag, and 197 Au in the intermediate range of bombarding energies 30 MeV ≤ E/A ≤ 84 MeV were measured. The systematic variation of the deduced isotope yield ratios with projectile and target is used to determine the degree of N/Z equilibration achieved and to establish time scales for the reaction process. A quantum statistical model is employed in order to derive entropies of the emitting systems from the measured isotope yield ratios. (orig.)

  5. Microfabricated sleeve devices for chemical reactions

    Science.gov (United States)

    Northrup, M. Allen

    2003-01-01

    A silicon-based sleeve type chemical reaction chamber that combines heaters, such as doped polysilicon for heating, and bulk silicon for convection cooling. The reaction chamber combines a critical ratio of silicon and non-silicon based materials to provide the thermal properties desired. For example, the chamber may combine a critical ratio of silicon and silicon nitride to the volume of material to be heated (e.g., a liquid) in order to provide uniform heating, yet low power requirements. The reaction chamber will also allow the introduction of a secondary tube (e.g., plastic) into the reaction sleeve that contains the reaction mixture thereby alleviating any potential materials incompatibility issues. The reaction chamber may be utilized in any chemical reaction system for synthesis or processing of organic, inorganic, or biochemical reactions, such as the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction, which are examples of a synthetic, thermal-cycling-based reaction. The reaction chamber may also be used in synthesis instruments, particularly those for DNA amplification and synthesis.

  6. Plasmon-driven sequential chemical reactions in an aqueous environment.

    Science.gov (United States)

    Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

    2014-06-24

    Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H(+) in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight.

  7. Radiation-induced chemical reactions of carbon monoxide and hydrogen mixture

    International Nuclear Information System (INIS)

    Sugimoto, S.; Nishii, M.; Sugiura, T.

    1984-01-01

    The radiation chemical reaction of CO-H 2 mixture has been studied in the pressure range from 10 4 to 1.3 x 10 5 Pa using 7 l. reaction vessel made of stainless steel. Various hydrocarbons and oxygen containing compounds such as methane, formaldehyde, acetaldehyde, and methanol have been obtained as radiolytic products. The amounts and the G values of these products depended upon the irradiation conditions such as composition of reactant, total pressure, reaction temperature, and dose. It was found that the irradiation at low dose produced small amounts of trioxane and tetraoxane, which have not yet been reported in literature. The yields of these cyclic ethers increased at high pressure and at low temperature. An experiment was also made on CO-H 2 mixture containing ammonia as a cation scavenger to investigate the precursor of these products. (author)

  8. Surface chemical reactions probed with scanning force microscopy

    NARCIS (Netherlands)

    Werts, M.P L; van der Vegte, E.W.; Hadziioannou, G

    1997-01-01

    In this letter we report the study of surface chemical reactions with scanning force microscopy (SFM) with chemical specificity. Using chemically modified SFM probes, we can determine the local surface reaction conversion during a chemical surface modification. The adhesion forces between a

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

    Science.gov (United States)

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

    2018-01-01

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

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

    Science.gov (United States)

    Gao, Mengdan; Dai, Rongji

    2017-12-01

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

  11. Sintering with a chemical reaction as applied to uranium monocarbide; Frittage-reaction dans le cas du monocarbure d'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Accary, A; Caillat, R [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1960-07-01

    The present paper provides a survey of different investigations whose aim was the preparation and fabrication of uranium monocarbide for nuclear use. If a chemical reaction takes place in the sample during the sintering operation, it may be expected that the atom rearrangements involved in this reaction should favour the sintering process and thereby lower the temperature needed to yield a body of a given density. With this hypothesis in mind, the following methods have been studied: - Sintering of U-C mixtures; - Sintering of UO{sub 2}-C mixtures; - Hot pressing of U-C mixtures; - Extrusion of U-C mixtures. To generalize our result, it could be said that a chemical reaction does not lead to high densification, if one depends on a simple contact between discrete particles. On the contrary, a chemical reaction can help sintering if, as our hot pressing experiments shows, the densification can be achieved prior to the reaction. (author) [French] Le present article resume les etudes faites pour le compte du Commissariat a l'Energie Atomique dans le but de preparer du monocarbure d'uranium pour usage nucleaire. Si, en meme temps que l'on fritte une poudre, celle-ci est le siege d'une reaction chimique, on peut s'attendre a ce que le rearrangement atomique d'une reaction chimique favorise le frittage et, ainsi abaisse la temperature de travail necessaire pour obtenir une densite donnee. Nous avons etudie les methodes suivantes: - frittage des melanges U-C; - frittage des melanges UO{sub 2}-C; - frittage sous charge des melanges U-C; - filage des melanges U-C. Nos resultats montrent qu'une reaction chimique en cours de frittage ne conduit pas a un produit de haute densite si on opere sur un melange de poudres. Par contre, elle permet d'atteindre de hautes densites si la densification peut etre obtenue avant la reaction chimique. (auteur)

  12. Investigation of a Monte Carlo model for chemical reactions

    International Nuclear Information System (INIS)

    Hamm, R.N.; Turner, J.E.; Stabin, M.G.

    1998-01-01

    Monte Carlo computer simulations are in use at a number of laboratories for calculating time-dependent yields, which can be compared with experiments in the radiolysis of water. We report here on calculations to investigate the validity and consistency of the procedures used for simulating chemical reactions in our code, RADLYS. Model calculations were performed of the rate constants themselves. The rates thus determined showed an expected rapid decline over the first few hundred ps and a very gradual decline thereafter out to the termination of the calculations at 4.5 ns. Results are reported for different initial concentrations and numbers of reactive species. Generally, the calculated rate constants are smallest when the initial concentrations of the reactants are largest. It is found that inhomogeneities that quickly develop in the initial random spatial distribution of reactants persist in time as a result of subsequent chemical reactions, and thus conditions may poorly approximate those assumed from diffusion theory. We also investigated the reaction of a single species of one type placed among a large number of randomly distributed species of another type with which it could react. The distribution of survival times of the single species was calculated by using three different combinations of the diffusion constants for the two species, as is sometimes discussed in diffusion theory. The three methods gave virtually identical results. (orig.)

  13. Runaway chemical reaction exposes community to highly toxic chemicals

    International Nuclear Information System (INIS)

    Kaszniak, Mark; Vorderbrueggen, John

    2008-01-01

    The U.S. Chemical Safety and Hazard Investigation Board (CSB) conducted a comprehensive investigation of a runaway chemical reaction at MFG Chemical (MFG) in Dalton, Georgia on April 12, 2004 that resulted in the uncontrolled release of a large quantity of highly toxic and flammable allyl alcohol and allyl chloride into the community. Five people were hospitalized and 154 people required decontamination and treatment for exposure to the chemicals. This included police officers attempting to evacuate the community and ambulance personnel who responded to 911 calls from residents exposed to the chemicals. This paper presents the findings of the CSB report (U.S. Chemical Safety and Hazard Investigation Board (CSB), Investigation Report: Toxic Chemical Vapor Cloud Release, Report No. 2004-09-I-GA, Washington DC, April 2006) including a discussion on tolling practices; scale-up of batch reaction processes; Process Safety Management (PSM) and Risk Management Plan (RMP) implementation; emergency planning by the company, county and the city; and emergency response and mitigation actions taken during the incident. The reactive chemical testing and atmospheric dispersion modeling conducted by CSB after the incident and recommendations adopted by the Board are also discussed

  14. Chemical reaction due to stronger Ramachandran interaction

    Indian Academy of Sciences (India)

    actions between two polarized atoms are responsible for initiating a chemical reaction, either before or after ... Chemical reaction; Ramachandran interaction; anisotropic and asymmetric polarization; ionization ..... man sequence exactly, including the generalized mech- ..... We now move on and rearrange Eq. (8) to arrive at.

  15. 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.

  16. Enhancing chemical reactions

    Science.gov (United States)

    Morrey, John R.

    1978-01-01

    Methods of enhancing selected chemical reactions. The population of a selected high vibrational energy state of a reactant molecule is increased substantially above its population at thermal equilibrium by directing onto the molecule a beam of radiant energy from a laser having a combination of frequency and intensity selected to pump the selected energy state, and the reaction is carried out with the temperature, pressure, and concentrations of reactants maintained at a combination of values selected to optimize the reaction in preference to thermal degradation by transforming the absorbed energy into translational motion. The reaction temperature is selected to optimize the reaction. Typically a laser and a frequency doubler emit radiant energy at frequencies of .nu. and 2.nu. into an optical dye within an optical cavity capable of being tuned to a wanted frequency .delta. or a parametric oscillator comprising a non-centrosymmetric crystal having two indices of refraction, to emit radiant energy at the frequencies of .nu., 2.nu., and .delta. (and, with a parametric oscillator, also at 2.nu.-.delta.). Each unwanted frequency is filtered out, and each desired frequency is focused to the desired radiation flux within a reaction chamber and is reflected repeatedly through the chamber while reactants are fed into the chamber and reaction products are removed therefrom.

  17. Optimizing Chemical Reactions with Deep Reinforcement Learning.

    Science.gov (United States)

    Zhou, Zhenpeng; Li, Xiaocheng; Zare, Richard N

    2017-12-27

    Deep reinforcement learning was employed to optimize chemical reactions. Our model iteratively records the results of a chemical reaction and chooses new experimental conditions to improve the reaction outcome. This model outperformed a state-of-the-art blackbox optimization algorithm by using 71% fewer steps on both simulations and real reactions. Furthermore, we introduced an efficient exploration strategy by drawing the reaction conditions from certain probability distributions, which resulted in an improvement on regret from 0.062 to 0.039 compared with a deterministic policy. Combining the efficient exploration policy with accelerated microdroplet reactions, optimal reaction conditions were determined in 30 min for the four reactions considered, and a better understanding of the factors that control microdroplet reactions was reached. Moreover, our model showed a better performance after training on reactions with similar or even dissimilar underlying mechanisms, which demonstrates its learning ability.

  18. Flows and chemical reactions in heterogeneous mixtures

    CERN Document Server

    Prud'homme, Roger

    2014-01-01

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

  19. Silicon-based sleeve devices for chemical reactions

    Science.gov (United States)

    Northrup, M. Allen; Mariella, Jr., Raymond P.; Carrano, Anthony V.; Balch, Joseph W.

    1996-01-01

    A silicon-based sleeve type chemical reaction chamber that combines heaters, such as doped polysilicon for heating, and bulk silicon for convection cooling. The reaction chamber combines a critical ratio of silicon and silicon nitride to the volume of material to be heated (e.g., a liquid) in order to provide uniform heating, yet low power requirements. The reaction chamber will also allow the introduction of a secondary tube (e.g., plastic) into the reaction sleeve that contains the reaction mixture thereby alleviating any potential materials incompatibility issues. The reaction chamber may be utilized in any chemical reaction system for synthesis or processing of organic, inorganic, or biochemical reactions, such as the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction, which are examples of a synthetic, thermal-cycling-based reaction. The reaction chamber may also be used in synthesis instruments, particularly those for DNA amplification and synthesis.

  20. Investigation of Evaluation method of chemical runaway reaction

    International Nuclear Information System (INIS)

    Sato, Yoshihiko; Sasaya, Shinji; Kurakata, Koichiro; Nojiri, Ichiro

    2002-02-01

    Safety study 'Study of evaluation of abnormal occurrence for chemical substances in the nuclear fuel facilities' will be carried out from 2001 to 2005. In this study, the prediction of thermal hazards of chemical substances will be investigated and prepared. The hazard prediction method of chemical substances will be constructed from these results. Therefore, the hazard prediction methods applied in the chemical engineering in which the chemical substances with the hazard of fire and explosion were often treated were investigated. CHETAH (The ASTM Computer Program for Chemical Thermodynamic and Energy Release Evaluation) developed by ASTM (American Society for Testing and Materials) and TSS (Thermal Safety Software) developed by CISP (ChemInform St. Petersburg) were introduced and the fire and explosion hazards of chemical substances and reactions in the reprocessing process were evaluated. From these evaluated results, CHETAH could almost estimate the heat of reaction at 10% accuracy. It was supposed that CHETAH was useful as a screening for the hazards of fire and explosion of the new chemical substances and so on. TSS could calculate the reaction rate and the reaction behavior from the data measured by the various calorimeters rapidly. It was supposed that TSS was useful as an evaluation method for the hazards of fire and explosion of the new chemical reactions and so on. (author)

  1. [Fission product yields of 60 fissioning reactions]. Final report

    International Nuclear Information System (INIS)

    Rider, B.F.

    1995-01-01

    In keeping with the statement of work, I have examined the fission product yields of 60 fissioning reactions. In co-authorship with the UTR (University Technical Representative) Talmadge R. England ''Evaluation and Compilation of Fission Product Yields 1993,'' LA-UR-94-3106(ENDF-349) October, (1994) was published. This is an evaluated set of fission product Yields for use in calculation of decay heat curves with improved accuracy has been prepared. These evaluated yields are based on all known experimental data through 1992. Unmeasured fission product yields are calculated from charge distribution, pairing effects, and isomeric state models developed at Los Alamos National Laboratory. The current evaluation has been distributed as the ENDF/B-VI fission product yield data set

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

    Science.gov (United States)

    Pathak, Tejas P; Miller, Scott J

    2013-06-05

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

  3. Aerosol simulation including chemical and nuclear reactions

    International Nuclear Information System (INIS)

    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

  4. Explorations into Chemical Reactions and Biochemical Pathways.

    Science.gov (United States)

    Gasteiger, Johann

    2016-12-01

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

  5. ReactionPredictor: prediction of complex chemical reactions at the mechanistic level using machine learning.

    Science.gov (United States)

    Kayala, Matthew A; Baldi, Pierre

    2012-10-22

    Proposing reasonable mechanisms and predicting the course of chemical reactions is important to the practice of organic chemistry. Approaches to reaction prediction have historically used obfuscating representations and manually encoded patterns or rules. Here we present ReactionPredictor, a machine learning approach to reaction prediction that models elementary, mechanistic reactions as interactions between approximate molecular orbitals (MOs). A training data set of productive reactions known to occur at reasonable rates and yields and verified by inclusion in the literature or textbooks is derived from an existing rule-based system and expanded upon with manual curation from graduate level textbooks. Using this training data set of complex polar, hypervalent, radical, and pericyclic reactions, a two-stage machine learning prediction framework is trained and validated. In the first stage, filtering models trained at the level of individual MOs are used to reduce the space of possible reactions to consider. In the second stage, ranking models over the filtered space of possible reactions are used to order the reactions such that the productive reactions are the top ranked. The resulting model, ReactionPredictor, perfectly ranks polar reactions 78.1% of the time and recovers all productive reactions 95.7% of the time when allowing for small numbers of errors. Pericyclic and radical reactions are perfectly ranked 85.8% and 77.0% of the time, respectively, rising to >93% recovery for both reaction types with a small number of allowed errors. Decisions about which of the polar, pericyclic, or radical reaction type ranking models to use can be made with >99% accuracy. Finally, for multistep reaction pathways, we implement the first mechanistic pathway predictor using constrained tree-search to discover a set of reasonable mechanistic steps from given reactants to given products. Webserver implementations of both the single step and pathway versions of Reaction

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

    NARCIS (Netherlands)

    Versteeg, Geert; van Beckum, F.P.H.; Kuipers, J.A.M.; van Swaaij, Willibrordus Petrus Maria

    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

  7. 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.; van Swaaij, 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

  8. Ozone-surface reactions in five homes: surface reaction probabilities, aldehyde yields, and trends.

    Science.gov (United States)

    Wang, H; Morrison, G

    2010-06-01

    Field experiments were conducted in five homes during three seasons (summer 2005, summer 2006 and winter 2007) to quantify ozone-initiated secondary aldehyde yields, surface reaction probabilities, and trends any temporal over a 1.5-year interval. Surfaces examined include living room carpets, bedroom carpets, kitchen floors, kitchen counters, and living room walls. Reaction probabilities for all surfaces for all seasons ranged from 9.4 x 10(-8) to 1.0 x 10(-4). There were no significant temporal trends in reaction probabilities for any surfaces from summer 2005 to summer 2006, nor over the entire 1.5-year period, indicating that it may take significantly longer than this period for surfaces to exhibit any 'ozone aging' or lowering of ozone-surface reactivity. However, all surfaces in three houses exhibited a significant decrease in reaction probabilities from summer 2006 to winter 2007. The total yield of aldehydes for the summer of 2005 were nearly identical to that for summer of 2006, but were significantly higher than for winter 2007. We also observed that older carpets were consistently less reactive than in newer carpets, but that countertops remained consistently reactive, probably because of occupant activities such as cooking and cleaning. Ozone reactions taking place at indoor surfaces significantly influence personal exposure to ozone and volatile reaction products. These field studies show that indoor surfaces only slowly lose their ability to react with ozone over several year time frames, and that this is probably because of a combination of large reservoirs of reactive coatings and periodic additions of reactive coatings in the form of cooking, cleaning, and skin-oil residues. When considering exposure to ozone and its reaction products and in the absence of dramatic changes in occupancy, activities or furnishings, indoor surface reactivity is expected to change very slowly.

  9. Modelling Students' Visualisation of Chemical Reaction

    Science.gov (United States)

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

    2017-01-01

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

  10. Non-equilibrium reaction rates in chemical kinetic equations

    Science.gov (United States)

    Gorbachev, Yuriy

    2018-05-01

    Within the recently proposed asymptotic method for solving the Boltzmann equation for chemically reacting gas mixture, the chemical kinetic equations has been derived. Corresponding one-temperature non-equilibrium reaction rates are expressed in terms of specific heat capacities of the species participate in the chemical reactions, bracket integrals connected with the internal energy transfer in inelastic non-reactive collisions and energy transfer coefficients. Reactions of dissociation/recombination of homonuclear and heteronuclear diatomic molecules are considered. It is shown that all reaction rates are the complex functions of the species densities, similarly to the unimolecular reaction rates. For determining the rate coefficients it is recommended to tabulate corresponding bracket integrals, additionally to the equilibrium rate constants. Correlation of the obtained results with the irreversible thermodynamics is established.

  11. Mesoscale simulations of shockwave energy dissipation via chemical reactions.

    Science.gov (United States)

    Antillon, Edwin; Strachan, Alejandro

    2015-02-28

    We use a particle-based mesoscale model that incorporates chemical reactions at a coarse-grained level to study the response of materials that undergo volume-reducing chemical reactions under shockwave-loading conditions. We find that such chemical reactions can attenuate the shockwave and characterize how the parameters of the chemical model affect this behavior. The simulations show that the magnitude of the volume collapse and velocity at which the chemistry propagates are critical to weaken the shock, whereas the energetics in the reactions play only a minor role. Shock loading results in transient states where the material is away from local equilibrium and, interestingly, chemical reactions can nucleate under such non-equilibrium states. Thus, the timescales for equilibration between the various degrees of freedom in the material affect the shock-induced chemistry and its ability to attenuate the propagating shock.

  12. Methyl salicylate: a reactive chemical warfare agent surrogate to detect reaction with hypochlorite.

    Science.gov (United States)

    Salter, W Bruce; Owens, Jeffery R; Wander, Joseph D

    2011-11-01

    Methyl salicylate (MeS) has a rich history as an inert physical simulant for the chemical warfare agents sulfur mustard and soman, where it is used extensively for liquid- and vapor-permeation testing. Here we demonstrate possible utility of MeS as a reactivity simulant for chlorine-based decontaminants. In these experiments MeS was reacted with sodium hypochlorite varying stoichiometry, temperature, reaction time, and pH. No colored oxidation products were observed; however, chlorination of the aromatic ring occurred ortho (methyl 3-chlorosalicylate) and para (methyl 5-chlorosalicylate) to the position bearing the -OH group in both the mono- and disubstituted forms. The monosubstituted para product accumulated initially, and the ortho and 3,5-dichloro products formed over the next several hours. Yields from reactions conducted below pH 11 declined rapidly with decreasing pH. Reactions run at 40 °C produced predominantly para substitution, while those run at 0 °C produced lower yields of ortho- and para-substituted products. Reactions were also carried out on textile substrates of cotton, 50/50 nylon-cotton, and a meta aramid. The textile data broadly reproduced reaction times and stoichiometry observed in the liquid phase, but are complicated by physical and possibly chemical interactions with the fabric. These data indicate that, for hypochlorite-containing neutralizing agents operating at strongly alkaline pH, one can expect MeS to react stoichiometrically with the hypochlorite it encounters. This suggests utility of MeS in lieu of such highly hazardous surrogates as monochloroalkyl sulfides as a simulant for threat scenarios involving the stoichiometric decomposition of sulfur mustard. Specifically, the extent of coverage of the simulant on a fabric by the neutralizing agent can be directly measured. Similar reactivity toward other halogen oxidizing agents is likely but remains to be demonstrated.

  13. Acoustic wave propagation in fluids with coupled chemical reactions

    International Nuclear Information System (INIS)

    Margulies, T.S.; Schwarz, W.H.

    1984-08-01

    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

  14. 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

  15. 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.

  16. Neutral theory of chemical reaction networks

    International Nuclear Information System (INIS)

    Lee, Sang Hoon; Holme, Petter; Minnhagen, Petter; Bernhardsson, Sebastian; Kim, Beom Jun

    2012-01-01

    To what extent do the characteristic features of a chemical reaction network reflect its purpose and function? In general, one argues that correlations between specific features and specific functions are key to understanding a complex structure. However, specific features may sometimes be neutral and uncorrelated with any system-specific purpose, function or causal chain. Such neutral features are caused by chance and randomness. Here we compare two classes of chemical networks: one that has been subjected to biological evolution (the chemical reaction network of metabolism in living cells) and one that has not (the atmospheric planetary chemical reaction networks). Their degree distributions are shown to share the very same neutral system-independent features. The shape of the broad distributions is to a large extent controlled by a single parameter, the network size. From this perspective, there is little difference between atmospheric and metabolic networks; they are just different sizes of the same random assembling network. In other words, the shape of the degree distribution is a neutral characteristic feature and has no functional or evolutionary implications in itself; it is not a matter of life and death. (paper)

  17. Experimental and numerical reaction analysis on sodium-water chemical reaction field

    International Nuclear Information System (INIS)

    Deguchi, Yoshihiro; Takata, Takashi; Yamaguchi, Akira; Kikuchi, Shin; Ohshima, Hiroyuki

    2015-01-01

    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. This process ends up damages on the heat transport equipment in the SFR. Therefore, the study on sodium-water chemical reactions is of paramount importance for security reasons. This study aims to clarify the sodium-water reaction mechanisms using an elementary reaction analysis. A quasi one-dimensional flame model is applied to a sodium-water counter-flow reaction field. The analysis contains 25 elementary reactions, which consist of 17 H_2-O_2 and 8 Na-H_2O reactions. Temperature and species concentrations in the counter-flow reaction field were measured using laser diagnostics such as LIF and CARS. The main reaction in the experimental conditions is Na+H_2O → NaOH+H and OH is produced by H_2O+H → H_2+OH. It is demonstrated that the reaction model in this study well explains the structure of the sodium-water counter-flow diffusion flame. (author)

  18. Reaction Hamiltonian and state-to-state description of chemical reactions

    International Nuclear Information System (INIS)

    Ruf, B.A.; Kresin, V.Z.; Lester, W.A. Jr.

    1985-08-01

    A chemical reaction is treated as a quantum transition from reactants to products. A specific reaction Hamiltonian (in second quantization formalism) is introduced. The approach leads to Franck-Condon-like factor, and adiabatic method in the framework of the nuclear motion problems. The influence of reagent vibrational state on the product energy distribution has been studied following the reaction Hamiltonian method. Two different cases (fixed available energy and fixed translational energy) are distinguished. Results for several biomolecular reactions are presented. 40 refs., 5 figs

  19. Heterogeneously Catalysed Chemical Reactions in Carbon Dioxide Medium

    DEFF Research Database (Denmark)

    Musko, Nikolai E.

    In this PhD-study the different areas of chemical engineering, heterogeneous catalysis, supercritical fluids, and phase equilibrium thermodynamics have been brought together for selected reactions. To exploit the beneficial properties of supercritical fluids in heterogeneous catalysis, experimental...... studies of catalytic chemical reactions in dense and supercritical carbon dioxide have been complemented by the theoretical calculations of phase equilibria using advanced thermodynamic models. In the recent years, the use of compressed carbon dioxide as innovative, non-toxic and non-flammable, cheap......, and widely available reaction medium for many practical and industrial applications has drastically increased. Particularly attractive are heterogeneously catalysed chemical reactions. The beneficial use of CO2 is attributed to its unique properties at dense and supercritical states (at temperatures...

  20. Helicity dependence of the {gamma}{yields}p{yields}{yields}n{pi}{sup +}{pi}{sup 0} reaction in the second resonance region

    Energy Technology Data Exchange (ETDEWEB)

    Ahrens, J.; Altieri, S.; Annand, J.R.M.; Anton, G.; Arends, H.-J.; Aulenbacher, K.; Beck, R.; Bradtke, C.; Braghieri, A.; Degrande, N.; D' Hose, N.; Dutz, H.; Goertz, S.; Grabmayr, P.; Hansen, K.; Harmsen, J.; Harrach, D. von; Hasegawa, S.; Hasegawa, T.; Heid, E.; Helbing, K.; Holvoet, H.; Van Hoorebeke, L.; Horikawa, N.; Iwata, T.; Jahn, O.; Jennewein, P.; Kageya, T.; Kiel, B.; Klein, F.; Kondratiev, R.; Kossert, K.; Krimmer, J.; Lang, M.; Lannoy, B.; Leukel, R.; Lisin, V.; Matsuda, T.; McGeorge, J.C.; Meier, A.; Menze, D.; Meyer, W.; Michel, T.; Naumann, J.; Panzeri, A.; Pedroni, P.; Pinelli, T.; Preobrajenski, I.; Radtke, E.; Reichert, E.; Reicherz, G.; Rohlof, Ch.; Rosner, G.; Rostomyan, T.; Rovelli, C.; Ryckbosch, D.; Sauer, M.; Schoch, B.; Schumacher, M.; Seitz, B.; Speckner, T.; Takabayashi, N.; Tamas, G.; Thomas, A.; Vyver, R. van de; Wakai, A.; Weihofen, W.; Wissmann, F.; Zapadtka, F.; Zeitler, G

    2003-01-02

    The helicity dependence of the total cross section for the {gamma}{yields}p{yields}{yields}n{pi}{sup +}{pi}{sup 0} reaction has been measured for the first time at incident photon energies from 400 to 800 MeV. The measurement was performed with the large acceptance detector DAPHNE at the tagged photon beam facility of the MAMI accelerator in Mainz. This channel is found to be excited predominantly when the photon and proton have a parallel spin orientation, due to the intermediate production of the D{sub 13} resonance.

  1. Fission fragment yields from heavy-ion-induced reactions measured with a fragment separator

    Science.gov (United States)

    Tarasov, O. B.; Delaune, O.; Farget, F.; Morrissey, D. J.; Amthor, A. M.; Bastin, B.; Bazin, D.; Blank, B.; Cacéres, L.; Chbihi, A.; Fernández-Dominguez, B.; Grévy, S.; Kamalou, O.; Lukyanov, S. M.; Mittig, W.; Pereira, J.; Perrot, L.; Saint-Laurent, M.-G.; Savajols, H.; Sherrill, B. M.; Stodel, C.; Thomas, J. C.; Villari, A. C.

    2018-04-01

    The systematic study of fission fragment yields under different initial conditions has provided valuable experimental data for benchmarking models of fission product yields. Nuclear reactions using inverse kinematics coupled to the use of a high-resolution spectrometer with good fragment identification are shown here to be a powerful tool to measure the inclusive isotopic yields of fission fragments. In-flight fusion-fission was used in this work to produce secondary beams of neutron-rich isotopes in the collisions of a 238U beam at 24 MeV/u with 9Be and 12C targets at GANIL using the LISE3 fragment separator. Unique identification of the A, Z, and atomic charge state, q, of fission products was attained with the Δ E- TKE-B ρ- ToF measurement technique. Mass, and atomic number distributions are reported for the two reactions. The results show the importance of different reaction mechanisms in the two cases. The optimal target material for higher yields of neutron-rich high- Z isotopes produced in fusion-fission reactions as a function of projectile energy is discussed.

  2. Chemical effects of (n,2n) reactions on iodate and periodates systems

    International Nuclear Information System (INIS)

    Mendonca, J.M.A. de.

    1975-12-01

    The chemical consequences of (n,2n) reactions on cristalline sodium iodate and periodates were investigated measuring the initial yield and the post irradiation thermal annealing yields (90 0 C) of the separated fractions I - , IO 3 - and IO 4 - . NaIO 3 , NaIO 3 .H 2 O and NaIO 4 , Na 4 H 2 IO 6 , Na 4 I 2 O 9 .3H 2 O containing 127 I and 129 I, or both, were irradiated with 14 MeV neutrons. Results obtained show different effects for each system and that 126 I and 128 I isotopes keep the same behaviour in the irradiated compounds containing only α 127 I or 129 I and in compounds having both 127 I and 129 I. Neither isotope effect nor qualitative differences on thermal annealing at 90 0 C were observed. The annealed fractions in the three studied periodates were IO - 3 and IO - 4 . These results differ from the ones reported previously for (n,γ) reactions on the same compounds [pt

  3. Chemical changes in groundwater and their reaction rates

    International Nuclear Information System (INIS)

    Talma, A.S.

    1981-01-01

    The evolution of the major ion concentrations of groundwater (Na, K, Ca, Mg, HCO 3 , SO 4 , Cl and NO 3 ) can be described as the consequence of a number of competing chemical reactions. With the aid of the naturally occuring radioactive and stable isotopes some of these reactions can be separated, identified and followed in space and time. In some field studies, especialy of artesian water, the rates of reactions can be estimated. A number of processes observed in South African sandstones aquifers are discussed and the variable reaction rates demonstrated. Reactions that can be identified include carbonate solution, chemical weathering, salt leaching, cation exchange and redox processes

  4. Correlations between reaction product yields as a tool for probing heavy-ion reaction scenarios

    International Nuclear Information System (INIS)

    Gawlikowicz, W.; Agnihotri, D. K.; Baldwin, S. A.; Schroeder, W. U.; Toke, J.; Charity, R. J.; Sarantites, D. G.; Sobotka, L. G.; Souza, R. T. de; Barczyk, T.; Grotowski, K.; Micek, S.; Planeta, R.; Sosin, Z.

    2010-01-01

    Experimental multidimensional joint distributions of neutrons and charged reaction products were analyzed for 136 Xe + 209 Bi reactions at E/A=28, 40, and 62 MeV and were found to exhibit several different types of prominent correlation patterns. Some of these correlations have a simple explanation in terms of the system excitation energy and pose little challenge to most statistical decay theories. However, several other types of correlation patterns are difficult to reconcile with some, but not other, possible reaction scenarios. In this respect, correlations between the average atomic numbers of intermediate-mass fragments, on the one hand, and light particle multiplicities, on the other, are notable. This kind of multiparticle correlation provides a useful tool for probing reaction scenarios, which is different from the traditional approach of interpreting inclusive yields of individual reaction products.

  5. Temperature dependence on sodium-water chemical reaction

    International Nuclear Information System (INIS)

    Tamura, Kenta; Deguchi, Yoshihiro; Suzuki, Koichi; Takata, Takashi; Yamaguchi, Akira; Kikuchi, Shin; Ohshima, Hiroyuki

    2012-01-01

    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. This process ends up damages on the heat transport equipment in the SFR. Therefore, the study on sodium-water chemical reactions is of paramount importance for security reasons. This study aims to clarify the sodium-water reaction mechanisms using laser diagnostics. A quasi one-dimensional flame model is also applied to a sodium-water counter-flow reaction field. Temperature, H 2 , H 2 O, OH, Na and Particulate matter were measured using laser induced fluorescence and CARS in the counter-flow reaction field. The temperature of the reaction field was also modified to reduce the condensation of Na in the reaction zone. (author)

  6. H + CH{sub 2}CO {yields} CH{sub 3} + CO at high temperature : a high pressure chemical activation reaction with positive barrier.

    Energy Technology Data Exchange (ETDEWEB)

    Hranisavljevic, J.; Kumaran, S. S.; Michael, J. V.

    1997-12-08

    The Laser Photolysis-Shock Tube (LP-ST) technique coupled with H-atom atomic resonance absorption spectrometry (ARAS) has been used to study reaction, H + CH{sub 2}CO {r_arrow} CH{sub 3} + CO, over the temperature range, 863-1400 K. The results can be represented by the Arrhenius expression, k = (4.85 {+-} 0.70) x 10{sup {minus}11} exp({minus}2328 {+-} 155 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The present data have been combined with the earlier low temperature flash photolysis-resonance fluorescence measurements to yield a joint three parameter expression, k = 5.44 x 10{sup {minus}14} T{sup 0.8513} exp({minus}1429 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. This is a chemical activation process that proceeds through vibrationally excited acetyl radicals. However, due to the presence of a low lying forward dissociation channel to CH{sub 3} + CO, the present results refer to the high pressure limiting rate constants. Hence, transition state theory with Eckart tunneling is used to explain the data.

  7. 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

    2016-04-27

    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.

  8. 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.

  9. CHEMICAL REACTIONS ON ADSORBING SURFACE: KINETIC LEVEL OF DESCRIPTION

    Directory of Open Access Journals (Sweden)

    P.P.Kostrobii

    2003-01-01

    Full Text Available Based on the effective Hubbard model we suggest a statistical description of reaction-diffusion processes for bimolecular chemical reactions of gas particles adsorbed on the metallic surface. The system of transport equations for description of particles diffusion as well as reactions is obtained. We carry out the analysis of the contributions of all physical processes to the formation of diffusion coefficients and chemical reactions constants.

  10. 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.

  11. Chemical memory reactions induced bursting dynamics in gene expression.

    Science.gov (United States)

    Tian, Tianhai

    2013-01-01

    Memory is a ubiquitous phenomenon in biological systems in which the present system state is not entirely determined by the current conditions but also depends on the time evolutionary path of the system. Specifically, many memorial phenomena are characterized by chemical memory reactions that may fire under particular system conditions. These conditional chemical reactions contradict to the extant stochastic approaches for modeling chemical kinetics and have increasingly posed significant challenges to mathematical modeling and computer simulation. To tackle the challenge, I proposed a novel theory consisting of the memory chemical master equations and memory stochastic simulation algorithm. A stochastic model for single-gene expression was proposed to illustrate the key function of memory reactions in inducing bursting dynamics of gene expression that has been observed in experiments recently. The importance of memory reactions has been further validated by the stochastic model of the p53-MDM2 core module. Simulations showed that memory reactions is a major mechanism for realizing both sustained oscillations of p53 protein numbers in single cells and damped oscillations over a population of cells. These successful applications of the memory modeling framework suggested that this innovative theory is an effective and powerful tool to study memory process and conditional chemical reactions in a wide range of complex biological systems.

  12. 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…

  13. An autonomous organic reaction search engine for chemical reactivity

    Science.gov (United States)

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

    2017-06-01

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

  14. A cellular automata approach to chemical reactions : 1 reaction controlled systems

    NARCIS (Netherlands)

    Korte, de A.C.J.; Brouwers, H.J.H.

    2013-01-01

    A direct link between the chemical reaction controlled (shrinking core) model and cellular automata, to study the dissolution of particles, is derived in this paper. Previous research on first and second order reactions is based on the concentration of the reactant. The present paper describes the

  15. Simulation of square wave voltammetry of three electrode reactions coupled by two reversible chemical reactions

    OpenAIRE

    Lovrić, Milivoj

    2017-01-01

    Three fast and reversible electrode reactions that are connected by two reversible chemical reactions that are permanently in the equilibrium are analysed theoretically for square wave voltammetry. The dependence of peak potentials on the dimensionless equilibrium constants of chemical reactions is calculated. The influence of the basic thermodynamic parameters on the square wave voltammetric responses is analysed.

  16. Versatile Dual Photoresponsive System for Precise Control of Chemical Reactions.

    Science.gov (United States)

    Xu, Can; Bing, Wei; Wang, Faming; Ren, Jinsong; Qu, Xiaogang

    2017-08-22

    A versatile method for photoregulation of chemical reactions was developed through a combination of near-infrared (NIR) and ultraviolet (UV) light sensitive materials. This regulatory effect was achieved through photoresponsive modulation of reaction temperature and pH values, two prominent factors influencing reaction kinetics. Photothermal nanomaterial graphene oxide (GO) and photobase reagent malachite green carbinol base (MGCB) were selected for temperature and pH regulation, respectively. Using nanocatalyst- and enzyme-mediated chemical reactions as model systems, we demonstrated the feasibility and high efficiency of this method. In addition, a photoresponsive, multifunctional "Band-aid"-like hydrogel platform was presented for programmable wound healing. Overall, this simple, efficient, and reversible system was found to be effective for controlling a wide variety of chemical reactions. Our work may provide a method for remote and sustainable control over chemical reactions for industrial and biomedical applications.

  17. Modelling Chemical Reasoning to Predict and Invent Reactions.

    Science.gov (United States)

    Segler, Marwin H S; Waller, Mark P

    2017-05-02

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

  18. Effect of Coatings on the Uptake Rate and HONO Yield in Heterogeneous Reaction of Soot with NO2

    Science.gov (United States)

    Cruz-Quiñones, M.; Khalizov, A. F.; Zhang, R.

    2009-12-01

    Heterogeneous reaction of nitrogen dioxide on carbon soot aerosols has been suggested as a possible source of nighttime nitrous acid (HONO) in atmosphere boundary layer. Available laboratory data show significant variability in the measured reaction probabilities and HONO yields, making it difficult to asses the atmospheric significance of this process. Moreover, little is known of how aging of soot aerosol through internal mixing with other atmospheric trace constituents will affect the heterogeneous reactivity and HONO production. In this work, the heterogeneous reaction of NO2 on fresh and aged soot films leading to HONO formation was studied through a series of kinetic uptake experiments and HONO yield measurements. Soot samples were prepared by incomplete combustion of propane and kerosene fuels under lean and rich flame conditions. Experiments were performed in a low-pressure, fast-flow reactor coupled to a chemical ionization mass spectrometer (CIMS), using atmospheric-level NO2 concentrations. Heterogeneous uptake coefficients, γ(geom) and γ(BET), were calculated using geometric and internal BET soot surface areas, respectively. The uptake coefficient and the HONO yield depend on the type of fuel and combustion regime and are the highest for soot samples prepared using rich kerosene flame. Although, the internal surface area of soot measured by BET method is a factor of 50 to 500 larger than the geometric surface area, only the top soot layers are involved in heterogeneous reaction with NO2 as follows from the observed weak dependence of γ(geom) and decrease in γ(BET) with increasing sample mass. Heating the soot samples before exposure to NO2 increases the BET surface area, the HONO yield, and the NO2 uptake coefficient due to the removal of the organic fraction from the soot backbone that unblocks active sites and makes them accessible for physical adsorption and chemical reactions. Our results support the oxidation-reduction mechanism involving

  19. 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.

  20. 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.

  1. Simultaneous measurements of reactive scalar and velocity in a planar liquid jet with a second-order chemical reaction

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Tomoaki; Sakai, Yasuhiko; Nagata, Kouji; Terashima, Osamu [Nagoya University, Department of Mechanical Science and Engineering, Nagoya (Japan); Kubo, Takashi [Meijo University, Faculty of Science and Technology, Nagoya (Japan)

    2012-11-15

    This paper presents a new experimental approach for simultaneous measurements of velocity and concentration in a turbulent liquid flow with a chemical reaction. For the simultaneous measurements, we developed a combined probe consisting of an I-type hot-film probe and an optical fiber probe based on the light absorption spectrometric method. In a turbulent planar liquid jet with a second-order chemical reaction (A+B{yields}R), streamwise velocity and concentrations of all reactive species are measured by the combined probe. The turbulent mass fluxes of the reactive species are estimated from the simultaneous measurements. The results show that the influence of the chemical reaction on the turbulent mass flux of the reactant species near the jet exit is different from its influence in other regions, and the turbulent mass flux of the product species has a negative value near the jet exit and a positive value in other regions. (orig.)

  2. 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.

  3. 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.

  4. Chemically ignited thermonuclear reactions: A near-term means for a high specific impulse - High thrust propulsion system

    International Nuclear Information System (INIS)

    Winterberg, F.

    1982-01-01

    A proposal for the fissionless ignition of small thermonuclear reactions is made which involves the combination of the magnetic booster target inertial fusion concept with the chemical implosion of metallic shells. The magnetic booster employs a very dense and magnetically confined low yield thermonuclear plasma to trigger an inertially confined high yield plasma. Fissionless ignition permits smaller yields than with fission- or fusion-induced fusion bombs, yields that are appropriate for use in a spacecraft propulsion system. Each bomb would release about 10 to the 18th erg or 100 tons of TNT, and with one explosion per second, an average thrust of 10 to the third tons and a specific impulse of about 3000 seconds can be expected

  5. Modular verification of chemical reaction network encodings via serializability analysis

    Science.gov (United States)

    Lakin, Matthew R.; Stefanovic, Darko; Phillips, Andrew

    2015-01-01

    Chemical reaction networks are a powerful means of specifying the intended behaviour of synthetic biochemical systems. A high-level formal specification, expressed as a chemical reaction network, may be compiled into a lower-level encoding, which can be directly implemented in wet chemistry and may itself be expressed as a chemical reaction network. Here we present conditions under which a lower-level encoding correctly emulates the sequential dynamics of a high-level chemical reaction network. We require that encodings are transactional, such that their execution is divided by a “commit reaction” that irreversibly separates the reactant-consuming phase of the encoding from the product-generating phase. We also impose restrictions on the sharing of species between reaction encodings, based on a notion of “extra tolerance”, which defines species that may be shared between encodings without enabling unwanted reactions. Our notion of correctness is serializability of interleaved reaction encodings, and if all reaction encodings satisfy our correctness properties then we can infer that the global dynamics of the system are correct. This allows us to infer correctness of any system constructed using verified encodings. As an example, we show how this approach may be used to verify two- and four-domain DNA strand displacement encodings of chemical reaction networks, and we generalize our result to the limit where the populations of helper species are unlimited. PMID:27325906

  6. Stochastic thermodynamics and entropy production of chemical reaction systems

    Science.gov (United States)

    Tomé, Tânia; de Oliveira, Mário J.

    2018-06-01

    We investigate the nonequilibrium stationary states of systems consisting of chemical reactions among molecules of several chemical species. To this end, we introduce and develop a stochastic formulation of nonequilibrium thermodynamics of chemical reaction systems based on a master equation defined on the space of microscopic chemical states and on appropriate definitions of entropy and entropy production. The system is in contact with a heat reservoir and is placed out of equilibrium by the contact with particle reservoirs. In our approach, the fluxes of various types, such as the heat and particle fluxes, play a fundamental role in characterizing the nonequilibrium chemical state. We show that the rate of entropy production in the stationary nonequilibrium state is a bilinear form in the affinities and the fluxes of reaction, which are expressed in terms of rate constants and transition rates, respectively. We also show how the description in terms of microscopic states can be reduced to a description in terms of the numbers of particles of each species, from which follows the chemical master equation. As an example, we calculate the rate of entropy production of the first and second Schlögl reaction models.

  7. Scattering theory and chemical reactions

    International Nuclear Information System (INIS)

    Kuppermann, A.

    1988-01-01

    In this course, scattering theory and chemical reactions are presented including scattering of one particle by a potential, n-particle systems, colinear triatomic molecules and the study of reactive scattering for 3-dimensional triatomic systems. (A.C.A.S.) [pt

  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. 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.

  10. The Theory of Thermodynamics for Chemical Reactions in Dispersed Heterogeneous Systems

    Science.gov (United States)

    Yongqiang; Baojiao; Jianfeng

    1997-07-01

    In this paper, the expressions of Gibbs energy change, enthalpy change, entropy change, and equilibrium constant for chemical reactions in dispersed heterogeneous systems are derived using classical thermodynamics theory. The thermodynamical relations for the same reaction system between the dispersed and the block state are also derived. The effects of degree of dispersion on thermodynamical properties, reaction directions, and chemical equilibria are discussed. The results show that the present equation of thermodynamics for chemical reactions is only a special case of the above-mentioned formulas and that the effect of the dispersity of a heterogeneous system on the chemical reaction obeys the Le Chatelier principle of movement of equilibria.

  11. Laser-induced chemical vapor deposition reactions

    International Nuclear Information System (INIS)

    Teslenko, V.V.

    1990-01-01

    The results of investigation of chemical reactions of deposition of different substances from the gas phase when using the energy of pulse quasicontinuous and continuous radiation of lasers in the wave length interval from 0.193 to 10.6 μm are generalized. Main attetion is paid to deposition of inorganic substances including nonmetals (C, Si, Ge and others), metals (Cu, Au, Zn, Cd, Al, Cr, Mo, W, Ni) and some simple compounds. Experimental data on the effect of laser radiation parameters and reagent nature (hydrides, halogenides, carbonyls, alkyl organometallic compounds and others) on the deposition rate and deposit composition are described in detail. Specific features of laser-chemical reactions of deposition and prospects of their application are considered

  12. Chemical reactions directed Peptide self-assembly.

    Science.gov (United States)

    Rasale, Dnyaneshwar B; Das, Apurba K

    2015-05-13

    Fabrication of self-assembled nanostructures is one of the important aspects in nanoscience and nanotechnology. The study of self-assembled soft materials remains an area of interest due to their potential applications in biomedicine. The versatile properties of soft materials can be tuned using a bottom up approach of small molecules. Peptide based self-assembly has significant impact in biology because of its unique features such as biocompatibility, straight peptide chain and the presence of different side chain functionality. These unique features explore peptides in various self-assembly process. In this review, we briefly introduce chemical reaction-mediated peptide self-assembly. Herein, we have emphasised enzymes, native chemical ligation and photochemical reactions in the exploration of peptide self-assembly.

  13. Supersonic molecular beam experiments on surface chemical reactions.

    Science.gov (United States)

    Okada, Michio

    2014-10-01

    The interaction of a molecule and a surface is important in various fields, and in particular in complex systems like biomaterials and their related chemistry. However, the detailed understanding of the elementary steps in the surface chemistry, for example, stereodynamics, is still insufficient even for simple model systems. In this Personal Account, I review our recent studies of chemical reactions on single-crystalline Cu and Si surfaces induced by hyperthermal oxygen molecular beams and by oriented molecular beams, respectively. Studies of oxide formation on Cu induced by hyperthermal molecular beams demonstrate a significant role of the translational energy of the incident molecules. The use of hyperthermal molecular beams enables us to open up new chemical reaction paths specific for the hyperthermal energy region, and to develop new methods for the fabrication of thin films. On the other hand, oriented molecular beams also demonstrate the possibility of understanding surface chemical reactions in detail by varying the orientation of the incident molecules. The steric effects found on Si surfaces hint at new ways of material fabrication on Si surfaces. Controlling the initial conditions of incoming molecules is a powerful tool for finely monitoring the elementary step of the surface chemical reactions and creating new materials on surfaces. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    DEFF Research Database (Denmark)

    Petrunin, Victor V.

    2011-01-01

    and 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....

  15. Calculation of the energetics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

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

    1988-01-01

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

  16. Lagrangian descriptors of driven chemical reaction manifolds.

    Science.gov (United States)

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

    2017-08-01

    The persistence of a transition state structure in systems driven by time-dependent environments allows the application of modern reaction rate theories to solution-phase and nonequilibrium chemical reactions. However, identifying this structure is problematic in driven systems and has been limited by theories built on series expansion about a saddle point. Recently, it has been shown that to obtain formally exact rates for reactions in thermal environments, a transition state trajectory must be constructed. Here, using optimized Lagrangian descriptors [G. T. Craven and R. Hernandez, Phys. Rev. Lett. 115, 148301 (2015)PRLTAO0031-900710.1103/PhysRevLett.115.148301], we obtain this so-called distinguished trajectory and the associated moving reaction manifolds on model energy surfaces subject to various driving and dissipative conditions. In particular, we demonstrate that this is exact for harmonic barriers in one dimension and this verification gives impetus to the application of Lagrangian descriptor-based methods in diverse classes of chemical reactions. The development of these objects is paramount in the theory of reaction dynamics as the transition state structure and its underlying network of manifolds directly dictate reactivity and selectivity.

  17. Limonene ozonolysis in the presence of nitric oxide: Gas-phase reaction products and yields

    Science.gov (United States)

    Ham, Jason E.; Harrison, Joel C.; Jackson, Stephen R.; Wells, J. R.

    2016-05-01

    The reaction products from limonene ozonolysis were investigated using the new carbonyl derivatization agent, O-tert-butylhydroxylamine hydrochloride (TBOX). With ozone (O3) as the limiting reagent, five carbonyl compounds were detected. The yields of the carbonyl compounds are discussed with and without the presence of a hydroxyl radical (OHrad) scavenger, giving insight into the influence secondary OH radicals have on limonene ozonolysis products. The observed reaction product yields for limonaketone (LimaKet), 7-hydroxyl-6-oxo-3-(prop-1-en-2-yl)heptanal (7H6O), and 2-acetyl-5-oxohexanal (2A5O) were unchanged suggesting OHrad generated by the limonene + O3 reaction does not contribute to their formation. The molar yields of 3-isopropenyl-6-oxo-heptanal (IPOH) and 3-acetyl-6-oxoheptanal (3A6O) decreased by 68% and >95%; respectively, when OHrad was removed. This suggests that OHrad radicals significantly impact the formation of these products. Nitric oxide (NO) did not significantly affect the molar yields of limonaketone or IPOH. However, NO (20 ppb) considerably decreased the molar reaction product yields of 7H6O (62%), 2A5O (63%), and 3A6O (47%), suggesting NO reacted with peroxyl intermediates, generated during limonene ozonolysis, to form other carbonyls (not detected) or organic nitrates. These studies give insight into the transformation of limonene and its reaction products that can lead to indoor exposures.

  18. Influence of reaction conditions and type of alcohol on biodiesel yields and process economics of supercritical transesterification

    International Nuclear Information System (INIS)

    Micic, Radoslav D.; Tomić, Milan D.; Kiss, Ferenc E.; Nikolić-Djorić, Emilija B.; Simikić, Mirko Ð.

    2014-01-01

    Highlights: • Transesterification in supercritical methanol, ethanol and 1-propanol investigated. • Effect of alcohol, reaction temperature, pressure and time on yields analyzed. • Temperature has the highest impact on yield, followed by time and pressure. • Direct material and energy costs for each of the production alternatives estimated. • Lowest costs are achieved at highest yields even at very low oil prices. - Abstract: Experiments with transesterification of rapeseed oil in supercritical alcohols (methanol, ethanol and 1-propanol) were carried out in a batch reactor at various reaction temperatures (250–350 °C), working pressure (8–12 MPa), reaction time, and constant 42:1 alcohol to oil molar ratio. Influence of different alcohols and reaction conditions on biodiesel yield was investigated using linear multiple regression models. Temperature had the highest impact on yields, followed by reaction time and pressure. With increased molecular weight of alcohols, relative importance of temperature for explanation of yields decreased and relative importance of time and pressure increased. Economic assessment has revealed that transesterification in supercritical methanol has the lowest direct material and energy costs. Yield has crucial impact on process economics. Direct costs decrease with increase in biodiesel yields. Even at very low prices of oil feedstock the lowest cost is achieved at the highest yield

  19. Transport Properties of a Kinetic Model for Chemical Reactions without Barriers

    International Nuclear Information System (INIS)

    Alves, Giselle M.; Kremer, Gilberto M.; Soares, Ana Jacinta

    2011-01-01

    A kinetic model of the Boltzmann equation for chemical reactions without energy barrier is considered here with the aim of evaluating the reaction rate and characterizing the transport coefficient of shear viscosity for the reactive system. The Chapman-Enskog solution of the Boltzmann equation is used to compute the chemical reaction effects, in a flow regime for which the reaction process is close to the final equilibrium state. Some numerical results are provided illustrating that the considered chemical reaction without energy barrier can induce an appreciable influence on the reaction rate and on the transport coefficient of shear viscosity.

  20. Ozone deposition velocities, reaction probabilities and product yields for green building materials

    Science.gov (United States)

    Lamble, S. P.; Corsi, R. L.; Morrison, G. C.

    2011-12-01

    Indoor surfaces can passively remove ozone that enters buildings, reducing occupant exposure without an energy penalty. However, reactions between ozone and building surfaces can generate and release aerosols and irritating and carcinogenic gases. To identify desirable indoor surfaces the deposition velocity, reaction probability and carbonyl product yields of building materials considered green (listed, recycled, sustainable, etc.) were quantified. Nineteen separate floor, wall or ceiling materials were tested in a 10 L, flow-through laboratory reaction chamber. Inlet ozone concentrations were maintained between 150 and 200 ppb (generally much lower in chamber air), relative humidity at 50%, temperature at 25 °C and exposure occurred over 24 h. Deposition velocities ranged from 0.25 m h -1 for a linoleum style flooring up to 8.2 m h -1 for a clay based paint; reaction probabilities ranged from 8.8 × 10 -7 to 6.9 × 10 -5 respectively. For all materials, product yields of C 1 thru C 12 saturated n-aldehydes, plus acetone ranged from undetectable to greater than 0.70 The most promising material was a clay wall plaster which exhibited a high deposition velocity (5.0 m h -1) and a low product yield (

  1. Nonequilibrium thermodynamics and a fluctuation theorem for individual reaction steps in a chemical reaction network

    International Nuclear Information System (INIS)

    Pal, Krishnendu; Das, Biswajit; Banerjee, Kinshuk; Gangopadhyay, Gautam

    2015-01-01

    We have introduced an approach to nonequilibrium thermodynamics of an open chemical reaction network in terms of the propensities of the individual elementary reactions and the corresponding reverse reactions. The method is a microscopic formulation of the dissipation function in terms of the relative entropy or Kullback-Leibler distance which is based on the analogy of phase space trajectory with the path of elementary reactions in a network of chemical process. We have introduced here a fluctuation theorem valid for each opposite pair of elementary reactions which is useful in determining the contribution of each sub-reaction on the nonequilibrium thermodynamics of overall reaction. The methodology is applied to an oligomeric enzyme kinetics at a chemiostatic condition that leads the reaction to a nonequilibrium steady state for which we have estimated how each step of the reaction is energy driven or entropy driven to contribute to the overall reaction. (paper)

  2. Molecular dynamics simulation of a chemical reaction

    International Nuclear Information System (INIS)

    Gorecki, J.; Gryko, J.

    1988-06-01

    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

  3. Chemical boundary layers in CVD II. Reversible reactions

    NARCIS (Netherlands)

    Croon, de M.H.J.M.; Giling, L.J.

    1990-01-01

    In addition to irreversible reactions, which were treated in part I, reversible reactions in the gas phase have beenstudied using the concept of the chemical boundary layer. The analysis is given for the situations in which either the forwardor the back reaction is dominant. Two conceptual models

  4. 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.

  5. Chemical Demonstrations with Consumer Chemicals: The Black and White Reaction

    Science.gov (United States)

    Wright, Stephen W.

    2002-01-01

    A color-change reaction is described in which two colorless solutions are combined to afford a black mixture. Two more colorless solutions are combined to afford a white mixture. The black and white mixtures are then combined to afford a clear, colorless solution. The reaction uses chemicals that are readily available on the retail market: vitamin C, tincture of iodine, vinegar, ammonia, bleach, Epsom salt, and laundry starch.

  6. MRI of chemical reactions and processes.

    Science.gov (United States)

    Britton, Melanie M

    2017-08-01

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

  7. 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...

  8. The effects of vermicompost and chemical fertilizers on yield and yield components of marshmallow (Altheae officinalis L.

    Directory of Open Access Journals (Sweden)

    A.A. Sadeghi

    2016-05-01

    Full Text Available In order to investigate the effects of vermicompost and chemical fertilizers on growth characteristics, yield and yield components of marshmallow (Altheaeofficinalis L., a field experiment was conducted as factorial layout based on a randomized complete block design with three replications at Faculty of Agriculture, Ferdowsi University of Mashhad, Iran, during growing season of 2012. Experimental treatments were designed based on 3 levels of vermicompost (0, 5 and 10 t ha-1 and 5 levels of nitrogen fertilizer (0, 25, 50, 75 and 100% of 200 kg N ha-1. Results indicated that applied vermicompost had significant effects on increasing leaf area, flower weight per plant and grain yield of marshmallow. Flower weight per plant and grain yield of marshmallow was increased by 2 to 3 times by applying vermicompost at 10 t. ha-1, as compared to control treatment. In addition, nitrogen fertilizer had a significant effect on increasing flower weight per plant and grain, mucilage and oil yields of marshmallow. It seems that applying vermicompost can be suitable strategy in reducing the problems caused by excessive using of chemical fertilizers.

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

    DEFF Research Database (Denmark)

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

    2011-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Deshmukh, Shivaraj D.; Tsori, Yoav, E-mail: tsori@bgu.ac.il [Department of Chemical Engineering, Ben-Gurion University of the Negev, Beer-Sheva 84105 (Israel)

    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.

  11. 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.

  12. Enrichment: CRISLA [chemical reaction by isotope selective activation] aims to reduce costs

    International Nuclear Information System (INIS)

    Eerkens, J.W.

    1989-01-01

    Every year, more than $3 billion is spent on enriching uranium. CRISLA (Chemical Reaction by Isotope Selective Activation) uses a laser-catalyzed chemical reaction which, its proponents claim, could substantially reduce these costs. In CRISLA, an infrared CO laser illuminates the intracavity reaction cell (IC) at a frequency tuned to excite primarily UF 6 . When UF 6 and co-reactant RX are passed through the IC, the tuned laser photons preferentially enhance the reaction of UF 6 with RX ten-thousand-fold over the thermal reaction rate. Thus the laser serves as an activator and the chemical energy for separation is largely chemical. (author)

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

    International Nuclear Information System (INIS)

    Wolery, T.J.

    1981-02-01

    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

  14. Reaction of sweetpotato clones to virus disease and their yield ...

    African Journals Online (AJOL)

    Although among the available control measures use of resistant and high yielding varieties is the cheapest and effective means of controlling the disease, reaction of several sweetpotato clones to the disease is largely unknown. A study was conducted in three geographical regions (Namulonge, Kachwekano, Bulegeni, ...

  15. Non-Equilibrium Heavy Flavored Hadron Yields from Chemical Equilibrium Strangeness-Rich QGP

    OpenAIRE

    Kuznetsova, Inga; Rafelski, Johann

    2008-01-01

    The yields of heavy flavored hadrons emitted from strangeness-rich QGP are evaluated within chemical non-equilibrium statistical hadronization model, conserving strangeness, charm, and entropy yields at hadronization.

  16. Radiation-chemical yields of molecular hydrogen formation in cyclohexane based alcohols

    International Nuclear Information System (INIS)

    Val'ter, A.I.; Kovalev, G.V.

    1988-01-01

    Molecular hydrogen radiation-chemical yields in γ-irradiated cyclohexanol, 1.2-cis- and 1.2-trans-cyclohexandiols and inositol are determined within the general problem frameworks of radiolysis mechanism for cyclohexanering-base alcohols. Irradiation was conducted at 77 and 293 K, dose rate - 4 Gy/s. Hydrogen concentration in all irradiated alcohols depends linearly on the dose. Radiation-chemical yields of H 2 and of stabilized radicals, as well, in the irradiated crystalline alcohols are analyzed depending on the irradiation temperature, alcohol molecular structure

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

    African Journals Online (AJOL)

    The effect of flow parameters on the coefficient of skin friction, Nusselt number and Sherwood number are also tabulated and discussed appropriately. It was observed that the increase in chemical reaction coefficient/parameter suppresses both velocity and concentration profiles. Keywords: Chemical Reaction, MHD, ...

  18. Barium and xenon isotope yields in photopion reactions in cesium-133

    International Nuclear Information System (INIS)

    Sakamoto, K.; Hamajima, Y.; Soto, M.

    1989-09-01

    The radiochemical yield measurements are reported of barium isotopes from 133 Cs(γ, π - xn) 133-x Ba for x=0, 2, 4, 5, 6, 7 and 9 for bremsstrahlung maximum end-point energies (E 0 )=30∼1050 MeV and of 133 Xe from 133 Cs(γ, π + ) 133m,g Xe for E 0 =300∼1000 MeV. An emphasis was placed on Ba measurements around pion threshold and on runs for different target thickness to assess the interfering secondary particle-induced reactions. A clear evidence of the secondary reactions was found in a form of a shoulder of the yield curves in a range of E 0 π -, the Q value of 133 Cs(γ, π - xn) reaction, and used for the correction at E 0 π - with aids of the reported measurements of the photoprotons from 12 C and other complex nuclei and the cross sections of ( 133 Cs+p) reactions. The yields corrected for the secondaries, σ q (E 0 ), were unfolded into cross sections per photon of energy k, σ(k). The characteristic features of σ q (E 0 ) and/or σ(k) are then discussed in terms of E 0 - and k-dependence and product mass (A P =133-x), by comparing the present results with those currently obtained in our group. It was found that the present results of σ(k) are grossly reproduced by a cascade-evaporation calculation based on the PICA code by Gabriel and Alsmiller, only if the calculated ones are shifted in photon energy by k=30 MeV higher and the cutoff energy for neutron is chosen to be 1 MeV. (author)

  19. Effects of Chemical and Organic Fertilizers on Growth, Yield and Yield Component of Tomato (Lycopersicon sculentum L.

    Directory of Open Access Journals (Sweden)

    R Mirzaei Talarposhti

    2017-03-01

    Full Text Available Introduction Although using animal manures and crop residues as a traditional method for increasing soil fertility and crop yield has a long history but Conventional agricultural systems rely on the use of chemical fertilizer due to its immediate availability of nutrients. In many of modern agricultural systems using chemical fertilizers as a fast and easiest way to reduce nutrient deficiency and increasing soil fertility is considered. Intensive and continuous use of chemical fertilizers leads to decreasing the stability and sustainability of agricultural systems and also poses major threat to environment and human health. Organic fertilizers have positive effects on physiochemical and biological attributes of soil and could be classified in three different groups (i.e. Animal manures, green manure and composts.Using animal manure not only increase soil fertility but also could result in increasing infiltration, aeration and water holding capacity of soil. The main role of these fertilizers is related to physical change in soil. Different types of composts such as municipal waste compost and vermicompost also have similar positive effects, but usually the farmers observe the main effect of these organic fertilizers in long term. In order to investigate the effects of different types of organic fertilizers on growth indexes, yield and yield component of tomato (Lycopersicon sculentum L. current experiment was conducted. Materials and Methods The experiment was conducted based on randomized complete block design (RCBD with three replications and six treatments in the research station of Shahid Beheshti University. The experimental treatments were: Control or no fertilizer (NF, chemical fertilizer (CF, cow manure (CM, poultry manure (PM, vermicompost (VC and municipal waste compost (MC. Considering nitrogen concentration in all of the treatments different amounts of these fertilizers were used based on nitrogen recommendation for the field, so in

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

    Science.gov (United States)

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

    2011-06-01

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

  1. Depressurization accident analysis of MPBR by PBRSIM with chemical reaction model

    International Nuclear Information System (INIS)

    No, Hee Cheon; Kadak, A. C.

    2002-01-01

    The simple model for natural circulation is implemented into PBR S IM to provide air inlet velocity from the containment air space. For the friction and form loss only the pebble region is considered conservatively modeling laminar flow through a packed bed. For the chemical reaction model of PBR S IM the oxidation rate is determined as the minimum value of three mechanisms estimated at each time step: oxygen mass flow rate entering the bottom of the reflector, oxidation rate by kinetics, and oxygen mass flow rate arriving at the graphite surface by diffusion. Oxygen mass flux arriving at the graphite surface by diffusion is estimated based on energy-mass analogy. Two types of exothermic chemical reaction are considered: (C + zO 2 → xCO + yCO 2 ) and (2CO + O 2 2CO 2 ). The heterogeneous and homogeneous chemical reaction rates by kinetics are determined by INEEL and Bruno correlations, respectively. The instantaneous depressurization accident of MPBR is simulated using PBR S IM with chemical model. The air inlet velocity is initially rapidly dropped within 10 hr and reaches a saturation value of about 1.5cm/s. The oxidation rate by the diffusion process becomes lower than that by the chemical kinetics above 600K. The maximum pebble bed temperatures without and with chemical reaction reach the peak values of 1560 and 1617 .deg. C at 80 hr and 92 hr, respectively. As the averaged temperatures in the bottom reflector and the pebble bed regions increase with time, (C+1/2O2 ->CO) reaction becomes dominant over (C+O 2 →CO 2 ) reaction. Also, the CO generated by (C+1/2O 2 →CO) reaction will be consumed by (2CO+O 2 →2CO 2 ) reaction and the energy homogeneously generated by this CO depletion reaction becomes dominant over the heterogeneous reaction

  2. Raman Spectral Determination of Chemical Reaction Rate Characteristics

    Science.gov (United States)

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

    2017-09-01

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

  3. Sputtering yields and surface chemical modification of tin-doped indium oxide in hydrocarbon-based plasma etching

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hu; Karahashi, Kazuhiro; Hamaguchi, Satoshi, E-mail: hamaguch@ppl.eng.osaka-u.ac.jp [Center for Atomic and Molecular Technologies, Osaka University, Yamadaoka 2-1, Suita 565-0871 (Japan); Fukasawa, Masanaga; Nagahata, Kazunori; Tatsumi, Tetsuya [Device and Material R& D Group, RDS Platform, Sony Corporation, Kanagawa 243-0014 (Japan)

    2015-11-15

    Sputtering yields and surface chemical compositions of tin-doped indium oxide (or indium tin oxide, ITO) by CH{sup +}, CH{sub 3}{sup +}, and inert-gas ion (He{sup +}, Ne{sup +}, and Ar{sup +}) incidence have been obtained experimentally with the use of a mass-selected ion beam system and in-situ x-ray photoelectron spectroscopy. It has been found that etching of ITO is chemically enhanced by energetic incidence of hydrocarbon (CH{sub x}{sup +}) ions. At high incident energy incidence, it appears that carbon of incident ions predominantly reduce indium (In) of ITO and the ITO sputtering yields by CH{sup +} and CH{sub 3}{sup +} ions are found to be essentially equal. At lower incident energy (less than 500 eV or so), however, a hydrogen effect on ITO reduction is more pronounced and the ITO surface is more reduced by CH{sub 3}{sup +} ions than CH{sup +} ions. Although the surface is covered more with metallic In by low-energy incident CH{sub 3}{sup +} ions than CH{sup +} ions and metallic In is in general less resistant against physical sputtering than its oxide, the ITO sputtering yield by incident CH{sub 3}{sup +} ions is found to be lower than that by incident CH{sup +} ions in this energy range. A postulation to account for the relation between the observed sputtering yield and reduction of the ITO surface is also presented. The results presented here offer a better understanding of elementary surface reactions observed in reactive ion etching processes of ITO by hydrocarbon plasmas.

  4. 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

    2014-11-12

    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.

  5. Chemical reactions of fission products with ethylene using the gas jet technique

    International Nuclear Information System (INIS)

    Contis, E.T.; Rengan, Krish; Griffin, Henry C.

    1994-01-01

    An understanding of the nature of the chemical reactions taking place between fission products and their carrier gases, and the designing of a fast separation procedure were the purposes of this investigation. Chemical reactions of short-lived (less than one minute half-life) fission products with carrier gases lead to various chemical species which can be separated in the gas phase. The Gas Jet Facility at the Ford Nuclear Reactor was used to study the yields of volatile selenium and bromine fission products of 235 U using a semi-automatic batch solvent extraction technique. Heptane and water were used as organic and inorganic solvents. A carrier gas mixture of ethylene to pre-purified nitrogen (1 : 3) was used to sweep the fission products from the target to the chemistry area for analysis. The results indicated that the volatile selenium products generated by the interaction of selenium fission fragments with ethylene were predominantly organic in nature (84%), possibly organoselenides. The selenium values were used to resolve the fractions of the bromine nuclides, which come from two major sources, viz., directly from fission and from the beta-decay of selenium. The data showed that the fractions of independent bromine fission products in the organic phase were much lower compared to selenium; the bromine values range from 10 to 22% and varied with mass number. Results indicated that the bromine products were inorganic in nature, as possibly hydrogen chloride. ((orig.))

  6. An investigation of oxidation products and SOA yields from OH + pesticide reactions

    Science.gov (United States)

    Murschell, T.; Friedman, B.; Link, M.; Farmer, D.

    2016-12-01

    Pesticides are used globally in agricultural and residential areas. After application and/or volatilization from a surface, these compounds can be transported over long distances in the atmosphere. However, their chemical fate, including oxidation and gas-particle partitioning in the atmosphere, is not well understood. We present gas and particle measurements of oxidation products from pesticide + OH reactions using a dynamic solution injection system coupled to an Oxidative Flow Reactor. Products were detected with a High Resolution Time of Flight Iodide Chemical Mass Spectrometer (HR-ToF-CIMS) and a Size Mobility Particle Scanner (SMPS). The OFR allows pesticides to react with variable OH radical exposures, ranging from the equivalent of one day to a full week of atmospheric oxidative aging. In this work, we explore pesticide oxidation products from reaction with OH and ozone, and compare those products to photolysis reactions. Pesticides of similar chemical structures were explored, including acetochlor / metolachlor and permethrin / cypermethrin, to explore mechanistic differences. We present chemical parameters including average product oxidation state, average oxygen to carbon ratio, and potential secondary organic aerosol formation for each of these compounds.

  7. Conservation-dissipation structure of chemical reaction systems.

    Science.gov (United States)

    Yong, Wen-An

    2012-12-01

    In this Brief Report, we show that balanced chemical reaction systems governed by the law of mass action have an elegant conservation-dissipation structure. From this structure a number of important conclusions can be easily deduced. In particular, with the help of this structure we can rigorously justify the classical partial equilibrium approximation in chemical kinetics.

  8. Photo- and radiation-chemical stability of molecules. Reactions of monomolecular hydrogen atom splitting off

    International Nuclear Information System (INIS)

    Plotnikov, V.G.; Ovchinnikov, A.A.

    1978-01-01

    In the review of works published up to 1978 one of the main problems of radiation chemistry is discussed, namely the relationship between the structure of organic molecules and their resistance to the effect of ionizing radiation. Theoretical aspects of this problem are considered for reactions of monomolecular hydrogen atom splitting off. It is shown that the radical yield in low-temperature radiation-chemical experiments is connected with the position of lower triplet states of molecules, ionization potentials, polarity of medium and the energy of C-H bonds in cation radicals

  9. Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2--The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates.

    Science.gov (United States)

    Luca, Oana R; Fenwick, Aidan Q

    2015-11-01

    The present review covers organic transformations involved in the reduction of CO2 to chemical fuels. In particular, we focus on reactions of CO2 with organic molecules to yield carboxylic acid derivatives as a first step in CO2 reduction reaction sequences. These biomimetic initial steps create opportunities for tandem electrochemical/chemical reductions. We draw parallels between long-standing knowledge of CO2 reactivity from organic chemistry, organocatalysis, surface science and electrocatalysis. We point out some possible non-faradaic chemical reactions that may contribute to product distributions in the production of solar fuels from CO2. These reactions may be accelerated by thermal effects such as resistive heating and illumination. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Thermo effect of chemical reaction in irreversible electrochemical systems

    International Nuclear Information System (INIS)

    Tran Vinh Quy; Nguyen Tang

    1989-01-01

    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

  11. Waste dissolution with chemical reaction, diffusion and advection

    International Nuclear Information System (INIS)

    Chambre, P.L.; Kang, C.H.; Lee, W.W.L.; Pigford, T.H.

    1987-06-01

    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

  12. Investigations on an environment friendly chemical reaction process (eco-chemistry). 2; Kankyo ni yasashii kagaku hanno process (eko chemistry) ni kansuru chosa. 2

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-03-01

    In order to structure a chemical reaction process that does not discharge a large amount of waste by-products or harmful chemical substances, or so-called environment friendly process, investigations and discussions were given based on the results derived in the previous fiscal year. A proposal was made to reduce environmental load on development of oxidized and dehydrogenated catalysts that can produce selectively ethylene, propylene and isobutylene in an oxidation process. In liquid phase oxidation, redox-based oxidation and solid catalyzation of automatic oxidation reaction were enumerated. In acid base catalyst reaction, development of ultra strong solid acid was described to structure no pollution discharging process. In the fine chemical and pharmaceutical fields, the optical active substance method and the position-selective aromatics displacement reaction were evaluated to reduce environmental load. A questionnaire survey performed on major chemical corporations inside and outside the country revealed the following processes as the ones that can cause hidden environmental problems: processes discharging large amount of wastes, processes treating dangerous materials, and processes consuming large amount of energy. Development of catalysts is important that can realize high yield, high selectivity and reactions under mild conditions as a future environment harmonizing chemical process. 117 refs., 23 figs., 22 tabs.

  13. Formal modeling of a system of chemical reactions under uncertainty.

    Science.gov (United States)

    Ghosh, Krishnendu; Schlipf, John

    2014-10-01

    We describe a novel formalism representing a system of chemical reactions, with imprecise rates of reactions and concentrations of chemicals, and describe a model reduction method, pruning, based on the chemical properties. We present two algorithms, midpoint approximation and interval approximation, for construction of efficient model abstractions with uncertainty in data. We evaluate computational feasibility by posing queries in computation tree logic (CTL) on a prototype of extracellular-signal-regulated kinase (ERK) pathway.

  14. Computational prediction of chemical reactions: current status and outlook.

    Science.gov (United States)

    Engkvist, Ola; Norrby, Per-Ola; Selmi, Nidhal; Lam, Yu-Hong; Peng, Zhengwei; Sherer, Edward C; Amberg, Willi; Erhard, Thomas; Smyth, Lynette A

    2018-06-01

    Over the past few decades, various computational methods have become increasingly important for discovering and developing novel drugs. Computational prediction of chemical reactions is a key part of an efficient drug discovery process. In this review, we discuss important parts of this field, with a focus on utilizing reaction data to build predictive models, the existing programs for synthesis prediction, and usage of quantum mechanics and molecular mechanics (QM/MM) to explore chemical reactions. We also outline potential future developments with an emphasis on pre-competitive collaboration opportunities. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. 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

  16. Reaction path analysis of sodium-water reaction phenomena in support of chemical reaction model development

    International Nuclear Information System (INIS)

    Kikuchi, Shin; Ohshima, Hiroyuki; Hashimoto, Kenro

    2011-01-01

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule to the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. The results are used as the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by JAEA toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR). (author)

  17. 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.

  18. 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.

  19. A Data-Driven Sparse-Learning Approach to Model Reduction in Chemical Reaction Networks

    OpenAIRE

    Harirchi, Farshad; Khalil, Omar A.; Liu, Sijia; Elvati, Paolo; Violi, Angela; Hero, Alfred O.

    2017-01-01

    In this paper, we propose an optimization-based sparse learning approach to identify the set of most influential reactions in a chemical reaction network. This reduced set of reactions is then employed to construct a reduced chemical reaction mechanism, which is relevant to chemical interaction network modeling. The problem of identifying influential reactions is first formulated as a mixed-integer quadratic program, and then a relaxation method is leveraged to reduce the computational comple...

  20. Curly arrows meet electron density transfers in chemical reaction mechanisms: from electron localization function (ELF) analysis to valence-shell electron-pair repulsion (VSEPR) inspired interpretation.

    Science.gov (United States)

    Andrés, Juan; Berski, Sławomir; Silvi, Bernard

    2016-07-07

    Probing the electron density transfers during a chemical reaction can provide important insights, making possible to understand and control chemical reactions. This aim has required extensions of the relationships between the traditional chemical concepts and the quantum mechanical ones. The present work examines the detailed chemical insights that have been generated through 100 years of work worldwide on G. N. Lewis's ground breaking paper on The Atom and the Molecule (Lewis, G. N. The Atom and the Molecule, J. Am. Chem. Soc. 1916, 38, 762-785), with a focus on how the determination of reaction mechanisms can be reached applying the bonding evolution theory (BET), emphasizing how curly arrows meet electron density transfers in chemical reaction mechanisms and how the Lewis structure can be recovered. BET that combines the topological analysis of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool providing insight into molecular mechanisms of chemical rearrangements. In agreement with physical laws and quantum theoretical insights, BET can be considered as an appropriate tool to tackle chemical reactivity with a wide range of possible applications. Likewise, the present approach retrieves the classical curly arrows used to describe the rearrangements of chemical bonds for a given reaction mechanism, providing detailed physical grounds for this type of representation. The ideas underlying the valence-shell-electron pair-repulsion (VSEPR) model applied to non-equilibrium geometries provide simple chemical explanations of density transfers. For a given geometry around a central atom, the arrangement of the electronic domain may comply or not with the VSEPR rules according with the valence shell population of the considered atom. A deformation yields arrangements which are either VSEPR defective (at least a domain is missing to match the VSEPR arrangement corresponding to the geometry of the ligands), VSEPR compliant

  1. 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

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

    Science.gov (United States)

    Zavialov, Ivan; Konyukhov, Andrey; Negodyaev, Sergey

    2015-04-01

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

  3. Strain-induced structural changes and chemical reactions. 1: Thermomechanical and kinetic models

    International Nuclear Information System (INIS)

    Levitas, V.I.; Nesterenko, V.F.; Meyers, M.A.

    1998-01-01

    Strain-induced chemical reactions were observed recently (Nesterenko et al) in experiments in the shear band in both Ti-Si and Nb-Si mixtures. Reactions can start in the solid state or after melting of at least one component. One of the aims is to find theoretically whether there are possible macroscopic mechanisms of mechanical intensification of the above and other chemical reactions due to plastic shear in the solid state. Continuum thermodynamical theory of structural changes with an athermal kinetics, which includes martensitic phase transformations, plastic strain-induced chemical reactions and polymorphic transformations, is developed at finite strains. The theory includes kinematics, criterion of structural change and extremum principle for determination of all unknown variable parameters for the case with neglected elastic strains. Thermodynamically consistent kinetic theory of thermally activated structural changes is suggested. The concept of the effective temperature is introduced which takes into account that temperature can vary significantly (on 1,000 K) during the chemical reactions under consideration. The theory will be applied in Part 2 of the paper for the description of chemical reactions in the shear band

  4. Comparative Analysis of the $^{178m2}$Hf Yield at Reactions with Different Projectiles

    CERN Document Server

    Karamian, S A

    2004-01-01

    The long-lived high-spin $^{178m2}$Hf $K$-isomer can be produced in nuclear reactions with different projectiles. The reaction yields and cross-sections have been measured in the series of experiments and the results are now overviewed. The systematics of isomer-to-ground state ratios are drawn and real production capabilities are estimated for the best reactions. Such a summary is relevant to the significance of the isomer studies both for the nuclear-science knowledge and for possible applications. Potential isomer applications have been earlier stressed in popular publications with probably overestimated expectations. The real possibilities are restricted in part by the production yield and by other shortcomings as well.

  5. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

    International Nuclear Information System (INIS)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Brooks, Scott C; Pace, Molly; Kim, Young Jin; Jardine, Philip M.; Watson, David B.

    2007-01-01

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M. partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M. species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M-NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions

  6. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions.

    Science.gov (United States)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C; Brooks, Scott C; Pace, Molly N; Kim, Young-Jin; Jardine, Philip M; Watson, David B

    2007-06-16

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  7. BGK-type models in strong reaction and kinetic chemical equilibrium regimes

    International Nuclear Information System (INIS)

    Monaco, R; Bianchi, M Pandolfi; Soares, A J

    2005-01-01

    A BGK-type procedure is applied to multi-component gases undergoing chemical reactions of bimolecular type. The relaxation process towards local Maxwellians, depending on mass and numerical densities of each species as well as common velocity and temperature, is investigated in two different cases with respect to chemical regimes. These cases are related to the strong reaction regime characterized by slow reactions, and to the kinetic chemical equilibrium regime where fast reactions take place. The consistency properties of both models are stated in detail. The trend to equilibrium is numerically tested and comparisons for the two regimes are performed within the hydrogen-air and carbon-oxygen reaction mechanism. In the spatial homogeneous case, it is also shown that the thermodynamical equilibrium of the models recovers satisfactorily the asymptotic equilibrium solutions to the reactive Euler equations

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

    CSIR Research Space (South Africa)

    Du Plessis, A

    2010-09-01

    Full Text Available Femtosecond laser control of chemical reactions is made possible through the use of pulse-shaping techniques coupled to a learning algorithm feedback loop – teaching the laser pulse to control the chemical reaction. This can result in controllable...

  9. Nanoparticle-triggered in situ catalytic chemical reactions for tumour-specific therapy.

    Science.gov (United States)

    Lin, Han; Chen, Yu; Shi, Jianlin

    2018-03-21

    Tumour chemotherapy employs highly cytotoxic chemodrugs, which kill both cancer and normal cells by cellular apoptosis or necrosis non-selectively. Catalysing/triggering the specific chemical reactions only inside tumour tissues can generate abundant and special chemicals and products locally to initiate a series of unique biological and pathologic effects, which may enable tumour-specific theranostic effects to combat cancer without bringing about significant side effects on normal tissues. Nevertheless, chemical reaction-initiated selective tumour therapy strongly depends on the advances in chemistry, materials science, nanotechnology and biomedicine. This emerging cross-disciplinary research area is substantially different from conventional cancer-theranostic modalities in clinics. In response to the fast developments in cancer theranostics based on intratumoural catalytic chemical reactions, this tutorial review summarizes the very-recent research progress in the design and synthesis of representative nanoplatforms with intriguing nanostructures, compositions, physiochemical properties and biological behaviours for versatile catalytic chemical reaction-enabled cancer treatments, mainly by either endogenous tumour microenvironment (TME) triggering or exogenous physical irradiation. These unique intratumoural chemical reactions can be used in tumour-starving therapy, chemodynamic therapy, gas therapy, alleviation of tumour hypoxia, TME-responsive diagnostic imaging and stimuli-responsive drug release, and even externally triggered versatile therapeutics. In particular, the challenges and future developments of such a novel type of cancer-theranostic modality are discussed in detail to understand the future developments and prospects in this research area as far as possible. It is highly expected that this kind of unique tumour-specific therapeutics by triggering specific in situ catalytic chemical reactions inside tumours would provide a novel but efficient

  10. Open complex-balanced mass action chemical reaction networks

    NARCIS (Netherlands)

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

    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.

  11. A chemical reaction in the movie The Ten Commandments

    Directory of Open Access Journals (Sweden)

    López Pérez, José Pedro;

    2012-04-01

    Full Text Available The study of natural sciences in the second year of Secondary Education must be complemented with a visit to the laboratory, where experiments should be permormed. The curriculum emphasizes the initial basis of Chemistry and the study of reactions. In this paper we describe a laboratory experience, useful for understanding the concept of chemical change. Also, we present the hypothesis that a chemical reaction was used in the classic movie The Ten Commandments.

  12. Adsorption and catalysis: The effect of confinement on chemical reactions

    International Nuclear Information System (INIS)

    Santiso, Erik E.; George, Aaron M.; Turner, C. Heath; Kostov, Milen K.; Gubbins, Keith E.; Buongiorno-Nardelli, Marco; Sliwinska-Bartkowiak, MaIgorzata

    2005-01-01

    Confinement within porous materials can affect chemical reactions through a host of different effects, including changes in the thermodynamic state of the system due to interactions with the pore walls, selective adsorption, geometrical constraints that affect the reaction mechanism, electronic perturbation due to the substrate, etc. In this work, we present an overview of some of our recent research on some of these effects, on chemical equilibrium, kinetic rates and reaction mechanisms. We also discuss our current and future directions for research in this area

  13. The Effect of Chemical, Biological and Organic Nutritional Treatments on Sunflowers Yield and Yield Components under the Influence of Water Deficit Stress

    Directory of Open Access Journals (Sweden)

    fatemeh soleymani

    2016-07-01

    Full Text Available Introduction To achieve the higher economic yield of crop plants, supplying enough nutrients to plants is very important. Moreover, nutrient uptakes by plants is influenced by the soil water contents. However, nowadays chemical fertilizer application is important agronomic factor that has significant effects on growth and quantity and quality of final yield, but traditional nutrient management and excessive use of chemical fertilizers may cause the environmental problems such as contamination of soil and water resources, low quality of agricultural products and reduction of soil fertility. These factors have drawn attention to health and ecological sustainable farming systems (Sharma, 2002. In this context, usage of organic and biological products for plant nutrition is considered as one of the solutions to achieve the goals of sustainable agriculture. Materials and methods To evaluate the effect of various feeding systems on yield and yield components of sunflower (Helianthus annuus L. under the influence of water deficit stress, a split-plot experiment based on randomized complete block design with three replications, was carried out in the Agricultural Faculty of Bu-Ali Sina University during the growing season of 2013-2014. Main plots consisted of two irrigation levels: optimum irrigation and deficit irrigation stress (irrigation after 60 and 120 mm evaporation from evaporation pan, class A, respectively and sub-plots included of nine nutrition systems: 1- no bio or chemical fertilizer application, 2- 100% of the recommended chemical fertilizer , 3- vermicompost, 4- phospho nitro kara, 5- vermicompost+ phospho nitro kara, 6- vermicompost+ ½ chemical fertilizer, 7- phospho nitro kara+ ½ chemical fertilizer, 8- vermicompost+ phospho nitro kara+ ½ chemical fertilizer, 9- ½ proposed chemical fertilizer. Phospho-nitro-kara which contains phosphate solubilizing and nitrogen fixing bacteria (Bacillus coagulans, azotobactr chroocuccum and

  14. Direct single-molecule dynamic detection of chemical reactions.

    Science.gov (United States)

    Guan, Jianxin; Jia, Chuancheng; Li, Yanwei; Liu, Zitong; Wang, Jinying; Yang, Zhongyue; Gu, Chunhui; Su, Dingkai; Houk, Kendall N; Zhang, Deqing; Guo, Xuefeng

    2018-02-01

    Single-molecule detection can reveal time trajectories and reaction pathways of individual intermediates/transition states in chemical reactions and biological processes, which is of fundamental importance to elucidate their intrinsic mechanisms. We present a reliable, label-free single-molecule approach that allows us to directly explore the dynamic process of basic chemical reactions at the single-event level by using stable graphene-molecule single-molecule junctions. These junctions are constructed by covalently connecting a single molecule with a 9-fluorenone center to nanogapped graphene electrodes. For the first time, real-time single-molecule electrical measurements unambiguously show reproducible large-amplitude two-level fluctuations that are highly dependent on solvent environments in a nucleophilic addition reaction of hydroxylamine to a carbonyl group. Both theoretical simulations and ensemble experiments prove that this observation originates from the reversible transition between the reactant and a new intermediate state within a time scale of a few microseconds. These investigations open up a new route that is able to be immediately applied to probe fast single-molecule physics or biophysics with high time resolution, making an important contribution to broad fields beyond reaction chemistry.

  15. The Dynamics of Chemical Reactions: Atomistic Visualizations of Organic Reactions, and Homage to van 't Hoff.

    Science.gov (United States)

    Yang, Zhongyue; Houk, K N

    2018-03-15

    Jacobus Henricus van 't Hoff was the first Nobel Laureate in Chemistry. He pioneered in the study of chemical dynamics, which referred at that time to chemical kinetics and thermodynamics. The term has evolved in modern times to refer to the exploration of chemical transformations in a time-resolved fashion. Chemical dynamics has been driven by the development of molecular dynamics trajectory simulations, which provide atomic visualization of chemical processes and illuminate how dynamic effects influence chemical reactivity and selectivity. In homage to the legend of van 't Hoff, we review the development of the chemical dynamics of organic reactions, our area of research. We then discuss our trajectory simulations of pericyclic reactions, and our development of dynamic criteria for concerted and stepwise reaction mechanisms. We also describe a method that we call environment-perturbed transition state sampling, which enables trajectory simulations in condensed-media using quantum mechanics and molecular mechanics (QM/MM). We apply the method to reactions in solvent and in enzyme. Jacobus Henricus van 't Hoff (1852, Rotterdam-1911, Berlin) received the Nobel Prize for Chemistry in 1901 "in recognition of the extraordinary services he has rendered by the discovery of the laws of chemical dynamics and osmotic pressure in solutions". van 't Hoff was born the Netherlands, and earned his doctorate in Utrecht in 1874. In 1896 he moved to Berlin, where he was offered a position with more research and less teaching. van 't Hoff is considered one of the founders of physical chemistry. A key step in establishing this new field was the start of Zeitschrift für Physikalische Chemie in 1887. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Studies in the reaction dynamics of beam-gas chemiluminescent reactions

    International Nuclear Information System (INIS)

    Prisant, M.G.

    1984-01-01

    This thesis develops techniques for the analysis and interpretation of data obtained from beam-gas chemiluminescence experiments. These techniques are applied to experimental studies of atom transfer reactions of the type A + BC → AB + C. A procedure is developed for determining the product rotational alignment in the center-of-mass frame from polarization measurements of chemiluminescent atom-diatom exchange reactions under beam-gas conditions. Knowledge of a vector property of a reaction, such as product alignment, provides information on the disposition of angular momentum by a chemical reaction. Fluorescence polarization and hence product alignment are measured for two prototype reactions. The reaction of metastable calcium atoms with hydrogen-chloride gas yields highly aligned calcium-chloride product which exhibits little variation of alignment with vibrational state. The reaction of ground-state calcium with fluorine gas yields moderately aligned product which shows strong variation of alignment with vibration. A multi-surface direct-interaction model is developed to interpret product alignment and population data. The predictions of this model for the reaction of calcium with fluorine show reasonable agreement with experiment

  17. The effects of vermicompost and chemical fertilizers on yield and yield components of marshmallow (Altheae officinalis L.)

    OpenAIRE

    A.A. Sadeghi; K. Bakhsh Kelarestaghi; K. Hajmohammadnia Ghalibaf

    2016-01-01

    In order to investigate the effects of vermicompost and chemical fertilizers on growth characteristics, yield and yield components of marshmallow (Altheaeofficinalis L.), a field experiment was conducted as factorial layout based on a randomized complete block design with three replications at Faculty of Agriculture, Ferdowsi University of Mashhad, Iran, during growing season of 2012. Experimental treatments were designed based on 3 levels of vermicompost (0, 5 and 10 t ha-1) and 5 levels of ...

  18. Mass transfer with chemical reaction in multiphase systems

    International Nuclear Information System (INIS)

    Alper, E.

    1983-01-01

    These volumes deal with the phenomenon of 'mass transfer with chemical reaction' which is of industrial, biological and physiological importance. In process engineering, it is encountered both in separation processes and in reaction engineering and both aspects are covered here in four sections: introduction; gas-liquid system; liquid-liquid system; and gas-liquid-solid system

  19. High yield neutron generators using the DD reaction

    Energy Technology Data Exchange (ETDEWEB)

    Vainionpaa, J. H.; Harris, J. L.; Piestrup, M. A.; Gary, C. K.; Williams, D. L.; Apodaca, M. D.; Cremer, J. T. [Adelphi technology, 2003 E. Bayshore Rd. 94061, Redwood City, CA (United States); Ji, Qing; Ludewigt, B. A. [Lawrence Berkeley National Lab, 1 Cyclotron Road, Berkeley, CA 94720 (United States); Jones, G. [G and J Enterprise, 1258 Quary Ln, Suite F, Pleasanton California 94566 (United States)

    2013-04-19

    A product line of high yield neutron generators has been developed at Adelphi technology inc. The generators use the D-D fusion reaction and are driven by an ion beam supplied by a microwave ion source. Yields of up to 5 Multiplication-Sign 10{sup 9} n/s have been achieved, which are comparable to those obtained using the more efficient D-T reaction. The microwave-driven plasma uses the electron cyclotron resonance (ECR) to produce a high plasma density for high current and high atomic ion species. These generators have an actively pumped vacuum system that allows operation at reduced pressure in the target chamber, increasing the overall system reliability. Since no radioactive tritium is used, the generators can be easily serviced, and components can be easily replaced, providing essentially an unlimited lifetime. Fast neutron source size can be adjusted by selecting the aperture and target geometries according to customer specifications. Pulsed and continuous operation has been demonstrated. Minimum pulse lengths of 50 {mu}s have been achieved. Since the generators are easily serviceable, they offer a long lifetime neutron generator for laboratories and commercial systems requiring continuous operation. Several of the generators have been enclosed in radiation shielding/moderator structures designed for customer specifications. These generators have been proven to be useful for prompt gamma neutron activation analysis (PGNAA), neutron activation analysis (NAA) and fast neutron radiography. Thus these generators make excellent fast, epithermal and thermal neutron sources for laboratories and industrial applications that require neutrons with safe operation, small footprint, low cost and small regulatory burden.

  20. 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.

  1. On Medium Chemical Reaction in Diffusion-Based Molecular Communication: a Two-Way Relaying Example

    OpenAIRE

    Farahnak-Ghazani, Maryam; Aminian, Gholamali; Mirmohseni, Mahtab; Gohari, Amin; Nasiri-Kenari, Masoumeh

    2016-01-01

    Chemical reactions are a prominent feature of molecular communication (MC) systems, with no direct parallels in wireless communications. While chemical reactions may be used inside the transmitter nodes, receiver nodes or the communication medium, we focus on its utility in the medium in this paper. Such chemical reactions can be used to perform computation over the medium as molecules diffuse and react with each other (physical-layer computation). We propose the use of chemical reactions for...

  2. Theoretical modeling of yields for proton-induced reactions on natural and enriched molybdenum targets

    Energy Technology Data Exchange (ETDEWEB)

    Celler, A; Hou, X [University of British Columbia, Vancouver, BC, Canada, (Canada); Benard, F; Ruth, T, E-mail: aceller@physics.ubc.ca, E-mail: xinchi@phas.ubc.ca, E-mail: fbenard@bccrc.ca, E-mail: truth@triumf.ca [BC Cancer Agency, Vancouver, BC (Canada)

    2011-09-07

    Recent acute shortage of medical radioisotopes prompted investigations into alternative methods of production and the use of a cyclotron and {sup 100}Mo(p,2n){sup 99m}Tc reaction has been considered. In this context, the production yields of {sup 99m}Tc and various other radioactive and stable isotopes which will be created in the process have to be investigated, as these may affect the diagnostic outcome and radiation dosimetry in human studies. Reaction conditions (beam and target characteristics, and irradiation and cooling times) need to be optimized in order to maximize the amount of {sup 99m}Tc and minimize impurities. Although ultimately careful experimental verification of these conditions must be performed, theoretical calculations can provide the initial guidance allowing for extensive investigations at little cost. We report the results of theoretically determined reaction yields for {sup 99m}Tc and other radioactive isotopes created when natural and enriched molybdenum targets are irradiated by protons. The cross-section calculations were performed using a computer program EMPIRE for the proton energy range 6-30 MeV. A computer graphical user interface for automatic calculation of production yields taking into account various reaction channels leading to the same final product has been created. The proposed approach allows us to theoretically estimate the amount of {sup 99m}Tc and its ratio relative to {sup 99g}Tc and other radioisotopes which must be considered reaction contaminants, potentially contributing to additional patient dose in diagnostic studies.

  3. Theoretical modeling of yields for proton-induced reactions on natural and enriched molybdenum targets.

    Science.gov (United States)

    Celler, A; Hou, X; Bénard, F; Ruth, T

    2011-09-07

    Recent acute shortage of medical radioisotopes prompted investigations into alternative methods of production and the use of a cyclotron and ¹⁰⁰Mo(p,2n)(99m)Tc reaction has been considered. In this context, the production yields of (99m)Tc and various other radioactive and stable isotopes which will be created in the process have to be investigated, as these may affect the diagnostic outcome and radiation dosimetry in human studies. Reaction conditions (beam and target characteristics, and irradiation and cooling times) need to be optimized in order to maximize the amount of (99m)Tc and minimize impurities. Although ultimately careful experimental verification of these conditions must be performed, theoretical calculations can provide the initial guidance allowing for extensive investigations at little cost. We report the results of theoretically determined reaction yields for (99m)Tc and other radioactive isotopes created when natural and enriched molybdenum targets are irradiated by protons. The cross-section calculations were performed using a computer program EMPIRE for the proton energy range 6-30 MeV. A computer graphical user interface for automatic calculation of production yields taking into account various reaction channels leading to the same final product has been created. The proposed approach allows us to theoretically estimate the amount of (99m)Tc and its ratio relative to (99g)Tc and other radioisotopes which must be considered reaction contaminants, potentially contributing to additional patient dose in diagnostic studies.

  4. Evaluation of Yield and Yield Components of Oilseed Rape in the Wheat-Oilseed Rape Strip Intercropping Influenced by Chemical and Biological Fertilizers

    Directory of Open Access Journals (Sweden)

    R Amirmardfar

    2015-01-01

    Full Text Available To evaluate the effects of wheat (Triticum aestivum and oilseed rape (Brassica napus strip intercropping on yield components, seed and biological yields of oilseed rape, field experiments were carried out as factorial based on randomized complete block design with three replications at Research Farm of Tabriz University, Tabriz, Iran during 2010-2012 cropping seasons. The first factor consisted of four types of wheat and oilseed rape cropping system, sole crop of oilseed rape (A1,: strip intercropping with 8:3 (A2, 12:4 (A3 and 16:5 (A4 of wheat and oilseed rape rows, respectively and the other factor consisted of two fertilizer levels, B1: 100% chemical fertilizers (urea and triple superphosphate and B2: 50% chemical fertilizers + biofertilizers (Nitrazhin and Barvar2. The results showed that strip intercropping of wheat- oilseed rape resulted in significant increase in yield components, seed yield per occupied unit area and biological yield per occupied unit area of oilseed rape as compared with mono-cropping. The number of silique per plant in intercropping systems was significantly higher than that of mono-cropping. The highest seed yield was obtained in the 16:5 rows of wheat-oilseed rape with 343.76 g.m-2 and the lowest mean was observed in mono-cropping of oilseed rape with 260.21 g.m-2. Biological yield per occupied unit area and seed yield per intercropped unit area in B1 were significantly greater than that of B2, but this treatment had no significant effect on the other traits. Because, B1 and B2 had no significant difference in seed yield per occupied unit area and due to the importance of reduction in chemical fertilizers consumption and food and environmental health care, strip intercropping of wheat-oilseed rape under 50% chemical fertilizers + biofertilizers can be recommended as a suitable cultural method.

  5. Chemical reaction between single hydrogen atom and graphene

    International Nuclear Information System (INIS)

    Ito, Atsushi; Nakamura, Hiroaki; Takayama, Arimichi

    2007-04-01

    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 sp 3 state. (3) The hexagonal hole of the graphene is expanded during the penetration of the hydrogen atom. (author)

  6. Functionalization of multi-walled carbon nanotubes with iron phthalocyanine via a liquid chemical reaction for oxygen reduction in alkaline media

    Science.gov (United States)

    Yan, Xiaomei; Xu, Xiao; Liu, Qin; Guo, Jia; Kang, Longtian; Yao, Jiannian

    2018-06-01

    Iron single-atom catalyst in form of iron-nitrogen-carbon structure possesses the excellent catalytic activity in various chemical reactions. However, exploring a sustainable and stable single-atom metal catalyst still faces a great challenge due to low yield and complicated synthesis. Here, we report a functional multi-wall carbon nanotubes modified with iron phthalocyanine molecules via a liquid chemical reaction and realize the performance of similar single-atom catalysis for oxygen reduction reaction. A serial of characterizations strongly imply the structure change of iron phthalocyanine molecule and its close recombination with multi-wall carbon nanotubes, which are in favor of ORR catalysis. Compared to commercial platinum-carbon catalyst, composites exhibit superior activity for oxygen reduction reaction with higher half-wave potential (0.86 V), lower Tafel slope (38 mV dec-1), higher limiting current density and excellent electrochemical stability. The corresponding Zinc-air battery also presents higher maximum power density and discharge stability. Therefore, these findings provide a facile route to synthesize a highly efficient non-precious metal carbon-based catalyst.

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

    International Nuclear Information System (INIS)

    Deguchi, Yoshihiro; Tamura, Kenta; Muranaka, Ryota; Kusano, Koji; Kikuchi, Shin; Kurihara, Akikazu

    2013-01-01

    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 + H 2 O → 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)

  8. Quantum indistinguishability in chemical reactions.

    Science.gov (United States)

    Fisher, Matthew P A; Radzihovsky, Leo

    2018-05-15

    Quantum indistinguishability plays a crucial role in many low-energy physical phenomena, from quantum fluids to molecular spectroscopy. It is, however, typically ignored in most high-temperature processes, particularly for ionic coordinates, implicitly assumed to be distinguishable, incoherent, and thus well approximated classically. We explore enzymatic chemical reactions involving small symmetric molecules and argue that in many situations a full quantum treatment of collective nuclear degrees of freedom is essential. Supported by several physical arguments, we conjecture a "quantum dynamical selection" (QDS) rule for small symmetric molecules that precludes chemical processes that involve direct transitions from orbitally nonsymmetric molecular states. As we propose and discuss, the implications of the QDS rule include ( i ) a differential chemical reactivity of para- and orthohydrogen, ( ii ) a mechanism for inducing intermolecular quantum entanglement of nuclear spins, ( iii ) a mass-independent isotope fractionation mechanism, ( iv ) an explanation of the enhanced chemical activity of "reactive oxygen species", ( v ) illuminating the importance of ortho-water molecules in modulating the quantum dynamics of liquid water, and ( vi ) providing the critical quantum-to-biochemical linkage in the nuclear spin model of the (putative) quantum brain, among others.

  9. Chemical reactions inside the plasma chamber of the SEAFP reactor plant models

    International Nuclear Information System (INIS)

    Gay, J.M.; Ebert, E.; Mazille, F.

    1995-01-01

    Loss of coolant or loss of vacuum accidents may lead to chemical reactions between the protecting materials of the plasma facing components and air or water. A production of energy, reaction products and hydrogen may be induced. The paper defines the operating conditions and chemical reactions and presents the main results from the underlying studies. (orig.)

  10. Chemical Reactions at Surfaces. Final Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    Freud, Hans-Joachim [Max-Planck-Gesellschaft, Berlin (Germany). Fritz-Haber-Inst.

    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.

  11. Chemical Ligation Reactions of Oligonucleotides for Biological and Medicinal Applications.

    Science.gov (United States)

    Abe, Hiroshi; Kimura, Yasuaki

    2018-01-01

    Chemical ligation of oligonucleotides (ONs) is the key reaction for various ON-based technologies. We have tried to solve the problems of RNA interference (RNAi) technology by applying ON chemical ligation to RNAi. We designed a new RNAi system, called intracellular buildup RNAi (IBR-RNAi), where the RNA fragments are built up into active small-interference RNA (siRNA) in cells through a chemical ligation reaction. Using the phosphorothioate and iodoacetyl groups as reactive functional groups for the ligation, we achieved RNAi effects without inducing immune responses. Additionally, we developed a new chemical ligation for IBR-RNAi, which affords a more native-like structure in the ligated product. The new ligation method should be useful not only for IBR-RNAi but also for the chemical synthesis of biofunctional ONs.

  12. 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...

  13. Acid-yield measurements of the gas-phase ozonolysis of ethene as a function of humidity using Chemical Ionisation Mass Spectrometry (CIMS

    Directory of Open Access Journals (Sweden)

    K. E. Leather

    2012-01-01

    Full Text Available Gas-phase ethene ozonolysis experiments were conducted at room temperature to determine formic acid yields as a function of relative humidity (RH using the integrated EXTreme RAnge chamber-Chemical Ionisation Mass Spectrometry technique, employing a CH3I ionisation scheme. RHs studied were <1, 11, 21, 27, 30 % and formic acid yields of (0.07±0.01 and (0.41±0.07 were determined at <1 % RH and 30 % RH respectively, showing a strong water dependence. It has been possible to estimate the ratio of the rate coefficient for the reaction of the Criegee biradical, CH2OO with water compared with decomposition. This analysis suggests that the rate of reaction with water ranges between 1×10−12–1×10−15 cm3 molecule−1 s−1 and will therefore dominate its loss with respect to bimolecular processes in the atmosphere. Global model integrations suggest that this reaction between CH2OO and water may dominate the production of HC(OOH in the atmosphere.

  14. Cover Crops Effects on Soil Chemical Properties and Onion Yield

    Directory of Open Access Journals (Sweden)

    Rodolfo Assis de Oliveira

    2016-01-01

    Full Text Available ABSTRACT Cover crops contribute to nutrient cycling and may improve soil chemical properties and, consequently, increase crop yield. The aim of this study was to evaluate cover crop residue decomposition and nutrient release, and the effects of these plants on soil chemical properties and on onion (Allium cepa L. yield in a no-tillage system. The experiment was carried out in an Inceptisol in southern Brazil, where cover crops were sown in April 2012 and 2013. In July 2013, shoots of weeds (WD, black oats (BO, rye (RY, oilseed radish (RD, oilseed radish + black oats (RD + BO, and oilseed radish + rye (RD + RY were cut at ground level and part of these material from each treatment was placed in litter bags. The litter bags were distributed on the soil surface and were collected at 0, 30, 45, 60, 75, and 90 days after distribution (DAD. The residues in the litter bags were dried, weighed, and ground, and then analyzed to quantify lignin, cellulose, non-structural biomass, total organic carbon (TOC, N, P, K, Ca, and Mg. In November 2012 and 2013, onion crops were harvested to quantify yield, and bulbs were classified according to diameter, and the number of rotted and flowering bulbs was determined. Soil in the 0.00-0.10 m layer was collected for chemical analysis before transplanting and after harvesting onion in December 2012 and 2013. The rye plant residues presented the highest half-life and they released less nutrients until 90 DAD. The great permanence of rye residue was considered a protection to soil surface, the opposite was observed with spontaneous vegetation. The cultivation and addition of dry residue of cover crops increased the onion yield at 2.5 Mg ha-1.

  15. Conversion of KCl into KBH4 by Mechano-Chemical Reaction and its Catalytic Decomposition

    Science.gov (United States)

    Bilen, Murat; Gürü, Metin; Çakanyildirim, Çetin

    2017-07-01

    Production of KBH4, in the presence of KCl, B2O3 and MgH2 by means of a mechanical reaction and a dehydrogenation kinetic, constitute the main parts of this study. Operating time and reactant ratio are considered as two parameters for the mechanical reaction to obtain the maximum yield. The production process was carried out in a ball milling reactor, and the product residue was purified with ethylene diamine (EDA) and subsequently characterized by Fourier Transform Infrared Spectroscopy (FT-IR) and x-ray Diffraction (XRD) analyses. Optimum time for mechano-chemical treatment and reactant ratio (MgH2/KCl) were obtained as 1000 min and 1.0, respectively. Synthesized and commercial KBH4 were compared by hydrolysis tests in the presence of Co1-xNix/Al2O3 heterogeneous catalyst. Hydrogen generation rates, activation energy and order of the KBH4 decomposition reaction were obtained as 1578 {mL}_{{{{H}}2 }} \\min^{ - 1} {g}_{{catalyst}}^{ - 1}, 39.2 kJ mol-1 and zero order, respectively.

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

    International Nuclear Information System (INIS)

    Takayanagi, Toshiyuki

    1998-01-01

    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 + H 2 → 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. Mapping students' ideas about chemical reactions at different educational levels

    Science.gov (United States)

    Yan, Fan

    Understanding chemical reactions is crucial in learning chemistry at all educational levels. Nevertheless, research in science education has revealed that many students struggle to understand chemical processes. Improving teaching and learning about chemical reactions demands that we develop a clearer understanding of student reasoning in this area and of how this reasoning evolves with training in the discipline. Thus, we have carried out a qualitative study using semi-structured interviews as the main data collection tool to explore students reasoning about reaction mechanism and causality. The participants of this study included students at different levels of training in chemistry: general chemistry students (n=22), organic chemistry students (n=16), first year graduate students (n=13) and Ph.D. candidates (n=14). We identified major conceptual modes along critical dimensions of analysis, and illustrated common ways of reasoning using typical cases. Main findings indicate that although significant progress is observed in student reasoning in some areas, major conceptual difficulties seem to persist even at the more advanced educational levels. In addition, our findings suggest that students struggle to integrate important concepts when thinking about mechanism and causality in chemical reactions. The results of our study are relevant to chemistry educators interested in learning progressions, assessment, and conceptual development.

  18. Effect of the Gouy phase on the coherent phase control of chemical reactions.

    Science.gov (United States)

    Gordon, Robert J; Barge, Vishal J

    2007-11-28

    We show how the spatial phase of a focused laser beam may be used as a tool for controlling the branching ratio of a chemical reaction. Guoy discovered [Acad. Sci., Paris, C. R. 110, 1250 (1890)] that when an electromagnetic wave passes through a focus its phase increases by pi. In a coherent control scheme involving the absorption of n photons of frequency omega(m) and m photons of frequency omega(n), the overall phase shift produced by the Gouy phase is (n-m)pi. At any given point in space, this phase shift is identical for all reaction products. Nevertheless, if the yields for different reaction channels have different intensity dependencies, the Gouy phase produces a net phase lag between the products that varies with the axial coordinate of the laser focus. We obtain here analytical and numerical values of this phase as the laser focus is scanned across the diameter of the molecular beam, taking into account the Rayleigh range and astigmatism of the laser beam and saturation of the transition. We also show that the modulation depth of the interference pattern may be increased by optimizing the relative intensities of the two fields.

  19. 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.

  20. Physio-chemical reactions in recycle aggregate concrete

    International Nuclear Information System (INIS)

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

    2009-01-01

    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 deg. C, 135 deg. C, 441 deg. C and 570 deg. 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

  1. Rate constant for the reaction SO + BrO yields SO2 + Br

    Science.gov (United States)

    Brunning, J.; Stief, L.

    1986-01-01

    The rate of the radical-radical reaction SO + BrO yields SO2 + Br has been determined at 298 K in a discharge flow system near 1 torr pressure with detection of SO and BrO via collision-free sampling mass spectrometry. The rate constant was determined using two different methods: measuring the decay of SO radicals in the presence of an excess of BrO and measuring the decay of BrO radicals in excess SO. The results from the two methods are in reasonable agreement and the simple mean of the two values gives the recommended rate constant at 298 K, k = (5.7 + or - 2.0) x 10 to the -11th cu cm/s. This represents the first determination of this rate constant and it is consistent with a previously derived lower limit based on SO2 formation. Comparison is made with other radical-radical reactions involving SO or BrO. The reaction SO + BrO yields SO2 + Br is of interest for models of the upper atmosphere of the earth and provides a potential coupling between atmospheric sulfur and bromine chemistry.

  2. Chemical looping coal gasification with calcium ferrite and barium ferrite via solid–solid reactions

    International Nuclear Information System (INIS)

    Siriwardane, Ranjani; Riley, Jarrett; Tian, Hanjing; Richards, George

    2016-01-01

    Highlights: • BaFe 2 O 4 and CaFe 2 O 4 are excellent for chemical looping coal gasification. • BaFe 2 O 4 and CaFe 2 O 4 have minimal reactivity with synthesis gas. • Steam enhances the gasification process with these oxygen carriers. • Reaction rates of steam gasification of coal with CaFe 2 O 4 was better than with gaseous oxygen. • Coal gasification appears to be via solid–solid interaction with the oxygen carrier. - Abstract: Coal gasification to produce synthesis gas by chemical looping was investigated with two oxygen carriers, barium ferrite (BaFe 2 O 4 ) and calcium ferrite (CaFe 2 O 4 ). 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 BaFe 2 O 4 and CaFe 2 O 4 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 (H 2 ) and carbon monoxide (CO), but carbon dioxide (CO 2 ) remained low because these oxygen carriers have minimal reactivity with H 2 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 H 2 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.

  3. Analysis of the behavior of tubular-type equipment for nuclear waste treatment: sensitivities of the parameters affecting mass transfer yield

    International Nuclear Information System (INIS)

    Yoo, Jae Hyung; Lee, Byung Jik; Shim, Joon Bo; Kim, Eung Ho

    2007-01-01

    It was intended in this study to investigate the effects of various parameters on the chemical reaction or mass transfer yield in a tubular-type nuclear waste treatment equipment. Since such equipment. as a tubular reactor, multistage solvent extractor, and adsorption column, accompany chemical reaction or mass transfer along the fluid-flowing direction, mathematical modeling for each equipment was carried out first. Then their behaviors of the chemical reaction or mass transfer were predicted through computer simulations. The inherent major parameters for each equipment were chosen and their sensitivities affecting the reaction or mass transfer yield were analyzed. For the tubular reactor, the effects of axial diffusion coefficient and reaction rate constant on the reaction yield were investigated. As for the multistage solvent extractor, the back mixing of continuous phase and the distribution coefficient between fluid and solvent were considered as the major parameters affecting the extraction yield as well as concentration profiles throughout the axial direction of the extractor. For the adsorption column, the equilibrium constant between fluid and adsorbent surface. and the overall mass transfer coefficient between the two phases were taken as the major factors that affect the adsorption rate

  4. Chemical reaction networks as a model to describe UVC- and radiolytically-induced reactions of simple compounds.

    Science.gov (United States)

    Dondi, Daniele; Merli, Daniele; Albini, Angelo; Zeffiro, Alberto; Serpone, Nick

    2012-05-01

    When a chemical system is submitted to high energy sources (UV, ionizing radiation, plasma sparks, etc.), as is expected to be the case of prebiotic chemistry studies, a plethora of reactive intermediates could form. If oxygen is present in excess, carbon dioxide and water are the major products. More interesting is the case of reducing conditions where synthetic pathways are also possible. This article examines the theoretical modeling of such systems with random-generated chemical networks. Four types of random-generated chemical networks were considered that originated from a combination of two connection topologies (viz., Poisson and scale-free) with reversible and irreversible chemical reactions. The results were analyzed taking into account the number of the most abundant products required for reaching 50% of the total number of moles of compounds at equilibrium, as this may be related to an actual problem of complex mixture analysis. The model accounts for multi-component reaction systems with no a priori knowledge of reacting species and the intermediates involved if system components are sufficiently interconnected. The approach taken is relevant to an earlier study on reactions that may have occurred in prebiotic systems where only a few compounds were detected. A validation of the model was attained on the basis of results of UVC and radiolytic reactions of prebiotic mixtures of low molecular weight compounds likely present on the primeval Earth.

  5. Solid-state reactions to synthesize nanostructured lead selenide semiconductor powders by high-energy milling

    Energy Technology Data Exchange (ETDEWEB)

    Rojas-Chavez, H., E-mail: uu_gg_oo@yahoo.com.mx [Centro de Investigacion e Innovacion Tecnologica - IPN, Cerrada de CECATI s/n, Col. Santa Catarina, Del. Azcapotzalco (Mexico) and Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada - IPN, Legaria 694, Col. Irrigacion, Del. Miguel Hidalgo (Mexico); Reyes-Carmona, F. [Facultad de Quimica - UNAM, Circuito de la Investigacion Cientifica s/n, C.U. Del. Coyoacan (Mexico); Jaramillo-Vigueras, D. [Centro de Investigacion e Innovacion Tecnologica - IPN, Cerrada de CECATI s/n, Col. Santa Catarina, Del. Azcapotzalco (Mexico)

    2011-10-15

    Highlights: {yields} PbSe synthesized from PbO instead of Pb powder do not require an inert atmosphere. {yields} During high-energy milling oxygen has to be chemically reduced from the lead oxide. {yields} Solid-state and solid-gas chemical reactions promote both solid and gaseous products. -- Abstract: Both solid-solid and gas-solid reactions have been traced during high-energy milling of Se and PbO powders under vial (P, T) conditions in order to synthesize the PbSe phase. Chemical and thermodynamic arguments are postulated to discern the high-energy milling mechanism to transform PbO-Se micropowders onto PbSe-nanocrystals. A set of reactions were evaluated at around room temperature. Therefore an experimental campaign was designed to test the nature of reactions in the PbO-Se system during high-energy milling.

  6. The Heck reaction in the production of fine chemicals

    NARCIS (Netherlands)

    Vries, Johannes G. de

    2001-01-01

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

  7. Effect of mass loss on the chemical yields from massive stars

    Energy Technology Data Exchange (ETDEWEB)

    Chiosi, C; Caimmi, R [Padua Univ. (Italy). Istituto di Astronomia

    1979-01-01

    Recent results on the calculation of the chemical yields from massive stars, are rediscussed by taking into account the occurrence of mass loss by stellar wind during the core H- and He-burning phases. The new yields are found to be compatible with the observed distribution of chemical abundances in the solar system, except for He. The net enrichment of several elements over the galaxy's lifetime is found to be consistent with the current estimate of the star formation rate, if we adopt a two phase process of galaxy formation (halodisk). The relative He to heavy element enrichment rate ..delta..Y/..delta..Z turns out to agree with the observational value when mass loss by stellar wind is taken into account.

  8. EFFECT OF THE REACTION CONDITIONS OVER THE YIELD AND PROPERTIES OF METHYLCELLULOSE OBTAINED FROM PINUS RADIATA KRAFT BLEACHED CELLULOSE

    OpenAIRE

    TAPIA, C.; SAPAG-HAGAR, J.; ANDRADE, C.T.; HASSÓN, J.; VALENZUELA, F.; BASUALTO, C.

    2002-01-01

    Kraft bleached cellulose from Pinus radiata was submitted to methylation reactions in heterogeneous media. After activation with 29% (w/w) NaOH solution, methylation reactions were carried out both with dimethyl sulfate (DMS) and methyl iodide (MI). The effects of the pressing ratio, reaction time and type of methylation agent were studied. The better yields were obtained with dimethylsulphate and the pressing ratio and reaction time were not signficant over the yield. Methylcellulose (MC) of...

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

    DEFF Research Database (Denmark)

    Andersen, Jens Enevold Thaulov

    2000-01-01

    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...... 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....

  10. Development of tight-binding, chemical-reaction-dynamics simulator for combinatorial computational chemistry

    International Nuclear Information System (INIS)

    Kubo, Momoji; Ando, Minako; Sakahara, Satoshi; Jung, Changho; Seki, Kotaro; Kusagaya, Tomonori; Endou, Akira; Takami, Seiichi; Imamura, Akira; Miyamoto, Akira

    2004-01-01

    Recently, we have proposed a new concept called 'combinatorial computational chemistry' to realize a theoretical, high-throughput screening of catalysts and materials. We have already applied our combinatorial, computational-chemistry approach, mainly based on static first-principles calculations, to various catalysts and materials systems and its applicability to the catalysts and materials design was strongly confirmed. In order to realize more effective and efficient combinatorial, computational-chemistry screening, a high-speed, chemical-reaction-dynamics simulator based on quantum-chemical, molecular-dynamics method is essential. However, to the best of our knowledge, there is no chemical-reaction-dynamics simulator, which has an enough high-speed ability to perform a high-throughput screening. In the present study, we have succeeded in the development of a chemical-reaction-dynamics simulator based on our original, tight-binding, quantum-chemical, molecular-dynamics method, which is more than 5000 times faster than the regular first-principles, molecular-dynamics method. Moreover, its applicability and effectiveness to the atomistic clarification of the methanol-synthesis dynamics at reaction temperature were demonstrated

  11. Comparing chemical reaction networks

    DEFF Research Database (Denmark)

    Cardelli, Luca; Tribastone, Mirco; Tschaikowski, Max

    2017-01-01

    We study chemical reaction networks (CRNs) as a kernel model of concurrency provided with semantics based on ordinary differential equations. We investigate the problem of comparing two CRNs, i.e., to decide whether the solutions of a source and of a target CRN can be matched for an appropriate...... choice of initial conditions. Using a categorical framework, we extend and unify model-comparison approaches based on dynamical (semantic) and structural (syntactic) properties of CRNs. Then, we provide an algorithm to compare CRNs, running linearly in time with respect to the cardinality of all possible...... comparisons. Finally, using a prototype implementation, CAGE, we apply our results to biological models from the literature....

  12. Method of operating a thermal engine powered by a chemical reaction

    Science.gov (United States)

    Ross, J.; Escher, C.

    1988-06-07

    The invention involves a novel method of increasing the efficiency of a thermal engine. Heat is generated by a non-linear chemical reaction of reactants, said heat being transferred to a thermal engine such as Rankine cycle power plant. The novel method includes externally perturbing one or more of the thermodynamic variables of said non-linear chemical reaction. 7 figs.

  13. Flows and chemical reactions in homogeneous mixtures

    CERN Document Server

    Prud'homme, Roger

    2013-01-01

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

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

    DEFF Research Database (Denmark)

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

    2011-01-01

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

  15. Conditions for extinction events in chemical reaction networks with discrete state spaces.

    Science.gov (United States)

    Johnston, Matthew D; Anderson, David F; Craciun, Gheorghe; Brijder, Robert

    2018-05-01

    We study chemical reaction networks with discrete state spaces and present sufficient conditions on the structure of the network that guarantee the system exhibits an extinction event. The conditions we derive involve creating a modified chemical reaction network called a domination-expanded reaction network and then checking properties of this network. Unlike previous results, our analysis allows algorithmic implementation via systems of equalities and inequalities and suggests sequences of reactions which may lead to extinction events. We apply the results to several networks including an EnvZ-OmpR signaling pathway in Escherichia coli.

  16. Current status of uranium enrichment by way of chemical exchange reactions

    International Nuclear Information System (INIS)

    El Basyouny, A.; Bechthold, H.C.; Knoechel, A.; Vollmer, H.J.

    1985-04-01

    For this report, conference proceedings, patents and other types of literature have been collected to present an account of the current status of uranium enrichment by way of chemical exchange reactions. The report further presents a new concept along with the relevant process strategy developed by the authors. The principal process of the new concept is a chemical exchange process with crown ethers, complexed or free, playing an important part in the reactions. The authors also describe their experiments carried out for establishing suitable chemical systems. (orig./PW) [de

  17. Empirical Force Fields for Mechanistic Studies of Chemical Reactions in Proteins.

    Science.gov (United States)

    Das, A K; Meuwly, M

    2016-01-01

    Following chemical reactions in atomistic detail is one of the most challenging aspects of current computational approaches to chemistry. In this chapter the application of adiabatic reactive MD (ARMD) and its multistate version (MS-ARMD) are discussed. Both methods allow to study bond-breaking and bond-forming processes in chemical and biological processes. Particular emphasis is put on practical aspects for applying the methods to investigate the dynamics of chemical reactions. The chapter closes with an outlook of possible generalizations of the methods discussed. © 2016 Elsevier Inc. All rights reserved.

  18. Proton conduction based on intracrystalline chemical reaction

    International Nuclear Information System (INIS)

    Schuck, G.; Lechner, R.E.; Langer, K.

    2002-01-01

    Proton conductivity in M 3 H(SeO 4 ) 2 crystals (M=K, Rb, Cs) is shown to be due to a dynamic disorder in the form of an intracrystalline chemical equilibrium reaction: alternation between the association of the monomers [HSeO 4 ] 1- and [SeO 4 ] 2- resulting in the dimer [H(SeO 4 ) 2 ] 3- (H-bond formation) and the dissociation of the latter into the two monomers (H-bond breaking). By a combination of quasielastic neutron scattering and FTIR spectroscopy, reaction rates were obtained, as well as rates of proton exchange between selenate ions, leading to diffusion. The results demonstrate that this reaction plays a central role in the mechanism of proton transport in these solid-state protonic conductors. (orig.)

  19. Chemical intervention in plant sugar signalling increases yield and resilience

    Science.gov (United States)

    Griffiths, Cara A.; Sagar, Ram; Geng, Yiqun; Primavesi, Lucia F.; Patel, Mitul K.; Passarelli, Melissa K.; Gilmore, Ian S.; Steven, Rory T.; Bunch, Josephine; Paul, Matthew J.; Davis, Benjamin G.

    2016-12-01

    The pressing global issue of food insecurity due to population growth, diminishing land and variable climate can only be addressed in agriculture by improving both maximum crop yield potential and resilience. Genetic modification is one potential solution, but has yet to achieve worldwide acceptance, particularly for crops such as wheat. Trehalose-6-phosphate (T6P), a central sugar signal in plants, regulates sucrose use and allocation, underpinning crop growth and development. Here we show that application of a chemical intervention strategy directly modulates T6P levels in planta. Plant-permeable analogues of T6P were designed and constructed based on a ‘signalling-precursor’ concept for permeability, ready uptake and sunlight-triggered release of T6P in planta. We show that chemical intervention in a potent sugar signal increases grain yield, whereas application to vegetative tissue improves recovery and resurrection from drought. This technology offers a means to combine increases in yield with crop stress resilience. Given the generality of the T6P pathway in plants and other small-molecule signals in biology, these studies suggest that suitable synthetic exogenous small-molecule signal precursors can be used to directly enhance plant performance and perhaps other organism function.

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

    Science.gov (United States)

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

    2017-04-01

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

  1. Recycling of poly(ethylene terephthalate – A review focusing on chemical methods

    Directory of Open Access Journals (Sweden)

    B. Geyer

    2016-07-01

    Full Text Available Recycling of poly(ethylene terephthalate (PET is of crucial importance, since worldwide amounts of PETwaste increase rapidly due to its widespread applications. Hence, several methods have been developed, like energetic, material, thermo-mechanical and chemical recycling of PET. Most frequently, PET-waste is incinerated for energy recovery, used as additive in concrete composites or glycolysed to yield mixtures of monomers and undefined oligomers. While energetic and thermo-mechanical recycling entail downcycling of the material, chemical recycling requires considerable amounts of chemicals and demanding processing steps entailing toxic and ecological issues. This review provides a thorough survey of PET-recycling including energetic, material, thermo-mechanical and chemical methods. It focuses on chemical methods describing important reaction parameters and yields of obtained reaction products. While most methods yield monomers, only a few yield undefined low molecular weight oligomers for impaired applications (dispersants or plasticizers. Further, the present work presents an alternative chemical recycling method of PET in comparison to existing chemical methods.

  2. Why Do Lithium-Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect.

    Science.gov (United States)

    Yao, Xiahui; Dong, Qi; Cheng, Qingmei; Wang, Dunwei

    2016-09-12

    As an electrochemical energy-storage technology with the highest theoretical capacity, lithium-oxygen batteries face critical challenges in terms of poor stabilities and low charge/discharge round-trip efficiencies. It is generally recognized that these issues are connected to the parasitic chemical reactions at the anode, electrolyte, and cathode. While the detailed mechanisms of these reactions have been studied separately, the possible synergistic effects between these reactions remain poorly understood. To fill in the knowledge gap, this Minireview examines literature reports on the parasitic chemical reactions and finds the reactive oxygen species a key chemical mediator that participates in or facilitates nearly all parasitic chemical reactions. Given the ubiquitous presence of oxygen in all test cells, this finding is important. It offers new insights into how to stabilize various components of lithium-oxygen batteries for high-performance operations and how to eventually materialize the full potentials of this promising technology. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  3. Phenomenological description of selected elementary chemical reaction mechanisms: An information-theoretic study

    International Nuclear Information System (INIS)

    Esquivel, R.O.; Flores-Gallegos, N.; Iuga, C.; Carrera, E.M.; Angulo, J.C.; Antolin, J.

    2010-01-01

    The information-theoretic description of the course of two elementary chemical reactions allows a phenomenological description of the chemical course of the hydrogenic abstraction and the S N 2 identity reactions by use of Shannon entropic measures in position and momentum spaces. The analyses reveal their synchronous/asynchronous mechanistic behavior.

  4. 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

  5. Study of the reaction {gamma}p {yields} p{pi}{sup 0}{eta}

    Energy Technology Data Exchange (ETDEWEB)

    Horn, I.; Bartholomy, O.; Beck, R.; Ehmanns, A.; Ernst, J.; Fabry, I.; Fuchs, M.; Funke, C.; Gutz, E.; Junkersfeld, J.; Kalinowsky, H.; Klempt, E.; Lotz, J.; Pee, H. van; Schmidt, C.; Szczepanek, T.; Thoma, U.; Walther, D.; Weinheimer, C. [Universitaet Bonn, Helmholtz-Institut fuer Strahlen- und Kernphysik, Bonn (Germany); Anisovich, A.V.; Nikonov, V.A.; Sarantsev, A.V. [Universitaet Bonn, Helmholtz-Institut fuer Strahlen- und Kernphysik, Bonn (Germany); Petersburg Nuclear Physics Institute, Gatchina (Russian Federation); Anton, G.; Bogendoerfer, R.; Foesel, A.; Hoessl, J.; Suft, G. [Universitaet Erlangen, Physikalisches Institut, Erlangen (Germany); Bantes, R.; Gothe, R.; Hoeffgen, S.; Klein, F.; Konrad, M.; Langheinrich, J.; Menze, D.; Ostrick, M.; Schmieden, H.; Schoch, B. [Universitaet Bonn, Physikalisches Institut, Bonn (Germany); Beloglazov, Y.; Gridnev, A.; Lopatin, I.; Novinski, D.; Sumachev, V. [Petersburg Nuclear Physics Institute, Gatchina (Russian Federation); Castelijns, R.; Loehner, H. [Kernfysisch Versneller Instituut, Groningen (Netherlands); Crede, V. [Florida State University, Department of Physics, Tallahassee, FL (United States); Flemming, H.; Koch, H.; Kopf, B.; Matthaey, H. [Universitaet Bochum, Institut fuer Experimentalphysik I, Bochum (Germany); Krusche, B. [Universitaet Basel, Institut fuer Physik, Basel (Switzerland); Messchendorp, J.; Metag, V. [Universitaet Giessen, II. Physikalisches Institut, Giessen (Germany)

    2008-11-15

    The reaction {gamma}p {yields} p{pi}{sup 0}{eta} has been studied with the CBELSA detector at the tagged photon beam of the Bonn electron stretcher facility. The reaction shows contributions from {delta}{sup +}(1232){eta}, N(1535){sup +}{pi}{sup 0} and pa{sub 0}(980) as intermediate states. A partial-wave analysis suggests that the reaction proceeds via formation of six {delta} -resonances, {delta}(1600)P{sub 33}, {delta}(1920)P{sub 33}, {delta}(1700)D{sub 33}, {delta}(1940)D{sub 33}, {delta}(1905)F{sub 35}, {delta}(2360)D{sub 33}, and two nucleon resonances N(1880)P{sub 11} and N(2200)P{sub 13}, for which pole positions and decay branching ratios are given. (orig.)

  6. Chemical modifications and reactions in DNA nanostructures

    DEFF Research Database (Denmark)

    Gothelf, Kurt Vesterager

    2017-01-01

    such as hydrocarbons or steroids have been introduced to change the surface properties of DNA origami structures, either to protect the DNA nanostructure or to dock it into membranes and other hydrophobic surfaces. DNA nanostructures have also been used to control covalent chemical reactions. This article provides......DNA nanotechnology has the power to form self-assembled and well-defined nanostructures, such as DNA origami, where the relative positions of each atom are known with subnanometer precision. Our ability to synthesize oligonucleotides with chemical modifications in almost any desired position...... provides rich opportunity to incorporate molecules, biomolecules, and a variety of nanomaterials in specific positions on DNA nanostructures. Several standard modifications for oligonucleotides are available commercially, such as dyes, biotin, and chemical handles, and such modified oligonucleotides can...

  7. Effects of chemical reaction on moving isothermal vertical plate with variable mass diffusion

    Directory of Open Access Journals (Sweden)

    Muthucumaraswamy R.

    2003-01-01

    Full Text Available An exact solution to the problem of flow past an impulsively started infinite vertical isothermal plate with variable mass diffusion is presented here, taking into account of the homogeneous chemical reaction of first-order. The dimensionless governing equations are solved by using the Laplace - transform technique. The velocity and skin-friction are studied for different parameters like chemical reaction parameter, Schmidt number and buoyancy ratio parameter. It is observed that the veloc­ity increases with decreasing chemical reaction parameter and increases with increasing buoyancy ratio parameter.

  8. 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.

  9. Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction

    Science.gov (United States)

    Minitti, M. P.; Budarz, J. M.; Kirrander, A.; Robinson, J. S.; Ratner, D.; Lane, T. J.; Zhu, D.; Glownia, J. M.; Kozina, M.; Lemke, H. T.; Sikorski, M.; Feng, Y.; Nelson, S.; Saita, K.; Stankus, B.; Northey, T.; Hastings, J. B.; Weber, P. M.

    2015-06-01

    Structural rearrangements within single molecules occur on ultrafast time scales. Many aspects of molecular dynamics, such as the energy flow through excited states, have been studied using spectroscopic techniques, yet the goal to watch molecules evolve their geometrical structure in real time remains challenging. By mapping nuclear motions using femtosecond x-ray pulses, we have created real-space representations of the evolving dynamics during a well-known chemical reaction and show a series of time-sorted structural snapshots produced by ultrafast time-resolved hard x-ray scattering. A computational analysis optimally matches the series of scattering patterns produced by the x rays to a multitude of potential reaction paths. In so doing, we have made a critical step toward the goal of viewing chemical reactions on femtosecond time scales, opening a new direction in studies of ultrafast chemical reactions in the gas phase.

  10. High-yield production of pure tagatose from fructose by a three-step enzymatic cascade reaction.

    Science.gov (United States)

    Lee, Seon-Hwa; Hong, Seung-Hye; Kim, Kyoung-Rok; Oh, Deok-Kun

    2017-08-01

    To produce tagatose from fructose with a high conversion rate and to establish a high-yield purification method of tagatose from the reaction mixture. Fructose at 1 M (180 g l -1 ) was converted to 0.8 M (144 g l -1 ) tagatose by a three-step enzymatic cascade reaction, involving hexokinase, plus ATP, fructose-1,6-biphosphate aldolase, phytase, over 16 h with a productivity of 9 g l -1 h -1 . No byproducts were detected. Tagatose was recrystallized from ethanol to a purity of 99.9% and a yield of 96.3%. Overall, tagatose at 99.9% purity was obtained from fructose with a yield of 77%. This is the first biotechnological production of tagatose from fructose and the first application of solvent recrystallization for the purification of rare sugars.

  11. Cellular automaton model of mass transport with chemical reactions

    International Nuclear Information System (INIS)

    Karapiperis, T.; Blankleider, B.

    1993-10-01

    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

  12. Mass transfer with complex reversible chemical reactions—I. Single reversible chemical reaction

    NARCIS (Netherlands)

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

    1989-01-01

    An improved numerical technique was used in order to develop an absorption model with which it is possible to calculate rapidly absorption rates for the phenomenon of mass transfer accompanied by a complex reversible chemical reaction. This model can be applied for the calculation of the mass

  13. 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)

    Amemiya, Kenta

    2015-01-01

    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)

  14. Chemical reaction due to stronger Ramachandran interaction

    Indian Academy of Sciences (India)

    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 ...

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

    Directory of Open Access Journals (Sweden)

    Jiří SLABOTINSKÝ

    2016-12-01

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

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

    NARCIS (Netherlands)

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

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

  17. Droplet heat transfer and chemical reactions during direct containment heating

    International Nuclear Information System (INIS)

    Baker, L. Jr.

    1986-01-01

    A simplified model of heat transfer and chemical reaction has been adapted to evaluate the expected behavior of droplets containing unreacted Zircaloy and stainless steel moving through the containment atmosphere during postulated accidents involving direct containment heating. The model includes internal and external diffusive resistances to reaction. The results indicate that reactions will be incomplete for many conditions characteristic of direct containment heating sequences

  18. Chemical yields from low-temperature pyrolysis of CCA-treated wood

    Science.gov (United States)

    Qirong Fu; Dimitris Argyropolous; Lucian Lucia; David Tilotta; Stan Lebow

    2009-01-01

    Low-temperature pyrolysis offers a feasible option for wood-waste management and the recovery of a variety of useful chemicals. The effect of chromated copper arsenate (CCA) wood preservative on the yield and composition of various pyrolysis products was investigated in the present research. A novel quantitative 31P nuclear magnetic resonance (...

  19. The Effects of Organic, Chemical and Biological Fertilizers on Seed Yield and Yield Components of Dwarf Chicory (Cichorium pumilum Jacq.

    Directory of Open Access Journals (Sweden)

    Farima Doaei

    2017-08-01

    Full Text Available Introduction: In order to response to greater demand for wild medicinal plants consumption, it has been recommended that wild medicinal plants can be brought into cultivation systems. Cichorium pumilum Jacq. is an annual species of Asteraceae family, that has a long history of herbal use and is especially of great value for its tonic effects upon the liver and digestive tract. The root and the leaves of chicory are digestive, hypoglycemic, diuretic, laxative and tonic. Using chemical fertilizers can be easily lost from soils through fixation, leaching or gas emission that can lead to reduced fertilizer efficiency. The applications of organic fertilizers such as compost and vermicompost can be considered as a good management practice to increase cropping system sustainability, reducing soil erosion and improving soil physical, chemical and biological properties. Soil microorganisms have a significant role in regulating the dynamics of organic matter breakdown and the availability of plant nutrients such as nitrogen, phosphate and sulfur. Materials and Methods: For evaluating the effects of organic, mineral and biological fertilizers on seed yield and yield components of dwarf chicory (Cichorium pumilum Jacq., a field experiment was conducted at the Agricultural Research Station, the Ferdowsi University of Mashhad (36016/ N, 59036/ E, elevation 985 m during growing season of 2011-2012. The experimental layout was factorial based on randomized complete block design with four replications. The experimental treatments were all combination of organic and chemical fertilizers (compost 4 t/ha, vermicompost 4 t/ha, urea fertilizer 130 kg/ha and control and biological fertilizer (biosulfur biofertilizer + pure sulfur 100 kg/ ha and control. Before conducting the experiment, soil sample were taken from the depth of 0-30 cm, and physical and chemical characteristics of the soil and also used compost and vermicompost were determined. All fertilizer

  20. Out-of-equilibrium catalysis of chemical reactions by electronic tunnel currents.

    Science.gov (United States)

    Dzhioev, Alan A; Kosov, Daniel S; von Oppen, Felix

    2013-04-07

    We present an escape rate theory for current-induced chemical reactions. We use Keldysh nonequilibrium Green's functions to derive a Langevin equation for the reaction coordinate. Due to the out of equilibrium electronic degrees of freedom, the friction, noise, and effective temperature in the Langevin equation depend locally on the reaction coordinate. As an example, we consider the dissociation of diatomic molecules induced by the electronic current from a scanning tunnelling microscope tip. In the resonant tunnelling regime, the molecular dissociation involves two processes which are intricately interconnected: a modification of the potential energy barrier and heating of the molecule. The decrease of the molecular barrier (i.e., the current induced catalytic reduction of the barrier) accompanied by the appearance of the effective, reaction-coordinate-dependent temperature is an alternative mechanism for current-induced chemical reactions, which is distinctly different from the usual paradigm of pumping vibrational degrees of freedom.

  1. Finite element modeling of contaminant transport in soils including the effect of chemical reactions.

    Science.gov (United States)

    Javadi, A A; Al-Najjar, M M

    2007-05-17

    The movement of chemicals through soils to the groundwater is a major cause of degradation of water resources. In many cases, serious human and stock health implications are associated with this form of pollution. Recent studies have shown that the current models and methods are not able to adequately describe the leaching of nutrients through soils, often underestimating the risk of groundwater contamination by surface-applied chemicals, and overestimating the concentration of resident solutes. Furthermore, the effect of chemical reactions on the fate and transport of contaminants is not included in many of the existing numerical models for contaminant transport. In this paper a numerical model is presented for simulation of the flow of water and air and contaminant transport through unsaturated soils with the main focus being on the effects of chemical reactions. The governing equations of miscible contaminant transport including advection, dispersion-diffusion and adsorption effects together with the effect of chemical reactions are presented. The mathematical framework and the numerical implementation of the model are described in detail. The model is validated by application to a number of test cases from the literature and is then applied to the simulation of a physical model test involving transport of contaminants in a block of soil with particular reference to the effects of chemical reactions. Comparison of the results of the numerical model with the experimental results shows that the model is capable of predicting the effects of chemical reactions with very high accuracy. The importance of consideration of the effects of chemical reactions is highlighted.

  2. Chemical-Reaction-Controlled Phase Separated Drops: Formation, Size Selection, and Coarsening

    Science.gov (United States)

    Wurtz, Jean David; Lee, Chiu Fan

    2018-02-01

    Phase separation under nonequilibrium conditions is exploited by biological cells to organize their cytoplasm but remains poorly understood as a physical phenomenon. Here, we study a ternary fluid model in which phase-separating molecules can be converted into soluble molecules, and vice versa, via chemical reactions. We elucidate using analytical and simulation methods how drop size, formation, and coarsening can be controlled by the chemical reaction rates, and categorize the qualitative behavior of the system into distinct regimes. Ostwald ripening arrest occurs above critical reaction rates, demonstrating that this transition belongs entirely to the nonequilibrium regime. Our model is a minimal representation of the cell cytoplasm.

  3. Measurement of mass yields from the 241Am(2nth,f reaction at the Lohengrin Spectrometer

    Directory of Open Access Journals (Sweden)

    Köster U.

    2013-03-01

    Full Text Available The study of fission yields has a major impact on the characterization and understanding of the fission process and is mandatory for reactor applications. While the yields are known for the major actinides (235U, 239Pu in the thermal neutron-induced fission, only few measurements have been performed on 242Am. The interest of 242Am concerns the reduction of radiotoxicity of 241Am in nuclear wastes using transmutation reactions. This paper presents the measurement of the fission mass yields from the reaction 241Am(2nth,f performed at the Lohengrin mass spectrometer (ILL, France for both the light and the heavy peaks: a total of 41 mass yields have been measured. The experiment was also meant to determine whether there is a difference in mass yields between the isomeric state and the ground state as it exists in fission and capture cross sections. The method used to address this question is based on a repeated measurement of a set of fission mass yields as a function of the ratio between the 242gAm and the 242mAm fission rates. The presented experiment is also a first step towards the measurement of the isotopic fission yields of 242Am.

  4. Investigations of chemical reactions between U-Zr alloy and FBR cladding materials

    International Nuclear Information System (INIS)

    Ishii, Tetsuya; Ukai, Shigeharu

    2005-07-01

    U-Pu-Zr alloys are candidate materials for commercial FBR fuel. However, informations about chemical reactions with cladding materials developed by JNC for commercial FBR have not been well obtained. In this work, the reaction zones formed in four diffusion couples U-10wt.%Zr/PNC-FMS, U-10wt.%Zr/9Cr-ODS, U-10wt.%Zr/12Cr-ODS, and U-10wt.%Zr/Fe at about 1013K have been examined and following results were obtained. 1) At about 1013K, in the U-10wt.%Zr/Fe couple, the liquid phase zones were obtained. In the other couples U-10wt.%Zr/PNC-FMS, U-10wt.%Zr/9Cr-ODS and U-10wt.%Zr/12Cr-ODS, no liquid phase zones were obtained. The obtained chemical reaction zones in the later 3 couples were similar to the reported ones obtained in U-Zr/Fe couples without liquid phase formation. In comparison with the reaction zones obtained in the U-10wt.%Zr/Fe couple, the reaction zones inside cladding materials obtained in the PNC-FMS, 9Cr-ODS, and 12Cr-ODS couples were thin. 2) From the investigations of relationship between the obtained depths of the chemical reaction zones inside cladding materials and composition of the cladding materials, it was considered that the depth of chemical reaction zone would depend on the Cr content of the cladding materials and the depth would decrease with increasing Cr content, resulting in prevention of liquid phase formation. 3) From the investigations of the mechanisms of chemical reactions between U-Pu-Zr/cladding materials, it was considered that the same effect of Cr obtained in the U-Zr/cladding materials would be expected in U-Pu-Zr/cladding materials. Those seemed to indicate that the threshold temperatures of liquid phase formation for U-Pu-Zr/PNC-FMS, U-Pu-Zr/9Cr-ODS, and U-Pu-Zr/12Cr-ODS might be higher than that for U-Pu-Zr/Fe. (author)

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

    OpenAIRE

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

    2014-01-01

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

  6. Diffusion-controlled reactions modeling in Geant4-DNA

    Energy Technology Data Exchange (ETDEWEB)

    Karamitros, M., E-mail: matkara@gmail.com [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); CNRS, INCIA, UMR 5287, F-33400 Talence (France); Luan, S. [University of New Mexico, Department of Computer Science, Albuquerque, NM (United States); Bernal, M.A. [Instituto de Física Gleb Wataghin, Universidade Estadual de Campinas, SP (Brazil); Allison, J. [Geant4 Associates International Ltd (United Kingdom); Baldacchino, G. [CEA Saclay, IRAMIS, LIDYL, Radiation Physical Chemistry Group, F-91191 Gif sur Yvette Cedex (France); CNRS, UMR3299, SIS2M, F-91191 Gif sur Yvette Cedex (France); Davidkova, M. [Nuclear Physics Institute of the ASCR, Prague (Czech Republic); Francis, Z. [Saint Joseph University, Faculty of Sciences, Department of Physics, Mkalles, Beirut (Lebanon); Friedland, W. [Helmholtz Zentrum München, German Research Center for Environmental Health, Institute of Radiation Protection, Ingolstädter Landstr. 1, 85764 Neuherberg (Germany); Ivantchenko, V. [Ecoanalytica, 119899 Moscow (Russian Federation); Geant4 Associates International Ltd (United Kingdom); Ivantchenko, A. [Geant4 Associates International Ltd (United Kingdom); Mantero, A. [SwHaRD s.r.l., via Buccari 9, 16153 Genova (Italy); Nieminem, P.; Santin, G. [ESA-ESTEC, 2200 AG Noordwijk (Netherlands); Tran, H.N. [Division of Nuclear Physics and Faculty of Applied Sciences, Ton Duc Thang University, Tan Phong Ward, District 7, Ho Chi Minh City (Viet Nam); Stepan, V. [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); Nuclear Physics Institute of the ASCR, Prague (Czech Republic); Incerti, S., E-mail: incerti@cenbg.in2p3.fr [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France)

    2014-10-01

    Context Under irradiation, a biological system undergoes a cascade of chemical reactions that can lead to an alteration of its normal operation. There are different types of radiation and many competing reactions. As a result the kinetics of chemical species is extremely complex. The simulation becomes then a powerful tool which, by describing the basic principles of chemical reactions, can reveal the dynamics of the macroscopic system. To understand the dynamics of biological systems under radiation, since the 80s there have been on-going efforts carried out by several research groups to establish a mechanistic model that consists in describing all the physical, chemical and biological phenomena following the irradiation of single cells. This approach is generally divided into a succession of stages that follow each other in time: (1) the physical stage, where the ionizing particles interact directly with the biological material; (2) the physico-chemical stage, where the targeted molecules release their energy by dissociating, creating new chemical species; (3) the chemical stage, where the new chemical species interact with each other or with the biomolecules; (4) the biological stage, where the repairing mechanisms of the cell come into play. This article focuses on the modeling of the chemical stage. Method This article presents a general method of speeding-up chemical reaction simulations in fluids based on the Smoluchowski equation and Monte-Carlo methods, where all molecules are explicitly simulated and the solvent is treated as a continuum. The model describes diffusion-controlled reactions. This method has been implemented in Geant4-DNA. The keys to the new algorithm include: (1) the combination of a method to compute time steps dynamically with a Brownian bridge process to account for chemical reactions, which avoids costly fixed time step simulations; (2) a k–d tree data structure for quickly locating, for a given molecule, its closest reactants. The

  7. 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…

  8. 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

  9. Apparent tunneling in chemical reactions

    DEFF Research Database (Denmark)

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

    2000-01-01

    A necessary condition for tunneling in a chemical reaction is that the probability of crossing a barrier is non-zero, when the energy of the reactants is below the potential energy of the barrier. Due to the non-classical nature (i.e, momentum uncertainty) of vibrational states this is, however......, not a sufficient condition in order to establish genuine tunneling as a result of quantum dynamics. This proposition is illustrated for a two-dimensional model potential describing dissociative sticking of N-2 on Ru(s). It is suggested that the remarkable heavy atom tunneling, found in this system, is related...

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

    International Nuclear Information System (INIS)

    Rosilio, Charles; Ruaudel-Teixier, Annie.

    1976-01-01

    Evidence is given for chemical reactions of hydrazine (NH 2 -NH 2 ) 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 [fr

  11. OH yields from the CH3CO+O-2 reaction using an internal standard\\ud

    OpenAIRE

    Carr, S.A.; Baeza-Romero, M.T.; Blitz, M.A.; Pilling, M.J.; Heard, D.E.; Seakins, P.W.

    2007-01-01

    Laser flash photolysis of CH3C(O)OH at 248 nm was used to create equal zero time yields of CH3CO and OH. The absolute OH yield from the CH3CO + O2 (+M) reaction was determined by following the OH temporal profile using the zero time\\ud OH concentration as an internal standard. The OH yield from CH3CO + O2 (+M) was observed to decrease with increasing pressure with an extrapolated zero pressure yield\\ud close to unity (1.1 ± 0.2, quoted uncertainties correspond to 95% confidence limits). The r...

  12. Real time monitoring of accelerated chemical reactions by ultrasonication-assisted spray ionization mass spectrometry.

    Science.gov (United States)

    Lin, Shu-Hsuan; Lo, Ta-Ju; Kuo, Fang-Yin; Chen, Yu-Chie

    2014-01-01

    Ultrasonication has been used to accelerate chemical reactions. It would be ideal if ultrasonication-assisted chemical reactions could be monitored by suitable detection tools such as mass spectrometry in real time. It would be helpful to clarify reaction intermediates/products and to have a better understanding of reaction mechanism. In this work, we developed a system for ultrasonication-assisted spray ionization mass spectrometry (UASI-MS) with an ~1.7 MHz ultrasonic transducer to monitor chemical reactions in real time. We demonstrated that simply depositing a sample solution on the MHz-based ultrasonic transducer, which was placed in front of the orifice of a mass spectrometer, the analyte signals can be readily detected by the mass spectrometer. Singly and multiply charged ions from small and large molecules, respectively, can be observed in the UASI mass spectra. Furthermore, the ultrasonic transducer used in the UASI setup accelerates the chemical reactions while being monitored via UASI-MS. The feasibility of using this approach for real-time acceleration/monitoring of chemical reactions was demonstrated. The reactions of Girard T reagent and hydroxylamine with steroids were used as the model reactions. Upon the deposition of reactant solutions on the ultrasonic transducer, the intermediate/product ions are readily generated and instantaneously monitored using MS within 1 s. Additionally, we also showed the possibility of using this reactive UASI-MS approach to assist the confirmation of trace steroids from complex urine samples by monitoring the generation of the product ions. Copyright © 2014 John Wiley & Sons, Ltd.

  13. 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…

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

    Science.gov (United States)

    Dudukovic, M. P.

    1987-01-01

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

  15. Students' Visualisation of Chemical Reactions--Insights into the Particle Model and the Atomic Model

    Science.gov (United States)

    Cheng, Maurice M. W.

    2018-01-01

    This paper reports on an interview study of 18 Grade 10-12 students' model-based reasoning of a chemical reaction: the reaction of magnesium and oxygen at the submicro level. It has been proposed that chemical reactions can be conceptualised using two models: (i) the "particle model," in which a reaction is regarded as the simple…

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

    Science.gov (United States)

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

    2017-05-07

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

  17. A phenomenological study of the {pi}{sup -} p {yields} {pi}{sup 0} n charge exchange reaction at high energy; Etude phenomenologique de la reaction d`echange de charge {pi}{sup -} p {yields} {pi}{sup 0} n a haute energie

    Energy Technology Data Exchange (ETDEWEB)

    Michaud, Y

    1995-09-21

    The aim of the study was to examine the behaviour of the proton-proton elastic scattering, for mass center energies around 10 GeV, and more especially to study the charge exchange reaction {pi}{sup -} p {yields} {pi}{sup 0} n for mass center energies between 3 and 20 GeV. A formalism based on the Glauber model has been used, and a Regge trajectory exchange term was introduced in the model in order to enable the description of the lower energy domain (inferior to 10 GeV) that is characterized by a large contribution of meson exchanges at the scattering amplitude. The Glauber model is then applied to the charge exchange reaction and the differential cross section is analyzed for a center mass energy comprised between 3 and 20 GeV, together with the polarization at 40 GeV/c. The approach is then validated through the study of the {pi}{sup -} p {yields} {eta} n reaction. The size of the kernel of proton and pion components implied in the {pi}{sup -} p {yields} {pi}{sup 0} n reaction, is also investigated. 90 refs., 48 figs., 4 tabs., 5 appends.

  18. Improving plasma resistance and lowering roughness in an ArF photoresist by adding a chemical reaction inhibitor

    International Nuclear Information System (INIS)

    Jinnai, Butsurin; Uesugi, Takuji; Koyama, Koji; Samukawa, Seiji; Kato, Keisuke; Yasuda, Atsushi; Maeda, Shinichi; Momose, Hikaru

    2010-01-01

    Major challenges associated with 193 nm lithography using an ArF photoresist are low plasma resistance and roughness formation in the ArF photoresist during plasma processes. We have previously found decisive factors affecting the plasma resistance and roughness formation in an ArF photoresist: plasma resistance is determined by UV/VUV radiation, and roughness formation is dominated by chemical reactions. In this study, based on our findings on the interaction between plasma radiation species and ArF photoresist polymers, we proposed an ArF photoresist with a chemical reaction inhibitor, which can trap reactive species from the plasma, and characterized the performances of the resultant ArF photoresist through neutral beam experiments. Hindered amine light stabilizers, i.e. 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (HO-TEMPO), were used as the chemical reaction inhibitor. Etching rates of the ArF photoresist films were not dependent on the HO-TEMPO content in the irradiations without chemical reactions or under UV/VUV radiation. However, in the irradiation with chemical reactions, the etching rates of the ArF photoresist films decreased as the HO-TEMPO content increased. In addition, the surface roughness decreased with the increase in the additive amount of chemical reaction inhibitor. According to FTIR analysis, a chemical reaction inhibitor can inhibit the chemical reactions in ArF photoresist films through plasma radicals. These results indicate that a chemical reaction inhibitor is effective against chemical reactions, resulting in improved plasma resistance and less roughness in an ArF photoresist. These results also support our suggested mechanism of plasma resistance and roughness formation in an ArF photoresist.

  19. High resolution time-of-flight spectrometer for crossed molecular beam study of elementary chemical reactions

    International Nuclear Information System (INIS)

    Qiu Minghui; Che Li; Ren Zefeng; Dai Dongxu; Wang Xiuyan; Yang Xueming

    2005-01-01

    In this article, we describe an apparatus in our laboratory for investigating elementary chemical reactions using the high resolution time-of-flight Rydberg tagging method. In this apparatus, we have adopted a rotating source design so that collision energy can be changed for crossed beam studies of chemical reactions. Preliminary results on the HI photodissociation and the F atom reaction with H 2 are reported here. These results suggest that the experimental apparatus is potentially a powerful tool for investigating state-to-state dynamics of elementary chemical reactions

  20. Formation yields of glyoxal and methylglyoxal from the gas-phase OH radical-initiated reactions of toluene, xylenes, and trimethylbenzenes as a function of NO2 concentration.

    Science.gov (United States)

    Nishino, Noriko; Arey, Janet; Atkinson, Roger

    2010-09-23

    Aromatic hydrocarbons comprise 20% of non-methane volatile organic compounds in urban areas and are transformed mainly by atmospheric chemical reactions with OH radicals during daytime. In this work we have measured the formation yields of glyoxal and methylglyoxal from the OH radical-initiated reactions of toluene, xylenes, and trimethylbenzenes over the NO2 concentration range (0.2-10.3) × 1013 molecules cm(-3). For toluene, o-, m-, and p-xylene, and 1,3,5-trimethylbenzene, the yields showed a dependence on NO2, decreasing with increasing NO2 concentration and with no evidence for formation of glyoxal or methylglyoxal from the reactions of the OH-aromatic adducts with NO2. In contrast, for 1,2,3- and 1,2,4-trimethylbenzene the glyoxal and methylglyoxal formation yields were independent of the NO2 concentration within the experimental uncertainties. Extrapolations of our results to NO2 concentrations representative of the ambient atmosphere results in the following glyoxal and methylglyoxal yields, respectively: for toluene, 26.0 ± 2.2% and 21.5 ± 2.9%; for o-xylene, 12.7 ± 1.9% and 33.1 ± 6.1%; for m-xylene, 11.4 ± 0.7% and 51.5 ± 8.5%; for p-xylene, 38.9 ± 4.7% and 18.7 ± 2.2%; for 1,2,3-trimethylbenzene, 4.7 ± 2.4% and 15.1 ± 3.3%; for 1,2,4-trimethylbenzene, 8.7 ± 1.6% and 27.2 ± 8.1%; and for 1,3,5-trimethylbenzene, 58.1 ± 5.3% (methylglyoxal).

  1. Iteration scheme for implicit calculations of kinetic and equilibrium chemical reactions in fluid dynamics

    International Nuclear Information System (INIS)

    Ramshaw, J.D.; Chang, C.H.

    1995-01-01

    An iteration scheme for the implicit treatment of equilibrium chemical reactions in partial equilibrium flow has previously been described. Here we generalize this scheme to kinetic reactions as well as equilibrium reactions. This extends the applicability of the scheme to problems with kinetic reactions that are fast in regions of the flow field but slow in others. The resulting scheme thereby provides a single unified framework for the implicit treatment of an arbitrary number of coupled equilibrium and kinetic reactions in chemically reacting fluid flow. 10 refs., 2 figs

  2. 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…

  3. Isotope dependence of chemical erosion of carbon

    International Nuclear Information System (INIS)

    Reinhold, C.O.; Krstic, P.S.; Stuart, S.J.; Zhang, H.; Harris, P.R.; Meyer, F.W.

    2010-01-01

    We study the chemical erosion of hydrogen-supersaturated carbon due to bombardment by hydrogen isotopes H, D, and T at energies of 1-30 eV using classical molecular dynamics simulations. The chemical structure at the hydrogen-saturated interface (the distribution of terminal hydrocarbon moieties, in particular) shows a weak dependence on the mass of the impinging atoms. However, the sputtering yields increase considerably with increasing projectile mass. We analyze the threshold energies of chemical sputtering reaction channels and show that they are nearly mass independent, as expected from elementary bond-breaking chemical reactions involving hydrocarbons. Chemical sputtering yields for D impact are compared with new experimental data. Good agreement is found for small hydrocarbons but the simulations overestimate the production of large hydrocarbons for energies larger than 15 eV. We present a thorough analysis of the dependence of our simulations on the parameters of the bombardment schemes and discuss open questions and possible avenues for development.

  4. Nonlinear magnetoacoustic wave propagation with chemical reactions

    Science.gov (United States)

    Margulies, Timothy Scott

    2002-11-01

    The magnetoacoustic problem with an application to sound wave propagation through electrically conducting fluids such as the ocean in the Earth's magnetic field, liquid metals, or plasmas has been addressed taking into account several simultaneous chemical reactions. Using continuum balance equations for the total mass, linear momentum, energy; as well as Maxwell's electrodynamic equations, a nonlinear beam equation has been developed to generalize the Khokhlov-Zabolotskaya-Kuznetsov (KZK) equation for a fluid with linear viscosity but nonlinear and diffraction effects. Thermodynamic parameters are used and not tailored to only an adiabatic fluid case. The chemical kinetic equations build on a relaxing media approach presented, for example, by K. Naugolnukh and L. Ostrovsky [Nonlinear Wave Processes in Acoustics (Cambridge Univ. Press, Cambridge, 1998)] for a linearized single reaction and thermodynamic pressure equation of state. Approximations for large and small relaxation times and for magnetohydrodynamic parameters [Korsunskii, Sov. Phys. Acoust. 36 (1990)] are examined. Additionally, Cattaneo's equation for heat conduction and its generalization for a memory process rather than a Fourier's law are taken into account. It was introduced for the heat flux depends on the temperature gradient at an earlier time to generate heat pulses of finite speed.

  5. On the mechanism of effective chemical reactions with turbulent mixing of reactants and finite rate of molecular reactions

    Energy Technology Data Exchange (ETDEWEB)

    Vorotilin, V. P., E-mail: VPVorotilin@yandex.ru [Russian Academy of Sciences, Institute of Applied Mechanics (Russian Federation)

    2017-01-15

    A generalization of the theory of chemical transformation processes under turbulent mixing of reactants and arbitrary values of the rate of molecular reactions is presented that was previously developed for the variant of an instantaneous reaction [13]. The use of the features of instantaneous reactions when considering the general case, namely, the introduction of the concept of effective reaction for the reactant volumes and writing a closing conservation equation for these volumes, became possible due to the partition of the whole amount of reactants into “active” and “passive” classes; the reactants of the first class are not mixed and react by the mechanism of instantaneous reactions, while the reactants of the second class approach each other only through molecular diffusion, and therefore their contribution to the reaction process can be neglected. The physical mechanism of reaction for the limit regime of an ideal mixing reactor (IMR) is revealed and described. Although formally the reaction rate in this regime depends on the concentration of passive fractions of the reactants, according to the theory presented, the true (hidden) mechanism of the reaction is associated only with the reaction of the active fractions of the reactants with vanishingly small concentration in the volume of the reactor. It is shown that the rate constant of fast chemical reactions can be evaluated when the mixing intensity of reactants is much less than that needed to reach the mixing conditions in an IMR.

  6. Achieving Chemical Equilibrium: The Role of Imposed Conditions in the Ammonia Formation Reaction

    Science.gov (United States)

    Tellinghuisen, Joel

    2006-01-01

    Under conditions of constant temperature T and pressure P, chemical equilibrium occurs in a closed system (fixed mass) when the Gibbs free energy G of the reaction mixture is minimized. However, when chemical reactions occur under other conditions, other thermodynamic functions are minimized or maximized. For processes at constant T and volume V,…

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

    DEFF Research Database (Denmark)

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

    2013-01-01

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

  8. 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.

  9. 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...

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

    International Nuclear Information System (INIS)

    Alves, Giselle M; Kremer, Gilberto M; Marques, Wilson Jr; Soares, Ana Jacinta

    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 solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman–Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal–diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode

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

    Science.gov (United States)

    Alves, Giselle M.; Kremer, Gilberto M.; Marques, Wilson, Jr.; Jacinta Soares, Ana

    2011-03-01

    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 solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman-Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal-diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode.

  12. Reaction Characteristics of Andrographolide and its Analogue AL-1 with GSH, as a Simple Chemical Simulation of NF-κB Inhibition

    Directory of Open Access Journals (Sweden)

    Yuqiang Wang

    2012-01-01

    Full Text Available 14-α-Lipoic acid-3,19-dihydroxyandrographolide (AL-1, 2 is an analogue of andrographolide (Andro, 1 coupled to α-lipoic acid (LA, 4. AL-1 was at least 10-fold more potent than the natural parent compound Andro in inhibiting nuclear factor (NF-κB activation in RIN-m cells. In the present study, glutathione (GSH, 3 was used as a simple chemical model molecule of NF-κB with cysteine 62. The characteristics of the reaction between AL-1 or Andro and GSH were investigated to trace some possible elucidation for the inhibitive mechanism and stronger inhibition of AL-1 to NF-κB activation. The results showed that the main reaction products of AL-1 and Andro were identical, sulfhydryl adduct and amino adduct. AL-1 reacted much faster than Andro with GSH. The product yield of AL-1 was much higher than that of Andro. It was speculated that AL-1 might inhibit NF-κB by the same mechanism as Andro. And the faster reaction rate and higher yield may account for the stronger NF-κB inhibition of AL-1 when compared with Andro.

  13. Phenomenon of quantum low temperature limit of chemical reaction rates

    International Nuclear Information System (INIS)

    Gol'danskij, V.I.

    1975-01-01

    The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerisation, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerisation reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau 0 ) required to add one new link to the polymer chain of formaldehyde during its polymerisation by radiation and during postpolymerisation and to establish that below 80K the increase of tau 0 slows down and that at T approximately equal to 10-4K the time tau 0 reaches a plateau (tau 0 approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon, which may be particularly common in combined electronic-confirmational transitions in complex biological molecules and may play a definite role in chemical and biological evolution (cold prehistory of life)

  14. Phenomenon of quantum low temperature limit of chemical reaction rates

    Energy Technology Data Exchange (ETDEWEB)

    Gol' danskii, V I [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

    1975-12-01

    The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius Law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerization, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerization reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau/sub 0/) required to add one new link to the polymer chain of formaldehyde during its polymerization by radiation and during postpolymerization and to establish that below 80K the increase of tau/sub 0/ slows down and that at T approximately equal to 10-4K the time tau/sub 0/ reaches a plateau (tau/sub 0/ approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon, which may be particularly common in combined electronic-confirmational transitions in complex biological molecules and may play a definite role in chemical and biological evolution (cold prehistory of life).

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

    International Nuclear Information System (INIS)

    Chu Juan; Jin Zhengguo; Cai Shu; Yang Jingxia; Hong Zhanglian

    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.

  16. Chemical reactions induced by fast neutron irradiation

    International Nuclear Information System (INIS)

    Katsumura, Y.

    1989-01-01

    Here, several studies on fast neutron irradiation effects carried out at the reactor 'YAYOI' are presented. Some indicate a significant difference in the effect from those by γ-ray irradiation but others do not, and the difference changes from subject to subject which we observed. In general, chemical reactions induced by fast neutron irradiation expand in space and time, and there are many aspects. In the time region just after the deposition of neutron energy in the system, intermediates are formed densely and locally reflecting high LET of fast neutrons and, with time, successive reactions proceed parallel to dissipation of localized energy and to diffusion of the intermediates. Finally the reactions are completed in longer time region. If we pick up the effects which reserve the locality of the initial processes, a significant different effect between in fast neutron radiolysis and in γ-ray radiolysis would be derived. If we observe the products generated after dissipation and diffusion in longer time region, a clear difference would not be observed. Therefore, in order to understand the fast neutron irradiation effects, it is necessary to know the fundamental processes of the reactions induced by radiations. (author)

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

    International Nuclear Information System (INIS)

    Bini, Roberto; Ceppatelli, Matteo; Citroni, Margherita; Schettino, Vincenzo

    2012-01-01

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

  18. Basic reactions induced by radiation

    International Nuclear Information System (INIS)

    Charlesby, A.

    1980-01-01

    This paper summarises some of the basic reactions resulting from exposure to high energy radiation. In the initial stages energy is absorbed, but not necessarily at random, giving radical and ion species which may then react to promote the final chemical change. However, it is possible to intervene at intermediate stages to modify or reduce the radiation effect. Under certain conditions enhanced reactions are also possible. Several expressions are given to calculate radiation yield in terms of energy absorbed. Some analogies between radiation-induced reactions in polymers, and those studied in radiobiology are outlined. (author)

  19. Hydrogenation of rapeseed oil for production of liquid bio-chemicals

    International Nuclear Information System (INIS)

    Pinto, F.; Martins, S.; Gonçalves, M.; Costa, P.; Gulyurtlu, I.; Alves, A.; Mendes, B.

    2013-01-01

    Highlights: ► Production of renewable liquid hydrocarbons through rapeseed oil hydrogenation. ► Hydrogenation at lower temperature and lower hydrogen pressures. ► Test of a catalyst commonly employed in petrochemical industry. ► Improve of hydrogenation process viability by decreasing operational costs. ► Analysis of hydrogenated product applications as bio-chemicals. -- Abstract: The main objective of rapeseed oil hydrogenation tests was the production of liquid bio-chemicals to be used as renewable raw material for the production of several chemicals and in chemical synthesis to substitute petroleum derived stuff. As, hydrogenation of vegetable oils is already applied for the production of biofuels, the work done focused in producing aromatic compounds, due to their economic value. The effect of experimental conditions on rapeseed oil hydrogenation was studied, namely, reaction temperature and time with the aim of selecting the most favourable conditions to convert rapeseed oil into liquid valuable bio-chemicals. Rapeseed oil was hydrogenated at a hydrogen initial pressure of 1.10 MPa. Reaction temperature varied in the range from 200 °C to 400 °C, while reaction times between 6 and 180 min were tested. The performance of a commercial cobalt and molybdenum catalyst was also studied. The highest hydrocarbons yields were obtained at the highest temperature and reaction times tested. At a temperature of 400 °C and at the reaction time of 120 min hydrocarbons yield was about 92% in catalyst presence, while in the absence of the catalyst this value decreased to 85%. Hydrocarbons yield was even higher when the reaction time of 180 min was used in the presence of catalyst, as the yield of 97% was observed. At these conditions hydrocarbons formed had a high content of aromatic compounds, around 50%. For this reason, the viscosity values of hydrogenated oils were lower than that established by EN590, which together with hydrogenated liquids composition

  20. A method for carrying out radiolysis and chemical reactions by means of the radiations resulting from a thermonuclear reaction

    International Nuclear Information System (INIS)

    Gomberg, H.J.

    1974-01-01

    The invention relates to the use of the radiations resulting from thermonuclear reactions. It deals with a method comprising a combination of thermo-chemical and radiolytic reactions for treating a molecule having a high absorption rate, by the radiations of a thermonuclear reaction. This is applicable to the dissociation of water into oxygen and hydrogen [fr

  1. Chemical markup, XML, and the world wide web. 6. CMLReact, an XML vocabulary for chemical reactions.

    Science.gov (United States)

    Holliday, Gemma L; Murray-Rust, Peter; Rzepa, Henry S

    2006-01-01

    A set of components (CMLReact) for managing chemical and biochemical reactions has been added to CML. These can be combined to support most of the strategies for the formal representation of reactions. The elements, attributes, and types are formally defined as XMLSchema components, and their semantics are developed. New syntax and semantics in CML are reported and illustrated with 10 examples.

  2. Thin layer chromatography coupled with surface-enhanced Raman scattering as a facile method for on-site quantitative monitoring of chemical reactions.

    Science.gov (United States)

    Zhang, Zong-Mian; Liu, Jing-Fu; Liu, Rui; Sun, Jie-Fang; Wei, Guo-Hua

    2014-08-05

    By coupling surface-enhanced Raman spectroscopy (SERS) with thin layer chromatography (TLC), a facile and powerful method was developed for on-site monitoring the process of chemical reactions. Samples were preseparated on a TLC plate following a common TLC procedure, and then determined by SERS after fabricating a large-area, uniform SERS substrate on the TLC plate by spraying gold nanoparticles (AuNPs). Reproducible and strong SERS signals were obtained with substrates prepared by spraying 42-nm AuNPs at a density of 5.54 × 10(10) N/cm(2) on the TLC plate. The capacity of this TLC-SERS method was evaluated by monitoring a typical Suzuki coupling reaction of phenylboronic acid and 2-bromopyridine as a model. Results showed that this proposed method is able to identify reaction product that is invisible to the naked eye, and distinguish the reactant 2-bromopyridine and product 2-phenylpyridine, which showed almost the same retention factors (R(f)). Under the optimized conditions, the peak area of the characteristic Raman band (755 cm(-1)) of the product 2-phenylpyridine showed a good linear correlation with concentration in the range of 2-200 mg/L (R(2) = 0.9741), the estimated detection limit (1 mg/L 2-phenylpyridine) is much lower than the concentration of the chemicals in the common organic synthesis reaction system, and the product yield determined by the proposed TLC-SERS method agreed very well with that by UPLC-MS/MS. In addition, a new byproduct in the reaction system was found and identified through continuous Raman detection from the point of sample to the solvent front. This facile TLC-SERS method is quick, easy to handle, low-cost, sensitive, and can be exploited in on-site monitoring the processes of chemical reactions, as well as environmental and biological processes.

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

    Science.gov (United States)

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

    2009-09-28

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

  4. 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…

  5. Cross section of α-induced reactions on iridium isotopes obtained from thick target yield measurement for the astrophysical γ process

    Directory of Open Access Journals (Sweden)

    T. Szücs

    2018-01-01

    Full Text Available The stellar reaction rates of radiative α-capture reactions on heavy isotopes are of crucial importance for the γ process network calculations. These rates are usually derived from statistical model calculations, which need to be validated, but the experimental database is very scarce. This paper presents the results of α-induced reaction cross section measurements on iridium isotopes carried out at first close to the astrophysically relevant energy region. Thick target yields of 191Ir(α,γ195Au, 191Ir(α,n194Au, 193Ir(α,n196mAu, 193Ir(α,n196Au reactions have been measured with the activation technique between Eα=13.4 MeV and 17 MeV. For the first time the thick target yield was determined with X-ray counting. This led to a previously unprecedented sensitivity. From the measured thick target yields, reaction cross sections are derived and compared with statistical model calculations. The recently suggested energy-dependent modification of the α+nucleus optical potential gives a good description of the experimental data.

  6. Fission Reaction Event Yield Algorithm FREYA 2.0.2

    Science.gov (United States)

    Verbeke, J. M.; Randrup, J.; Vogt, R.

    2018-01-01

    FREYA (Fission Reaction Event Yield Algorithm) is a fission event generator which models complete fission events. As such, it automatically includes fluctuations as well as correlations between observables, resulting from conservation of energy and momentum. The purpose of this paper is to present the main differences between FREYA versions 1.0 and 2.0.2 : additional fissionable isotopes, angular momentum conservation, Giant Dipole Resonance form factor for the statistical emission of photons, improved treatment of fission photon emission using RIPL database, and dependence on the incident neutron direction. FREYA 2.0.2 has been integrated into the LLNL Fission Library 2.0.2, which has itself been integrated into MCNP6.2, TRIPOLI-4.10, and can be called from Geant4.10.

  7. The gas phase reaction of ozone with 1,3-butadiene: formation yields of some toxic products

    Science.gov (United States)

    Kramp, Franz; Paulson, Suzanne E.

    The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product yields. In separate experiments, small quantities of 1,3,5-trimethyl benzene were added as a tracer for OH. Formation yields of acrolein of (52±7)%, 1,2-epoxy-3-butene of (3.1±0.5)% and OH radicals of (13±3)% were observed. In addition, the rate coefficient of the gas-phase reaction of ozone with 1,2-epoxy-3-butene was measured both directly and relative to propene, finding an average of (1.6±0.4)×10 -18 cm 3 molecule -1 s -1, respectively, at 296±2 K. The results are briefly discussed in terms of the effect of atmospheric processing on the toxicity of 1,3-butadiene.

  8. 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.

  9. On microscopic simulations of systems with model chemical reactions

    International Nuclear Information System (INIS)

    Gorecki, J.; Gorecka, J.N.

    1998-01-01

    Large scale computer simulations of model chemical systems play the role of idealized experiments in which theories may be tested. In this paper we present two applications of microscopic simulations based on the reactive hard sphere model. We investigate the influence of internal fluctuations on an oscillating chemical system and observe how they modify the phase portrait of it. Another application, we consider, is concerned with the propagation of a chemical wave front associated with a thermally activated reaction. It is shown that the nonequilibrium effects increase the front velocity if compared with the velocity of the front generated by a nonactivated process characterized by the same rate constant. (author)

  10. Fractal sets generated by chemical reactions discrete chaotic dynamics

    International Nuclear Information System (INIS)

    Gontar, V.; Grechko, O.

    2007-01-01

    Fractal sets composed by the parameters values of difference equations derived from chemical reactions discrete chaotic dynamics (DCD) and corresponding to the sequences of symmetrical patterns were obtained in this work. Examples of fractal sets with the corresponding symmetrical patterns have been presented

  11. Invariant boxes and stability of some systems from biomathematics and chemical reactions

    International Nuclear Information System (INIS)

    Pavel, N.H.

    1984-08-01

    A general theorem on the flow-invariance of a time-dependent rectangular box with respect to a differential system is first recalled [''Analysis of some non-linear problems'' in Banach Spaces and Applications, Univ. of Iasi (Romania) (1982)]. Then a theorem applicable to the study of some differential systems from biomathematics and chemical reactions is given and proved. The theorem can be applied to enzymatic reactions, the chemical mechanism in the Belousov reaction, and the kinetic system for the chemical scheme of Hanusse of two processes with three intermediate species [in Pavel, N.H., Differential Equations, Flow-invariance and Applications, Pitman Publishing, Ltd., London (to appear)]. Next, the matrices A for which the corresponding linear system x'=Ax is component-wise positive asymptotically stable are characterized. In the Appendix a partial answer to an open problem regarding the preservation of both continuity and dissipativity in the extension of functions to a Banach space is given

  12. Reactions driving conformational movements (molecular motors) in gels: conformational and structural chemical kinetics.

    Science.gov (United States)

    Otero, Toribio F

    2017-01-18

    In this perspective the empirical kinetics of conducting polymers exchanging anions and solvent during electrochemical reactions to get dense reactive gels is reviewed. The reaction drives conformational movements of the chains (molecular motors), exchange of ions and solvent with the electrolyte and structural (relaxation, swelling, shrinking and compaction) gel changes. Reaction-driven structural changes are identified and quantified from electrochemical responses. The empirical reaction activation energy (E a ), the reaction coefficient (k) and the reaction orders (α and β) change as a function of the conformational energy variation during the reaction. This conformational energy becomes an empirical magnitude. E a , k, α and β include and provide quantitative conformational and structural information. The chemical kinetics becomes structural chemical kinetics (SCK) for reactions driving conformational movements of the reactants. The electrochemically stimulated conformational relaxation model describes empirical results and some results from the literature for biochemical reactions. In parallel the development of an emerging technological world of soft, wet, multifunctional and biomimetic tools and anthropomorphic robots driven by reactions of the constitutive material, as in biological organs, can be now envisaged being theoretically supported by the kinetic model.

  13. Chemical repair activity of free radical scavenger edaravone. Reduction reactions with dGMP hydroxyl radical adducts and suppression of base lesions and AP sites on irradiated plasmid DNA

    International Nuclear Information System (INIS)

    Hata, Kuniki; Katsumura, Yosuke; Urushibara, Ayumi; Yamashita, Shinichi; Lin Mingzhang; Muroya, Yusa; Shikazono, Naoya; Yokoya, Akinari; Fu Haiying

    2015-01-01

    Reactions of edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one) with deoxyguanosine monophosphate (dGMP) hydroxyl radical adducts were investigated by pulse radiolysis technique. Edaravone was found to reduce the dGMP hydroxyl radical adducts through electron transfer reactions. The rate constants of the reactions were greater than 4 × 10 8 dm 3 mol -1 s -1 and similar to those of the reactions of ascorbic acid, which is a representative antioxidant. Yields of single-strand breaks, base lesions, and abasic sites produced in pUC18 plasmid DNA by gamma ray irradiation in the presence of low concentrations (10–1000 μmol dm -3 ) of edaravone were also quantified, and the chemical repair activity of edaravone was estimated by a method recently developed by the authors. By comparing suppression efficiencies to the induction of each DNA lesion, it was found that base lesions and abasic sites were suppressed by the chemical repair activity of edaravone, although the suppression of single-strand breaks was not very effective. This phenomenon was attributed to the chemical repair activity of edaravone toward base lesions and abasic sites. However, the chemical repair activity of edaravone for base lesions was lower than that of ascorbic acid. (author)

  14. High yield fabrication of chemically reduced graphene oxide field effect transistors by dielectrophoresis

    International Nuclear Information System (INIS)

    Joung, Daeha; Chunder, A; Zhai, Lei; Khondaker, Saiful I

    2010-01-01

    We demonstrate high yield fabrication of field effect transistors (FET) using chemically reduced graphene oxide (RGO) sheets. The RGO sheets suspended in water were assembled between prefabricated gold source and drain electrodes using ac dielectrophoresis. With the application of a backgate voltage, 60% of the devices showed p-type FET behavior, while the remaining 40% showed ambipolar behavior. After mild thermal annealing at 200 deg. C, all ambipolar RGO FET remained ambipolar with increased hole and electron mobility, while 60% of the p-type RGO devices were transformed to ambipolar. The maximum hole and electron mobilities of the devices were 4.0 and 1.5 cm 2 V -1 s -1 respectively. High yield assembly of chemically derived RGO FET will have significant impact in scaled up fabrication of graphene based nanoelectronic devices.

  15. On energetics of hydrocarbon chemical reactions by ionizing irradiation

    International Nuclear Information System (INIS)

    Zaykin, Yu.A.; Zaykina, R.F.; Mirkin, G.

    2002-01-01

    Complete text of publication follows. The present global energy crisis requires the industry to look for technologies that are more effective and, particularly, less energy consuming. The hydrocarbon processing technology based on the electron radiation-induced thermal chemical conversion has a great potential. Comparing the presently predominant thermocatalytic processing, it is much more energy efficient, because chemical conversions go at a minimal processing temperature and pressure. To compare energy consumption by electron irradiation with thermal and thermocatalytic technologies of hydrocarbon processing one must see major differences between them. While traditional thermocatalytic processes are equilibrium and their energetics can be evaluated based on principles of classic thermodynamics, HEET processing is non-equilibrium and this evaluation approach is not valid for it. However, a theoretical description of radiation-chemical conversion using reaction rate constants determined in thermally equilibrium systems is approximately adequate to radiation processes by substituting equilibrium concentrations of reacting particles as their non-equilibrium concentrations under irradiation. In particular, description of radical reactions initiated by radiation requires substitution of thermally equilibrium radical concentration by much higher concentration defined by the dynamic equilibrium of radical radiation generation and their recombination. The paper presents the comparative analysis of energy consumption in different stages of hydrocarbon processing using classic thermal cracking by heating versus radiation induced cracking. It is shown that in the most energy-consuming stage of processing - the chain reaction initiation necessary for concentration of active radicals, irradiation processing has the great advantage compared to thermal cracking by heating and allows cutting down the total energy consumption by approximately 40%

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

    CSIR Research Space (South Africa)

    Du Plessis, A

    2011-07-01

    Full Text Available Results from experiments aimed at bimolecular chemical reaction control of CO and H2 at room temperature and pressure, without any catalyst, using shaped femtosecond laser pulses are presented. A stable reaction product (CO2) was measured after...

  17. Reactions of recoil tritium generated by the 3He(n,p)3H reaction with aromatic compounds -intramolecular tritium distribution and radiochemical yield

    International Nuclear Information System (INIS)

    Nogawa, N.; Morikawa, Naotake; Oohashi, Kunio; Matuoka, H.; Moki, T.; Moriya, T.

    1986-01-01

    Reactions of recoil tritium with benzoic acid, acetanilide and β-phenethyl alcohol were studied using the 3 He(=n,p) 3 H reaction. The tritium distribution in the aromatic ring is approximately uniform in all the irradiated compounds and the tritium activity per C-H bond in the methyl and ethylene groups is 7 to 8 relative to that of the corresponding ring as standard. These findings are substantially the same as those obtained previously by the 6 Li(n,α) 3 H reactions, suggesting the same mechanism of tritiation for both recoil reactions. The tritiated parent compounds were obtained in high radiochemical yields: 45% for benzoic acid, 30% for acetanilide, 12% for β-phenethyl alcohol. (author)

  18. Method and apparatus for controlling gas evolution from chemical reactions

    Science.gov (United States)

    Skorpik, James R.; Dodson, Michael G.

    1999-01-01

    The present invention is directed toward monitoring a thermally driven gas evolving chemical reaction with an acoustic apparatus. Signals from the acoustic apparatus are used to control a heater to prevent a run-away condition. A digestion module in combination with a robotic arm further automate physical handling of sample material reaction vessels. The invention is especially useful for carrying out sample procedures defined in EPA Methods SW-846.

  19. Localized temperature and chemical reaction control in nanoscale space by nanowire array.

    Science.gov (United States)

    Jin, C Yan; Li, Zhiyong; Williams, R Stanley; Lee, K-Cheol; Park, Inkyu

    2011-11-09

    We introduce a novel method for chemical reaction control with nanoscale spatial resolution based on localized heating by using a well-aligned nanowire array. Numerical and experimental analysis shows that each individual nanowire could be selectively and rapidly Joule heated for local and ultrafast temperature modulation in nanoscale space (e.g., maximum temperature gradient 2.2 K/nm at the nanowire edge; heating/cooling time chemical reactions such as polymer decomposition/cross-linking and direct and localized hydrothermal synthesis of metal oxide nanowires were demonstrated.

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

    International Nuclear Information System (INIS)

    Karapiperis, T.

    1994-01-01

    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

  1. Approximate method for stochastic chemical kinetics with two-time scales by chemical Langevin equations

    International Nuclear Information System (INIS)

    Wu, Fuke; Tian, Tianhai; Rawlings, James B.; Yin, George

    2016-01-01

    The frequently used reduction technique is based on the chemical master equation for stochastic chemical kinetics with two-time scales, which yields the modified stochastic simulation algorithm (SSA). For the chemical reaction processes involving a large number of molecular species and reactions, the collection of slow reactions may still include a large number of molecular species and reactions. Consequently, the SSA is still computationally expensive. Because the chemical Langevin equations (CLEs) can effectively work for a large number of molecular species and reactions, this paper develops a reduction method based on the CLE by the stochastic averaging principle developed in the work of Khasminskii and Yin [SIAM J. Appl. Math. 56, 1766–1793 (1996); ibid. 56, 1794–1819 (1996)] to average out the fast-reacting variables. This reduction method leads to a limit averaging system, which is an approximation of the slow reactions. Because in the stochastic chemical kinetics, the CLE is seen as the approximation of the SSA, the limit averaging system can be treated as the approximation of the slow reactions. As an application, we examine the reduction of computation complexity for the gene regulatory networks with two-time scales driven by intrinsic noise. For linear and nonlinear protein production functions, the simulations show that the sample average (expectation) of the limit averaging system is close to that of the slow-reaction process based on the SSA. It demonstrates that the limit averaging system is an efficient approximation of the slow-reaction process in the sense of the weak convergence.

  2. Theoretical study of chemical reaction effects on vertical oscillating plate with variable temperature

    Directory of Open Access Journals (Sweden)

    Muthucumaraswamy R.

    2006-01-01

    Full Text Available An exact solution to the flow of a viscous incompressible unsteady flow past an infinite vertical oscillating plate with variable temperature and mass diffusion is presented here, taking into account of the homogeneous chemical reaction of first-order. Both the plate temperature and the concentration level near the plate are raised linearly with respect to time. The dimensionless governing equations has been obtained by the Laplace transform method, when the plate is oscillating harmonically in its own plane. The effects of velocity and concentration are studied for different parameters like phase angle, chemical reaction parameter, thermal Grashof number, mass Grashof number, Schmidt number and time are studied. The solutions are valid only for small values of time t. It is observed that the velocity increases with decreasing phase angle ωt or chemical reaction parameter. .

  3. Coupling between solute transport and chemical reactions models

    International Nuclear Information System (INIS)

    Samper, J.; Ajora, C.

    1993-01-01

    During subsurface transport, reactive solutes are subject to a variety of hydrodynamic and chemical processes. The major hydrodynamic processes include advection and convection, dispersion and diffusion. The key chemical processes are complexation including hydrolysis and acid-base reactions, dissolution-precipitation, reduction-oxidation, adsorption and ion exchange. The combined effects of all these processes on solute transport must satisfy the principle of conservation of mass. The statement of conservation of mass for N mobile species leads to N partial differential equations. Traditional solute transport models often incorporate the effects of hydrodynamic processes rigorously but oversimplify chemical interactions among aqueous species. Sophisticated chemical equilibrium models, on the other hand, incorporate a variety of chemical processes but generally assume no-flow systems. In the past decade, coupled models accounting for complex hydrological and chemical processes, with varying degrees of sophistication, have been developed. The existing models of reactive transport employ two basic sets of equations. The transport of solutes is described by a set of partial differential equations, and the chemical processes, under the assumption of equilibrium, are described by a set of nonlinear algebraic equations. An important consideration in any approach is the choice of primary dependent variables. Most existing models cannot account for the complete set of chemical processes, cannot be easily extended to include mixed chemical equilibria and kinetics, and cannot handle practical two and three dimensional problems. The difficulties arise mainly from improper selection of the primary variables in the transport equations. (Author) 38 refs

  4. Room-temperature and temperature-dependent QSRR modelling for predicting the nitrate radical reaction rate constants of organic chemicals using ensemble learning methods.

    Science.gov (United States)

    Gupta, S; Basant, N; Mohan, D; Singh, K P

    2016-07-01

    Experimental determinations of the rate constants of the reaction of NO3 with a large number of organic chemicals are tedious, and time and resource intensive; and the development of computational methods has widely been advocated. In this study, we have developed room-temperature (298 K) and temperature-dependent quantitative structure-reactivity relationship (QSRR) models based on the ensemble learning approaches (decision tree forest (DTF) and decision treeboost (DTB)) for predicting the rate constant of the reaction of NO3 radicals with diverse organic chemicals, under OECD guidelines. Predictive powers of the developed models were established in terms of statistical coefficients. In the test phase, the QSRR models yielded a correlation (r(2)) of >0.94 between experimental and predicted rate constants. The applicability domains of the constructed models were determined. An attempt has been made to provide the mechanistic interpretation of the selected features for QSRR development. The proposed QSRR models outperformed the previous reports, and the temperature-dependent models offered a much wider applicability domain. This is the first report presenting a temperature-dependent QSRR model for predicting the nitrate radical reaction rate constant at different temperatures. The proposed models can be useful tools in predicting the reactivities of chemicals towards NO3 radicals in the atmosphere, hence, their persistence and exposure risk assessment.

  5. Kinetics of methane fermentation yield in biogas reactors: Genetic variation and association with chemical composition in maize

    International Nuclear Information System (INIS)

    Grieder, Christoph; Mittweg, Greta; Dhillon, Baldev S.; Montes, Juan M.; Orsini, Elena; Melchinger, Albrecht E.

    2012-01-01

    Maize (Zea mays L.) is the most competitive crop for methane production in Germany. Methane fermentation yield per unit of dry matter (MFY) is a determinant of methane yield, but little information is available on this trait. Our objectives were to investigate the kinetics of MFY during fermentation of maize, estimate quantitative-genetic parameters for different traits related to MFY and examine the relationship of MFY with chemical composition and silage quality. Whole-plant material of 16 inbreds and their 32 testcrosses was analyzed for MFY over 35 days of fermentation using a discontinuous laboratory assay. Data were also generated on chemical composition and in vitro digestible organic matter (IVDOM). Significant genotypic variances and high heritabilities were observed for MFY at early fermentation stages (up to 5 days) probably due to different concentrations of easily degradable chemical components. However, genotypic variances and heritability of MFY reduced as fermentation progressed, because of complete or partial degradation of all chemical components. Further, there were strong correlations of MFY with chemical components at early fermentation stages but not at later stages. Therefore, MFY at later stages, which is closer to potential MFY, does not seem to be amenable to selection. High heritability of IVDOM and its strong correlation with MFY in testcrosses indicated its possible use for preliminary or indirect selection. Keeping in view the magnitude of genetic variance that was low for MFY and high for dry matter yield (DMY), the other component of methane yield, more emphasis on breeding for DMY seems appropriate. -- Highlights: ► We investigated methane fermentation yield (MFY) of diverse germplasm of maize. ► The kinetics of MFY and its correlations with chemical composition were examined. ► Genetic variance and heritability for MFY decreased with fermentation time. ► Complete fermentation (35 d) reduced correlations of MFY with chemical

  6. Inflow, Outflow, Yields, and Stellar Population Mixing in Chemical Evolution Models

    Energy Technology Data Exchange (ETDEWEB)

    Andrews, Brett H. [PITT PACC, Department of Physics and Astronomy, University of Pittsburgh, Pittsburgh, PA 15260 (United States); Weinberg, David H.; Schönrich, Ralph; Johnson, Jennifer A., E-mail: andrewsb@pitt.edu [Department of Astronomy, The Ohio State University, 140 West 18th Avenue, Columbus, OH 43210 (United States)

    2017-02-01

    Chemical evolution models are powerful tools for interpreting stellar abundance surveys and understanding galaxy evolution. However, their predictions depend heavily on the treatment of inflow, outflow, star formation efficiency (SFE), the stellar initial mass function, the SN Ia delay time distribution, stellar yields, and stellar population mixing. Using flexCE, a flexible one-zone chemical evolution code, we investigate the effects of and trade-offs between parameters. Two critical parameters are SFE and the outflow mass-loading parameter, which shift the knee in [O/Fe]–[Fe/H] and the equilibrium abundances that the simulations asymptotically approach, respectively. One-zone models with simple star formation histories follow narrow tracks in [O/Fe]–[Fe/H] unlike the observed bimodality (separate high- α and low- α sequences) in this plane. A mix of one-zone models with inflow timescale and outflow mass-loading parameter variations, motivated by the inside-out galaxy formation scenario with radial mixing, reproduces the two sequences better than a one-zone model with two infall epochs. We present [X/Fe]–[Fe/H] tracks for 20 elements assuming three different supernova yield models and find some significant discrepancies with solar neighborhood observations, especially for elements with strongly metallicity-dependent yields. We apply principal component abundance analysis to the simulations and existing data to reveal the main correlations among abundances and quantify their contributions to variation in abundance space. For the stellar population mixing scenario, the abundances of α -elements and elements with metallicity-dependent yields dominate the first and second principal components, respectively, and collectively explain 99% of the variance in the model. flexCE is a python package available at https://github.com/bretthandrews/flexCE.

  7. Inflow, Outflow, Yields, and Stellar Population Mixing in Chemical Evolution Models

    International Nuclear Information System (INIS)

    Andrews, Brett H.; Weinberg, David H.; Schönrich, Ralph; Johnson, Jennifer A.

    2017-01-01

    Chemical evolution models are powerful tools for interpreting stellar abundance surveys and understanding galaxy evolution. However, their predictions depend heavily on the treatment of inflow, outflow, star formation efficiency (SFE), the stellar initial mass function, the SN Ia delay time distribution, stellar yields, and stellar population mixing. Using flexCE, a flexible one-zone chemical evolution code, we investigate the effects of and trade-offs between parameters. Two critical parameters are SFE and the outflow mass-loading parameter, which shift the knee in [O/Fe]–[Fe/H] and the equilibrium abundances that the simulations asymptotically approach, respectively. One-zone models with simple star formation histories follow narrow tracks in [O/Fe]–[Fe/H] unlike the observed bimodality (separate high- α and low- α sequences) in this plane. A mix of one-zone models with inflow timescale and outflow mass-loading parameter variations, motivated by the inside-out galaxy formation scenario with radial mixing, reproduces the two sequences better than a one-zone model with two infall epochs. We present [X/Fe]–[Fe/H] tracks for 20 elements assuming three different supernova yield models and find some significant discrepancies with solar neighborhood observations, especially for elements with strongly metallicity-dependent yields. We apply principal component abundance analysis to the simulations and existing data to reveal the main correlations among abundances and quantify their contributions to variation in abundance space. For the stellar population mixing scenario, the abundances of α -elements and elements with metallicity-dependent yields dominate the first and second principal components, respectively, and collectively explain 99% of the variance in the model. flexCE is a python package available at https://github.com/bretthandrews/flexCE.

  8. Hydrothermal Liquefaction of Dried Distillers Grains with solubles: A reaction temperature study

    DEFF Research Database (Denmark)

    Mørup, Anders; Christensen, Per Runge; Aarup, David Friis

    2012-01-01

    provides rapid heating of biomass feeds and the option of performing multiple sequential repetitions. This bypasses long, uncontrollable temperature gradients and unintended changes in the reaction chemistry. The product, a crude bio-oil, was characterized in terms of yield, elemental composition......The effect of the reaction temperature on hydrothermal liquefaction of dried distillers grains with solubles (DDGS) was investigated using a novel stop-flow reactor system at varying temperatures (300–400 °C), fixed pressure (250 bar), and fixed reaction time (15 min). The stop-flow reactor......, and chemical composition. Higher reaction temperatures resulted in improved bio-oil yields, less char formation, and higher heating values of the bio-oil. A supercritical reaction temperature of 400 °C was found to produce bio-oil in the highest yields and of the best quality....

  9. Chemical Exchange Saturation Transfer in Chemical Reactions: A Mechanistic Tool for NMR Detection and Characterization of Transient Intermediates.

    Science.gov (United States)

    Lokesh, N; Seegerer, Andreas; Hioe, Johnny; Gschwind, Ruth M

    2018-02-07

    The low sensitivity of NMR and transient key intermediates below detection limit are the central problems studying reaction mechanisms by NMR. Sensitivity can be enhanced by hyperpolarization techniques such as dynamic nuclear polarization or the incorporation/interaction of special hyperpolarized molecules. However, all of these techniques require special equipment, are restricted to selective reactions, or undesirably influence the reaction pathways. Here, we apply the chemical exchange saturation transfer (CEST) technique for the first time to NMR detect and characterize previously unobserved transient reaction intermediates in organocatalysis. The higher sensitivity of CEST and chemical equilibria present in the reaction pathway are exploited to access population and kinetics information on low populated intermediates. The potential of the method is demonstrated on the proline-catalyzed enamine formation for unprecedented in situ detection of a DPU stabilized zwitterionic iminium species, the elusive key intermediate between enamine and oxazolidinones. The quantitative analysis of CEST data at 250 K revealed the population ratio of [Z-iminium]/[exo-oxazolidinone] 0.02, relative free energy +8.1 kJ/mol (calculated +7.3 kJ/mol), and free energy barrier of +45.9 kJ/mol (ΔG ⧧ calc. (268 K) = +42.2 kJ/mol) for Z-iminium → exo-oxazolidinone. The findings underpin the iminium ion participation in enamine formation pathway corroborating our earlier theoretical prediction and help in better understanding. The reliability of CEST is validated using 1D EXSY-build-up techniques at low temperature (213 K). The CEST method thus serves as a new tool for mechanistic investigations in organocatalysis to access key information, such as chemical shifts, populations, and reaction kinetics of intermediates below the standard NMR detection limit.

  10. On the deduction of chemical reaction pathways from measurements of time series of concentrations.

    Science.gov (United States)

    Samoilov, Michael; Arkin, Adam; Ross, John

    2001-03-01

    We discuss the deduction of reaction pathways in complex chemical systems from measurements of time series of chemical concentrations of reacting species. First we review a technique called correlation metric construction (CMC) and show the construction of a reaction pathway from measurements on a part of glycolysis. Then we present two new improved methods for the analysis of time series of concentrations, entropy metric construction (EMC), and entropy reduction method (ERM), and illustrate (EMC) with calculations on a model reaction system. (c) 2001 American Institute of Physics.

  11. Purification of free hydrogen or hydrogen combined in a gaseous mixture by chemical reactions with uranium

    International Nuclear Information System (INIS)

    Caron-Charles, M.; Gilot, B.

    1989-01-01

    Within the framework of the European fusion program, the authors are dealing with the tritium technology aspect. Hydrogen, free or under a combined form within a H 2 , N 2 , NH 3 , O 2 , gaseous mixture, can be purified by chemical reactions with uranium metal. The resulting reactions consist in absorbing the impurities without holding back H 2 . Working conditions have been defined according to two main goals: the formation of stable solid products, especially under hydrogenated atmosphere and the optimization of the material quantities to be used. Thermodynamical considerations have shown that the 950-1300 K temperature range should be suitable for this chemical process. Experiments performed with massive uranium set in a closed reactor at 973 K, have produced hydrogen according to the predicted reactions rates. But they have also pointed out the importance of interferences that might occur in the uranium-gas system, on the gases conversion rates. The comparison between the chemical kinetic ratings of the reactions of pure gases and the chemical kinetic ratings of the reactions of the same gases in mixture, has been set up. It proves that simultaneous reactions can modify the working conditions of the solid products formation, and particularly modify their structure. In this case, chemical kinetic ratings are increased up to their maximal value; that means surface phenomena are favoured as with uranium powder gases reactions. (orig.)

  12. Experimental and Theoretical Investigation of Shock-Induced Reactions in Energetic Materials

    Energy Technology Data Exchange (ETDEWEB)

    Kay, Jeffrey J. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Park, Samuel [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Kohl, Ian Thomas [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Knepper, Robert [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Farrow, Darcie [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Tappan, Alexander S. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2017-09-01

    In this work, shock-induced reactions in high explosives and their chemical mechanisms were investigated using state-of-the-art experimental and theoretical techniques. Experimentally, ultrafast shock interrogation (USI, an ultrafast interferometry technique) and ultrafast absorption spectroscopy were used to interrogate shock compression and initiation of reaction on the picosecond timescale. The experiments yielded important new data that appear to indicate reaction of high explosives on the timescale of tens of picoseconds in response to shock compression, potentially setting new upper limits on the timescale of reaction. Theoretically, chemical mechanisms of shock-induced reactions were investigated using density functional theory. The calculations generated important insights regarding the ability of several hypothesized mechanisms to account for shock-induced reactions in explosive materials. The results of this work constitute significant advances in our understanding of the fundamental chemical reaction mechanisms that control explosive sensitivity and initiation of detonation.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-06-10

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

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

    Science.gov (United States)

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

    2017-08-01

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

  15. Application of Molecular Topology for the Prediction of Reaction Yields and Anti-Inflammatory Activity of Heterocyclic Amidine Derivatives

    Directory of Open Access Journals (Sweden)

    Ramón García-Domenech

    2011-02-01

    Full Text Available Topological-mathematical models based on multiple linear regression analyses have been built to predict the reaction yields and the anti-inflammatory activity of a set of heterocylic amidine derivatives, synthesized under environmental friendly conditions, using microwave irradiation. Two models with three variables each were selected. The models were validated by cross-validation and randomization tests. The final outcome demonstrates a good agreement between the predicted and experimental results, confirming the robustness of the method. These models also enabled the screening of virtual libraries for new amidine derivatives predicted to show higher values of reaction yields and anti-inflammatory activity.

  16. Radical Reactions in the Gas Phase: Recent Development and Application in Biomolecules

    Directory of Open Access Journals (Sweden)

    Yang Gao

    2014-01-01

    Full Text Available This review summarizes recent literature describing the use of gas phase radical reactions for structural characterization of complex biomolecules other than peptides. Specifically, chemical derivatization, in-source chemical reaction, and gas phase ion/ion reactions have been demonstrated as effective ways to generate radical precursor ions that yield structural informative fragments complementary to those from conventional collision-induced dissociation (CID. Radical driven dissociation has been applied to a variety of biomolecules including peptides, nucleic acids, carbohydrates, and phospholipids. The majority of the molecules discussed in this review see limited fragmentation from conventional CID, and the gas phase radical reactions open up completely new dissociation channels for these molecules and therefore yield high fidelity confirmation of the structures of the target molecules. Due to the extensively studied peptide fragmentation, this review focuses only on nonpeptide biomolecules such as nucleic acids, carbohydrates, and phospholipids.

  17. Potential design modifications for the High Yield Lithium Injection Fusion Energy (HYLIFE) reaction chamber

    International Nuclear Information System (INIS)

    Pitts, J.H.; Hovingh, J.; Meier, W.R.; Monsler, M.J.; Powell, E.G.; Walker, P.E.

    1979-01-01

    Generation of electric power from inertial confinement fusion requires a reaction chamber. One promising type, the High Yield Lithium Injection Fusion Energy (HYLIFE) chamber, includes a falling array of liquid lithium jets. These jets act as: (1) a renewable first wall and blanket to shield metal components from x-ray and neutron exposure, (2) a tritium breeder to replace tritium burned during the fusion process, and (3) an absorber and transfer medium for fusion energy. Over 90% of the energy produced in the reaction chamber is absorbed in the lithium jet fall. Design aspects are included

  18. Resonance analysis of the {sup 12}C,{sup 13}C({alpha},n) reactions and evaluation of neutron yield data of the reaction

    Energy Technology Data Exchange (ETDEWEB)

    Murata, Toru [AITEL Corp., Tokyo (Japan)

    1998-03-01

    The {sup 12}C({alpha},n){sup 15}O reaction and the {sup 13}C({alpha},n){sup 16}O reaction were analyzed with a resonance formula in the incident {alpha}-particle energy range of 1.0 to 16.0 MeV. With the obtained resonance parameters, branching ratios of the emitted neutrons to the several levels of the residual nucleus and their angular distributions were calculated to obtain the energy spectrum of emitted neutrons. Thick target neutron yield of carbon were also calculated and compared with the experimental data. (author)

  19. 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.

  20. Chemical reactions in the presence of surface modulation and stirring

    OpenAIRE

    Kamhawi, Khalid; Náraigh, Lennon Ó

    2009-01-01

    We study the dynamics of simple reactions where the chemical species are confined on a general, time-modulated surface, and subjected to externally-imposed stirring. The study of these inhomogeneous effects requires a model based on a reaction-advection-diffusion equation, which we derive. We use homogenization methods to show that up to second order in a small scaling parameter, the modulation effects on the concentration field are asymptotically equivalent for systems with or without stirri...

  1. Mapping the dark space of chemical reactions with extended nanomole synthesis and MALDI-TOF MS.

    Science.gov (United States)

    Lin, Shishi; Dikler, Sergei; Blincoe, William D; Ferguson, Ronald D; Sheridan, Robert P; Peng, Zhengwei; Conway, Donald V; Zawatzky, Kerstin; Wang, Heather; Cernak, Tim; Davies, Ian W; DiRocco, Daniel A; Sheng, Huaming; Welch, Christopher J; Dreher, Spencer D

    2018-05-24

    Understanding the practical limitations of chemical reactions is critically important for efficiently planning the synthesis of compounds in pharmaceutical, agrochemical and specialty chemical research and development. However, literature reports of the scope of new reactions are often cursory and biased toward successful results, severely limiting the ability to predict reaction outcomes for untested substrates. We herein illustrate strategies for carrying out large scale surveys of chemical reactivity using a material-sparing nanomole-scale automated synthesis platform with greatly expanded synthetic scope combined with ultra-high throughput (uHT) matrix assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS). Copyright © 2018, American Association for the Advancement of Science.

  2. Influence of tumbling and phosphate on the yield, sensory and chemical characteristics of pork liver loaf

    NARCIS (Netherlands)

    Percel, P.J.; Parrett, N.A.; Plimpton, R.F.; Ockerman, H.W.; Krol, B.; Roon, P.S. van

    1982-01-01

    Yield, sensory and chemical properties of pork liver loaves manufactured using varying processing treatments (tumbling vs immersion) and phosphate levels (0 vs 6.4%) were studied. Tumbling significantly improved liver cure uptake, total cure and loaf cooked yield when compared to immersion as a

  3. Assessing the Effect of Organic Compounds, Biofertilizers and Chemical Fertilizers on Morphological Properties,yield and Yield Components of Forage Sorghum (Sorghum bicolor

    Directory of Open Access Journals (Sweden)

    A.H Saeidnejad

    2012-12-01

    Full Text Available Recently, using the source of organic fertilizers and biofertilizers in sustainable crop production is growing. In order to evaluate the effect of organic compounds, biofertilizers and chemical fertilizer on morphological properties, yield and yield components of forage Sorghum (sorghum bicolor a field experiment was conducted in the Research Farm, College of Agriculture, Ferdowsi University of Mashhad in 2008.The treatments were seed inoculation with the combination of Azotobacter chroococcum and Azospirillum brasilense, Compost (15 t/ha, Vermicompost (10 t/ha, seed inoculation with Azotobacter and Azospirillum and compost (10t/ha, seed inoculation with Azotobacter chroococcum and Azospirillum brasilense and Vermicompost (7t/ha, seed inoculation with Pseudomonas flurescence, seed inoculation with Pseudomonas flurescence and Azotobacter chroococcum and Azospirillum brasilense combination, seed inoculation with Pseudomonas flurescence and compost (15t/ha, chemical fertilizer (80 kg/h urea fertilizer and 50 kg/h super phosphate fertilizer and control. Harvesting was performed in 2 cuts in flowering stage. Plant height, number of tiller per plant and SPAD reading was significantly affected by the treatments. Stem diameter was not affected by any treatments. There was a significant difference among all treatments in terms of fresh and dry forage yield. There were no significant differences among all treatments in terms of stem and leaf dry matter. In general, result of this experiment indicated that organic amendments and biofertilizers could be acceptable alternatives for chemical fertilizers.

  4. 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…

  5. On some limitations of reaction-diffusion chemical computers in relation to Voronoi diagram and its inversion

    International Nuclear Information System (INIS)

    Adamatzky, Andrew; Lacy Costello, Benjamin de

    2003-01-01

    A reaction-diffusion chemical computer in this context is a planar uniform chemical reactor, where data and results of a computation are represented by concentration profiles of reactants and the computation itself is implemented via the spreading and interaction of diffusive and phase waves. This class of chemical computers are efficient at solving problems with a 'natural' parallelism where data sets are decomposable onto a large number of geographically neighboring domains which are then processed in parallel. Typical problems of this type include image processing, geometrical transformations and optimisation. When chemical based devices are used to solve such problems questions regarding their reproducible, efficiency and the accuracy of their computations arise. In addition to these questions what are the limitations of reaction-diffusion chemical processors--what type of problems cannot currently and are unlikely ever to be solved? To answer the questions we study how a Voronoi diagram is constructed and how it is inverted in a planar chemical processor. We demonstrate that a Voronoi diagram is computed only partially in the chemical processor. We also prove that given a specific Voronoi diagram it is impossible to reconstruct the planar set (from which diagram was computed) in the reaction-diffusion chemical processor. In the Letter we open the first ever line of enquiry into the computational inability of reaction-diffusion chemical computers

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

    OpenAIRE

    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 concentration profiles for a wide range of processes and conditions, for both film and penetration model. With the aid of this mass transfer model it is demonstrated that the absorption rates in syst...

  7. Non-invasive estimation of dissipation from non-equilibrium fluctuations in chemical reactions.

    Science.gov (United States)

    Muy, S; Kundu, A; Lacoste, D

    2013-09-28

    We show how to extract an estimate of the entropy production from a sufficiently long time series of stationary fluctuations of chemical reactions. This method, which is based on recent work on fluctuation theorems, is direct, non-invasive, does not require any knowledge about the underlying dynamics and is applicable even when only partial information is available. We apply it to simple stochastic models of chemical reactions involving a finite number of states, and for this case, we study how the estimate of dissipation is affected by the degree of coarse-graining present in the input data.

  8. Chemical repair activity of free radical scavenger edaravone: reduction reactions with dGMP hydroxyl radical adducts and suppression of base lesions and AP sites on irradiated plasmid DNA.

    Science.gov (United States)

    Hata, Kuniki; Urushibara, Ayumi; Yamashita, Shinichi; Lin, Mingzhang; Muroya, Yusa; Shikazono, Naoya; Yokoya, Akinari; Fu, Haiying; Katsumura, Yosuke

    2015-01-01

    Reactions of edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one) with deoxyguanosine monophosphate (dGMP) hydroxyl radical adducts were investigated by pulse radiolysis technique. Edaravone was found to reduce the dGMP hydroxyl radical adducts through electron transfer reactions. The rate constants of the reactions were greater than 4 × 10(8) dm(3) mol(-1) s(-1) and similar to those of the reactions of ascorbic acid, which is a representative antioxidant. Yields of single-strand breaks, base lesions, and abasic sites produced in pUC18 plasmid DNA by gamma ray irradiation in the presence of low concentrations (10-1000 μmol dm(-3)) of edaravone were also quantified, and the chemical repair activity of edaravone was estimated by a method recently developed by the authors. By comparing suppression efficiencies to the induction of each DNA lesion, it was found that base lesions and abasic sites were suppressed by the chemical repair activity of edaravone, although the suppression of single-strand breaks was not very effective. This phenomenon was attributed to the chemical repair activity of edaravone toward base lesions and abasic sites. However, the chemical repair activity of edaravone for base lesions was lower than that of ascorbic acid. © The Author 2014. Published by Oxford University Press on behalf of The Japan Radiation Research Society and Japanese Society for Radiation Oncology.

  9. Monitoring chemical reactions by low-field benchtop NMR at 45 MHz: pros and cons.

    Science.gov (United States)

    Silva Elipe, Maria Victoria; Milburn, Robert R

    2016-06-01

    Monitoring chemical reactions is the key to controlling chemical processes where NMR can provide support. High-field NMR gives detailed structural information on chemical compounds and reactions; however, it is expensive and complex to operate. Conversely, low-field NMR instruments are simple and relatively inexpensive alternatives. While low-field NMR does not provide the detailed information as the high-field instruments as a result of their smaller chemical shift dispersion and the complex secondary coupling, it remains of practical value as a process analytical technology (PAT) tool and is complimentary to other established methods, such as ReactIR and Raman spectroscopy. We have tested a picoSpin-45 (currently under ThermoFisher Scientific) benchtop NMR instrument to monitor three types of reactions by 1D (1) H NMR: a Fischer esterification, a Suzuki cross-coupling, and the formation of an oxime. The Fischer esterification is a relatively simple reaction run at high concentration and served as proof of concept. The Suzuki coupling is an example of a more complex, commonly used reaction involving overlapping signals. Finally, the oxime formation involved a reaction in two phases that cannot be monitored by other PAT tools. Here, we discuss the pros and cons of monitoring these reactions at a low-field of 45 MHz by 1D (1) H NMR. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

  10. Low-energy reaction yields for 18O(p,γ) and 18O(α,γ)

    International Nuclear Information System (INIS)

    Vogelaar, R.B.; Wang, T.R.; Kellogg, S.E.; Kavanagh, R.W.

    1990-01-01

    Resonance yields, γ-ray branching, and low-energy limits have been measured for 18 O(p,γ) and 18 O(α,γ), for E p α <0.78 MeV, using a 4π array of NaI detectors. The results confirm previous resonance strengths, and set additional constraints on possible low-energy contributions to stellar reaction rates

  11. Spatial distribution of the chemical properties of the soil and of soybean yield in the field

    Directory of Open Access Journals (Sweden)

    Alexandre Gazolla-Neto

    2016-06-01

    Full Text Available ABSTRACT The aim of this study was to evaluate the spatial dependence between chemical properties of the soil and yield components in the soybean using precision farming techniques. Samples of the soil and plants were taken from georeferenced points to determine the chemical properties of the soil and the yield components. The results were submitted to Pearson correlation analysis, descriptive statistics and geostatistics. The coefficient of variation showed a wide range of distribution for the chemical attributes of the soil, with the highest indices being found for the levels of available phosphorus (102% and potassium (72.65%. Soil pH and organic matter showed a coefficient of variation of 5.96 and 15.93% respectively. Semivariogram analysis of the yield components (productivity, 1,000-seed weight and number of seeds and the chemical properties of the soil (organic matter, pH, phosphorus, potassium, calcium, magnesium, boron, manganese and zinc fitted the spherical model with moderate spatial dependence, with values ranging from 200 to 700 m. Spatial distribution by means of map interpolation was efficient in evaluating spatial variability, allowing the identification and quantification of regions of low and high productivity in the production area, together with the distribution of soil attributes and their respective levels of availability to the soybean plants.

  12. Influence of density on radiation-chemical yield of molecular hydrogen formed at radiolysis of aqueous solution of NaOH

    International Nuclear Information System (INIS)

    Jafarov, Y.D.; Hajiyeva, S.R.; Ramazanova, N.K.; Aliyev, S.M.; Alasgarov, A.M.

    2014-01-01

    Full text : In atom and nuclear energy the specialists knowledge about radiation-chemical yield of the initial products formed under the influence of ionizing rays on water is of great importance from the point of security. The radiation-chemical yields of molecular hydrogen have been defined according to the graph and the obtained results

  13. Effect of Chemical Fertilizer, Cow Manure and Municipal Compost on Yield, Yield Components and Oil Quantity of three Sesame (Sesamum indicum L. Cultivars in Mashhad

    Directory of Open Access Journals (Sweden)

    P Rezvani Moghaddam

    2013-10-01

    Full Text Available In order to evaluate the effects of different organic and chemical fertilizers on yield, yield components and seed oil content of sesame an experiment was conducted in a split plot layout based on randomized complete block design with four replications at Research Station, Faculty of Agriculture, Ferdowsi University of Mashhad in year 2006. Four types of fertilizer, including chemical fertilizer, cow manure, municipal compost and no fertilizer (control were allocated as main plots and three sesame cultivars (two local varieties of Kalat and Esfarayen, and Oltan cultivar were used as sub plots. The results showed that fertilizer treatments had significant effect (P

  14. Simulating chemical reactions in ionic liquids using QM/MM methodology.

    Science.gov (United States)

    Acevedo, Orlando

    2014-12-18

    The use of ionic liquids as a reaction medium for chemical reactions has dramatically increased in recent years due in large part to the numerous reported advances in catalysis and organic synthesis. In some extreme cases, ionic liquids have been shown to induce mechanistic changes relative to conventional solvents. Despite the large interest in the solvents, a clear understanding of the molecular factors behind their chemical impact is largely unknown. This feature article reviews our efforts developing and applying mixed quantum and molecular mechanical (QM/MM) methodology to elucidate the microscopic details of how these solvents operate to enhance rates and alter mechanisms for industrially and academically important reactions, e.g., Diels-Alder, Kemp eliminations, nucleophilic aromatic substitutions, and β-eliminations. Explicit solvent representation provided the medium dependence of the activation barriers and atomic-level characterization of the solute-solvent interactions responsible for the experimentally observed "ionic liquid effects". Technical advances are also discussed, including a linear-scaling pairwise electrostatic interaction alternative to Ewald sums, an efficient polynomial fitting method for modeling proton transfers, and the development of a custom ionic liquid OPLS-AA force field.

  15. Regression analysis of a chemical reaction fouling model

    International Nuclear Information System (INIS)

    Vasak, F.; Epstein, N.

    1996-01-01

    A previously reported mathematical model for the initial chemical reaction fouling of a heated tube is critically examined in the light of the experimental data for which it was developed. A regression analysis of the model with respect to that data shows that the reference point upon which the two adjustable parameters of the model were originally based was well chosen, albeit fortuitously. (author). 3 refs., 2 tabs., 2 figs

  16. Time-resolved resonance fluorescence spectroscopy for study of chemical reactions in laser-induced plasmas.

    Science.gov (United States)

    Liu, Lei; Deng, Leimin; Fan, Lisha; Huang, Xi; Lu, Yao; Shen, Xiaokang; Jiang, Lan; Silvain, Jean-François; Lu, Yongfeng

    2017-10-30

    Identification of chemical intermediates and study of chemical reaction pathways and mechanisms in laser-induced plasmas are important for laser-ablated applications. Laser-induced breakdown spectroscopy (LIBS), as a promising spectroscopic technique, is efficient for elemental analyses but can only provide limited information about chemical products in laser-induced plasmas. In this work, time-resolved resonance fluorescence spectroscopy was studied as a promising tool for the study of chemical reactions in laser-induced plasmas. Resonance fluorescence excitation of diatomic aluminum monoxide (AlO) and triatomic dialuminum monoxide (Al 2 O) was used to identify these chemical intermediates. Time-resolved fluorescence spectra of AlO and Al 2 O were used to observe the temporal evolution in laser-induced Al plasmas and to study their formation in the Al-O 2 chemistry in air.

  17. Force-induced chemical reactions on the metal centre in a single metalloprotein molecule

    Science.gov (United States)

    Zheng, Peng; Arantes, Guilherme M.; Field, Martin J.; Li, Hongbin

    2015-01-01

    Metalloproteins play indispensable roles in biology owing to the versatile chemical reactivity of metal centres. However, studying their reactivity in many metalloproteins is challenging, as protein three-dimensional structure encloses labile metal centres, thus limiting their access to reactants and impeding direct measurements. Here we demonstrate the use of single-molecule atomic force microscopy to induce partial unfolding to expose metal centres in metalloproteins to aqueous solution, thus allowing for studying their chemical reactivity in aqueous solution for the first time. As a proof-of-principle, we demonstrate two chemical reactions for the FeS4 centre in rubredoxin: electrophilic protonation and nucleophilic ligand substitution. Our results show that protonation and ligand substitution result in mechanical destabilization of the FeS4 centre. Quantum chemical calculations corroborated experimental results and revealed detailed reaction mechanisms. We anticipate that this novel approach will provide insights into chemical reactivity of metal centres in metalloproteins under biologically more relevant conditions. PMID:26108369

  18. 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.

  19. Catalytic subcritical water liquefaction of flax straw for high yield of furfural

    International Nuclear Information System (INIS)

    Harry, Inibehe; Ibrahim, Hussameldin; Thring, Ron; Idem, Raphael

    2014-01-01

    There is substantial interest in the application of biomass as a renewable fuel or for production of chemicals. Flax straw can be converted into valuable chemicals and biofuels via liquefaction in sub-critical water. In this study, the yield of furfural and the kinetics of flax straw liquefaction under sub-critical water conditions were investigated using a high-pressure autoclave reactor. The liquefaction was conducted in the temperature range of 175–325 °C, pressure of 0.1 MPa–8 MPa, retention time in the range of 0 min–120 min, and flax straw mass fraction (w F ) of 5–20 %. Also, the effect of acid catalysts on furfural yield was studied. The kinetic parameters of flax straw liquefaction were determined using nonlinear regression of the experimental data, assuming second-order kinetics. The apparent activation energy was found to be 27.97 kJ mol −1 while the reaction order was 2.0. The optimum condition for furfural yield was at 250 °C, 6.0 MPa, w F of 5% and 0 retention time after reaching set conditions. An acid catalyst was found to selectively favour furfural yield with 40% flax straw conversion. - Highlights: • Flax straw liquefaction in subcritical water. • Creation of a reaction pathway that can be used to optimized furfural production. • Acid catalyst selectively favoured furfural yield with respect to other liquid products. • At the highest process temperature of 325 °C, a carbon conversion of 40% was achieved. • Activation energy and reaction order was 28 kJ/mol and 2.0 respectively

  20. Systematic evaluation and optimization of modification reactions of oligonucleotides with amines and carboxylic acids for the synthesis of DNA-encoded chemical libraries.

    Science.gov (United States)

    Franzini, Raphael M; Samain, Florent; Abd Elrahman, Maaly; Mikutis, Gediminas; Nauer, Angela; Zimmermann, Mauro; Scheuermann, Jörg; Hall, Jonathan; Neri, Dario

    2014-08-20

    DNA-encoded chemical libraries are collections of small molecules, attached to DNA fragments serving as identification barcodes, which can be screened against multiple protein targets, thus facilitating the drug discovery process. The preparation of large DNA-encoded chemical libraries crucially depends on the availability of robust synthetic methods, which enable the efficient conjugation to oligonucleotides of structurally diverse building blocks, sharing a common reactive group. Reactions of DNA derivatives with amines and/or carboxylic acids are particularly attractive for the synthesis of encoded libraries, in view of the very large number of building blocks that are commercially available. However, systematic studies on these reactions in the presence of DNA have not been reported so far. We first investigated conditions for the coupling of primary amines to oligonucleotides, using either a nucleophilic attack on chloroacetamide derivatives or a reductive amination on aldehyde-modified DNA. While both methods could be used for the production of secondary amines, the reductive amination approach was generally associated with higher yields and better purity. In a second endeavor, we optimized conditions for the coupling of a diverse set of 501 carboxylic acids to DNA derivatives, carrying primary and secondary amine functions. The coupling efficiency was generally higher for primary amines, compared to secondary amine substituents, but varied considerably depending on the structure of the acids and on the synthetic methods used. Optimal reaction conditions could be found for certain sets of compounds (with conversions >80%), but multiple reaction schemes are needed when assembling large libraries with highly diverse building blocks. The reactions and experimental conditions presented in this article should facilitate the synthesis of future DNA-encoded chemical libraries, while outlining the synthetic challenges that remain to be overcome.

  1. Chemical reaction dynamics using the Advanced Light Source

    International Nuclear Information System (INIS)

    Yang, X.; Blank, D.A.; Heimann, P.A.; Lee, Y.T.; Suits, A.G.; Lin, J.; Wodtke, A.M.

    1995-01-01

    The recently commissioned Advanced Light Source (ALS) at Berkeley provides a high brightness, tunable VUV light source for chemical dynamics studies. A dedicated chemical dynamics beamline has been built at the ALS for studies of fundamental chemical processes. High flux (10(sup 16) photon/s with 2% bandwidth) VUV synchrotron radiation from 5 to 30 eV can be obtained from the beamline, whose source is the U8/10 undulator. Three endstations will be in operation for studies ranging from crossed beam reaction dynamics and photodissociation to high resolution photoionization dynamics and spectroscopy. A rotatable source crossed molecular beam apparatus (endstation one) has been established for unimolecular and bimolecular reactive scattering studies. Photodissociation of methylamine and ozone were carried out using VUV synchrotron radiation as the ionization detection technique at this endstation. Results show the advantages of the new endstation using VUV ionization as the detection scheme over similar machines using electron bombardment as the ionization source

  2. Chemical reaction dynamics using the Advanced Light Source

    International Nuclear Information System (INIS)

    Yang, X.; Blank, D.A.; Heimann, P.A.; Lee, Y.T.; Suits, A.G.; Lin, J.; Wodtke, A.M.

    1995-09-01

    The recently commissioned Advanced Light Source (ALS) at Berkeley provides a high brightness, tunable VUV light source for chemical dynamics studies. A dedicated chemical dynamics beamline has been built at the ALS for studies of fundamental chemical processes. High flux (10 16 photon/s with 2% bandwidth) VUV synchrotron radiation from 5 to 30 eV can be obtained from the beamline, whose source is the U8/10 undulator. Three endstations will be in operation for studies ranging from crossed beam reaction dynamics and photodissociation to high resolution photoionization dynamics and spectroscopy. A rotatable source crossed molecular beam apparatus (endstation one) has been established for unimolecular and bimolecular reactive scattering studies. Photodissociation of methylamine and ozone were carried out using VUV synchrotron radiation as the ionization detection technique at this endstation. Results show the advantages of the new endstation using VUV ionization as the detection scheme over similar machines using electron bombardment as the ionization source

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

    Science.gov (United States)

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

    2017-08-15

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

  4. Coarse grain model for coupled thermo-mechano-chemical processes and its application to pressure-induced endothermic chemical reactions

    International Nuclear Information System (INIS)

    Antillon, Edwin; Banlusan, Kiettipong; Strachan, Alejandro

    2014-01-01

    We extend a thermally accurate model for coarse grain dynamics (Strachan and Holian 2005 Phys. Rev. Lett. 94 014301) to enable the description of stress-induced chemical reactions in the degrees of freedom internal to the mesoparticles. Similar to the breathing sphere model, we introduce an additional variable that describes the internal state of the particles and whose dynamics is governed both by an internal potential energy function and by interparticle forces. The equations of motion of these new variables are derived from a Hamiltonian and the model exhibits two desired features: total energy conservation and Galilean invariance. We use a simple model material with pairwise interactions between particles and study pressure-induced chemical reactions induced by hydrostatic and uniaxial compression. These examples demonstrate the ability of the model to capture non-trivial processes including the interplay between mechanical, thermal and chemical processes of interest in many applications. (paper)

  5. Tunneling in the CH{sub 3} + H{sub 2} {yields} CH{sub 4} + H reaction and its isotopic analog: an anomalous isotope effect

    Energy Technology Data Exchange (ETDEWEB)

    Kurosaki, Yuzuru; Takayanagi, Toshiyuki [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1998-10-01

    Vibrationally adiabatic ground-state potential curves for the CH{sub 3} + H{sub 2} {yields} CH{sub 4} + H (I) and CD{sub 3} + H{sub 2} {yields} CD{sub 4}H + H (II) reactions were obtained by adding zero-point energies of harmonic vibrations orthogonal to intrinsic reaction coordinate (IRC) to bare potential curves along IRC. It was clarified that both the barrier height and barrier width of reaction II are smaller than those of reaction I. This computational result qualitatively explains the experimental observation of Momose et al. (J. Chem. Phys. 108 (1998) 7334) that reaction II occurs but reaction I does not occur in solid parahydrogen at 5 K. (author)

  6. 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.

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

    International Nuclear Information System (INIS)

    Kustova, Elena V.; Kremer, Gilberto M.

    2014-01-01

    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, N 2 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

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

    Energy Technology Data Exchange (ETDEWEB)

    Kustova, Elena V., E-mail: e.kustova@spbu.ru [Department of Mathematics and Mechanics, Saint Petersburg State University, 198504 Universitetskiy pr. 28, Saint Petersburg (Russian Federation); Kremer, Gilberto M., E-mail: kremer@fisica.ufpr.br [Departamento de Física, Universidade Federal do Paraná, Caixa Postal 19044, 81531-980 Curitiba (Brazil)

    2014-12-05

    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, N{sub 2} 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.

  9. Two-Dimensional Resonance Raman Signatures of Vibronic Coherence Transfer in Chemical Reactions.

    Science.gov (United States)

    Guo, Zhenkun; Molesky, Brian P; Cheshire, Thomas P; Moran, Andrew M

    2017-11-02

    Two-dimensional resonance Raman (2DRR) spectroscopy has been developed for studies of photochemical reaction mechanisms and structural heterogeneity in condensed phase systems. 2DRR spectroscopy is motivated by knowledge of non-equilibrium effects that cannot be detected with traditional resonance Raman spectroscopy. For example, 2DRR spectra may reveal correlated distributions of reactant and product geometries in systems that undergo chemical reactions on the femtosecond time scale. Structural heterogeneity in an ensemble may also be reflected in the 2D spectroscopic line shapes of both reactive and non-reactive systems. In this chapter, these capabilities of 2DRR spectroscopy are discussed in the context of recent applications to the photodissociation reactions of triiodide. We show that signatures of "vibronic coherence transfer" in the photodissociation process can be targeted with particular 2DRR pulse sequences. Key differences between the signal generation mechanisms for 2DRR and off-resonant 2D Raman spectroscopy techniques are also addressed. Overall, recent experimental developments and applications of the 2DRR method suggest that it will be a valuable tool for elucidating ultrafast chemical reaction mechanisms.

  10. Accurate and approximate thermal rate constants for polyatomic chemical reactions

    International Nuclear Information System (INIS)

    Nyman, Gunnar

    2007-01-01

    In favourable cases it is possible to calculate thermal rate constants for polyatomic reactions to high accuracy from first principles. Here, we discuss the use of flux correlation functions combined with the multi-configurational time-dependent Hartree (MCTDH) approach to efficiently calculate cumulative reaction probabilities and thermal rate constants for polyatomic chemical reactions. Three isotopic variants of the H 2 + CH 3 → CH 4 + H reaction are used to illustrate the theory. There is good agreement with experimental results although the experimental rates generally are larger than the calculated ones, which are believed to be at least as accurate as the experimental rates. Approximations allowing evaluation of the thermal rate constant above 400 K are treated. It is also noted that for the treated reactions, transition state theory (TST) gives accurate rate constants above 500 K. TST theory also gives accurate results for kinetic isotope effects in cases where the mass of the transfered atom is unchanged. Due to neglect of tunnelling, TST however fails below 400 K if the mass of the transferred atom changes between the isotopic reactions

  11. Kinetics of heterogeneous chemical reactions: a theoretical model for the accumulation of pesticides in soil.

    Science.gov (United States)

    Lin, S H; Sahai, R; Eyring, H

    1971-04-01

    A theoretical model for the accumulation of pesticides in soil has been proposed and discussed from the viewpoint of heterogeneous reaction kinetics with a basic aim to understand the complex nature of soil processes relating to the environmental pollution. In the bulk of soil, the pesticide disappears by diffusion and a chemical reaction; the rate processes considered on the surface of soil are diffusion, chemical reaction, vaporization, and regular pesticide application. The differential equations involved have been solved analytically by the Laplace-transform method.

  12. Computer aided design, analysis and experimental investigation of membrane assisted batch reaction-separation systems

    DEFF Research Database (Denmark)

    Mitkowski, Piotr Tomasz; Buchaly, Carsten; Kreis, Peter

    2009-01-01

    Membrane assisted batch reaction operation offers an interesting option for equilibrium limited reaction systems in chemical and biochemical manufacturing by selective removal of one of the products and thereby increasing the product yield. The design of such hybrid systems need to take into acco......Membrane assisted batch reaction operation offers an interesting option for equilibrium limited reaction systems in chemical and biochemical manufacturing by selective removal of one of the products and thereby increasing the product yield. The design of such hybrid systems need to take...... into account the performance of each constituent element and the optimisation of the design must take into consideration their interdependency. In this paper use of a membrane, to assist in the synthesis of propyl-propionate is investigated through the use of a hybrid process design framework, which consists...... and separation functionalities and to design/analyse the hybrid scheme. The generated hybrid scheme has been validated through experiments involving an esterification reaction....

  13. Study of the reaction {pi}{sup -}p {yields} {pi}{sup +}{pi}{sup -}n at 870 MeV; Etude de la reaction {pi}{sup -}p {yields} {pi}{sup +}{pi}{sup -}n a 870 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Zsembery, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1969-07-01

    In the reaction {pi}{sup -}p {yields}{pi}{sup +}{pi}{sup -}n, we have measured the {pi}{sup +} momentum spectrum at various angles, from which the distributions (d{sup 2}{sigma}/dMd{omega}) of the ({pi}{sup -}n) system have been deduced. These distributions are compared with those obtained by a phenomenological model. This comparison allows a determination of the amplitude of the inelastic waves. It is found that the resonant waves D15 and F15 are no strongly coupled to the channel {delta}(1238) + {pi}. (author) [French] Dans la reaction {pi}{sup -}p {yields} {pi}{sup +}{pi}{sup -}n, nous avons mesure le spectre en impulsion des {pi}{sup +} a differents angles. Les distributions (d{sup 2}{sigma}/dMd{omega}) du systeme ({pi}{sup -}n) en ont ete deduites. Ces distributions sont comparees a celles obtenues par un modele phenomenologique. De la comparaison on determine l'amplitude des ondes inelastiques. Les ondes resonnantes D15 et FIS ne sont pas liees fortement a la voie {delta}(1238) + {pi}. (auteur)

  14. Nanoscale control of reversible chemical reaction between fullerene C60 molecules using scanning tunneling microscope.

    Science.gov (United States)

    Nakaya, Masato; Kuwahara, Yuji; Aono, Masakazu; Nakayama, Tomonobu

    2011-04-01

    The nanoscale control of reversible chemical reactions, the polymerization and depolymerization between C60 molecules, has been investigated. Using a scanning tunneling microscope (STM), the polymerization and depolymerization can be controlled at designated positions in ultrathin films of C60 molecules. One of the two chemical reactions can be selectively induced by controlling the sample bias voltage (V(s)); the application of negative and positive values of V(s) results in polymerization and depolymerization, respectively. The selectivity between the two chemical reactions becomes extremely high when the thickness of the C60 film increases to more than three molecular layers. We conclude that STM-induced negative and positive electrostatic ionization are responsible for the control of the polymerization and depolymerization, respectively.

  15. Quantum chemical modeling of enzymatic reactions: the case of 4-oxalocrotonate tautomerase.

    Science.gov (United States)

    Sevastik, Robin; Himo, Fahmi

    2007-12-01

    The reaction mechanism of 4-oxalocrotonate tautomerase (4-OT) is studied using the density functional theory method B3LYP. This enzyme catalyzes the isomerisation of unconjugated alpha-keto acids to their conjugated isomers. Two different quantum chemical models of the active site are devised and the potential energy curves for the reaction are computed. The calculations support the proposed reaction mechanism in which Pro-1 acts as a base to shuttle a proton from the C3 to the C5 position of the substrate. The first step (proton transfer from C3 to proline) is shown to be the rate-limiting step. The energy of the charge-separated intermediate (protonated proline-deprotonated substrate) is calculated to be quite low, in accordance with measured pKa values. The results of the two models are used to evaluate the methodology employed in modeling enzyme active sites using quantum chemical cluster models.

  16. Analysis of mechanism of complex chemical reaction taking radiation chemical purification of gases from impurities as an example

    International Nuclear Information System (INIS)

    Gerasimov, G.Ya.; Makarov, V.N.

    1997-01-01

    Algorithm of selecting optimal mechanism of complex chemical reaction, enabling to reduce the number of its stages, is suggested. Main steps of constructing the kinetic model of the medium are considered, taking the radiation chemical purification (using fast electron radiation) of gases (N 2 , CO 2 , O 2 and others) from impurities as an example. 17 refs., 3 figs., 2 tabs

  17. Measurement of thick target neutron yield from the reaction (p+181 Ta) with projectiles in the range of 6-20 MeV

    Science.gov (United States)

    Paul, Sabyasachi; Sahoo, G. S.; Tripathy, S. P.; Sharma, S. C.; Joshi, D. S.; Bandyopadhyay, T.

    2018-02-01

    181Ta is a commonly used backing material for many targets in nuclear reaction studies. When the target thickness is less than the range of bombarded projectiles, the interaction via Ta(p,n) reactions in the backing can be a significant source of background. In this study, the neutron spectral yields from the reaction of protons of different energies (between 6 to 20 MeV) with a thick Ta target were determined using CR-39 detectors. The results from this study can be used as a correction factor in such situations. The parameters of registered tracks in CR-39 were analysed using an in-house image analysing program autoTRAK_n and then to derive the associated dose values. The spectral yields obtained experimentally were compared with those obtained from the theoretical calculations. The neutron yield was found to increase with increase in projectile energy mainly due to the opening of reaction channels from (p, n) to (p, 3n).

  18. Analysis of energy cascade utilization in a chemically recuperated scramjet with indirect combustion

    International Nuclear Information System (INIS)

    Qin, Jiang; Cheng, Kunlin; Zhang, Silong; Zhang, Duo; Bao, Wen; Han, Jiecai

    2016-01-01

    The working process of scramjet with regenerative cooling, which was actually the chemical recuperation process, was analyzed in view of energy cascade utilization. The indirect combustion was realized through pyrolysis reaction of fuel. The relative yields of thermal exergy obtained by indirect combustion have been predicted both assuming an ideal pyrolysis reaction and using the experimental results of thermal pyrolysis of n-decane. The results showed that the influence mechanism of regenerative cooling improved the scramjet engine performance by the energy cascade utilization, and the combustion process was supposed to be designed with the cooling process together to utilize the chemical energy of fuel in a more effective way. A maximum value of 11% of the relative yield was obtained with the ideal pyrolysis reaction while a value less than 3% existed in the thermal pyrolysis experiments because of the domination of chemical kinetics rather than chemical thermodynamics in the real experiments. In spite of the difference between the ideal and the present experimental results, the indirect combustion was prospective to achieve a better energy cascade utilization in a chemically recuperated scramjet if the pyrolysis reaction was further optimized. The results in this paper were beneficial for the performance optimization of a regenerative cooling scramjet. - Highlights: • A new method of energy cascade utilization in a chemically recuperated scramjet. • 11% exergy loss is reduced by ideal pyrolysis reaction with indirect combustion. • Regenerative cooling with chemical recuperation can improve engine performance.

  19. KEMOD: A mixed chemical kinetic and equilibrium model of aqueous and solid phase geochemical reactions

    International Nuclear Information System (INIS)

    Yeh, G.T.; Iskra, G.A.

    1995-01-01

    This report presents the development of a mixed chemical Kinetic and Equilibrium MODel in which every chemical species can be treated either as a equilibrium-controlled or as a kinetically controlled reaction. The reaction processes include aqueous complexation, adsorption/desorption, ion exchange, precipitation/dissolution, oxidation/reduction, and acid/base reactions. Further development and modification of KEMOD can be made in: (1) inclusion of species switching solution algorithms, (2) incorporation of the effect of temperature and pressure on equilibrium and rate constants, and (3) extension to high ionic strength

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

    Science.gov (United States)

    Poros, Eszter; Kurin-Csörgei, Krisztina

    2014-01-01

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

  1. Fast screening of analytes for chemical reactions by reactive low-temperature plasma ionization mass spectrometry.

    Science.gov (United States)

    Zhang, Wei; Huang, Guangming

    2015-11-15

    Approaches for analyte screening have been used to aid in the fine-tuning of chemical reactions. Herein, we present a simple and straightforward analyte screening method for chemical reactions via reactive low-temperature plasma ionization mass spectrometry (reactive LTP-MS). Solution-phase reagents deposited on sample substrates were desorbed into the vapor phase by action of the LTP and by thermal desorption. Treated with LTP, both reagents reacted through a vapor phase ion/molecule reaction to generate the product. Finally, protonated reagents and products were identified by LTP-MS. Reaction products from imine formation reaction, Eschweiler-Clarke methylation and the Eberlin reaction were detected via reactive LTP-MS. Products from the imine formation reaction with reagents substituted with different functional groups (26 out of 28 trials) were successfully screened in a time of 30 s each. Besides, two short-lived reactive intermediates of Eschweiler-Clarke methylation were also detected. LTP in this study serves both as an ambient ionization source for analyte identification (including reagents, intermediates and products) and as a means to produce reagent ions to assist gas-phase ion/molecule reactions. The present reactive LTP-MS method enables fast screening for several analytes from several chemical reactions, which possesses good reagent compatibility and the potential to perform high-throughput analyte screening. In addition, with the detection of various reactive intermediates (intermediates I and II of Eschweiler-Clarke methylation), the present method would also contribute to revealing and elucidating reaction mechanisms. Copyright © 2015 John Wiley & Sons, Ltd.

  2. Generic Model-Based Tailor-Made Design and Analysis of Biphasic Reaction Systems

    DEFF Research Database (Denmark)

    Anantpinijwatna, Amata

    systems have a broad range of application, such as the manufacture of petroleum based chemicals, pharmaceuticals, and agro-bio products. Major considerations in the design and analysis of biphasic reaction systems are physical and chemical equilibria, kinetic mechanisms, and reaction rates. The primary...... contribution of this thesis is the development of a systematic modelling framework for the biphasic reaction system. The developed framework consists of three modules describing phase equilibria, reactions and mass transfer, and material balances of such processes. Correlative and predictive thermodynamic......Biphasic reaction systems are composed of immiscible aqueous and organic liquid phases where reactants, products, and catalysts are partitioned. These biphasic conditions point to novel synthesis paths, higher yields, and faster reactions, as well as facilitate product separation. The biphasic...

  3. 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...

  4. In Situ Monitoring of Chemical Reactions at a Solid-Water Interface by Femtosecond Acoustics.

    Science.gov (United States)

    Shen, Chih-Chiang; Weng, Meng-Yu; Sheu, Jinn-Kong; Yao, Yi-Ting; Sun, Chi-Kuang

    2017-11-02

    Chemical reactions at a solid-liquid interface are of fundamental importance. Interfacial chemical reactions occur not only at the very interface but also in the subsurface area, while existing monitoring techniques either provide limited spatial resolution or are applicable only for the outmost atomic layer. Here, with the aid of the time-domain analysis with femtosecond acoustics, we demonstrate a subatomic-level-resolution technique to longitudinally monitor chemical reactions at solid-water interfaces, capable of in situ monitoring even the subsurface area under atmospheric conditions. Our work was proven by monitoring the already-known anode oxidation process occurring during photoelectrochemical water splitting. Furthermore, whenever the oxide layer thickness equals an integer  number of the effective atomic layer thickness, the measured acoustic echo will show higher signal-to-noise ratios with reduced speckle noise, indicating the quantum-like behavior of this coherent-phonon-based technique.

  5. Driving Chemical Reactions in Plasmonic Nanogaps with Electrohydrodynamic Flow.

    Science.gov (United States)

    Thrift, William J; Nguyen, Cuong Q; Darvishzadeh-Varcheie, Mahsa; Zare, Siavash; Sharac, Nicholas; Sanderson, Robert N; Dupper, Torin J; Hochbaum, Allon I; Capolino, Filippo; Abdolhosseini Qomi, Mohammad Javad; Ragan, Regina

    2017-11-28

    Nanoparticles from colloidal solution-with controlled composition, size, and shape-serve as excellent building blocks for plasmonic devices and metasurfaces. However, understanding hierarchical driving forces affecting the geometry of oligomers and interparticle gap spacings is still needed to fabricate high-density architectures over large areas. Here, electrohydrodynamic (EHD) flow is used as a long-range driving force to enable carbodiimide cross-linking between nanospheres and produces oligomers exhibiting sub-nanometer gap spacing over mm 2 areas. Anhydride linkers between nanospheres are observed via surface-enhanced Raman scattering (SERS) spectroscopy. The anhydride linkers are cleavable via nucleophilic substitution and enable placement of nucleophilic molecules in electromagnetic hotspots. Atomistic simulations elucidate that the transient attractive force provided by EHD flow is needed to provide a sufficient residence time for anhydride cross-linking to overcome slow reaction kinetics. This synergistic analysis shows assembly involves an interplay between long-range driving forces increasing nanoparticle-nanoparticle interactions and probability that ligands are in proximity to overcome activation energy barriers associated with short-range chemical reactions. Absorption spectroscopy and electromagnetic full-wave simulations show that variations in nanogap spacing have a greater influence on optical response than variations in close-packed oligomer geometry. The EHD flow-anhydride cross-linking assembly method enables close-packed oligomers with uniform gap spacings that produce uniform SERS enhancement factors. These results demonstrate the efficacy of colloidal driving forces to selectively enable chemical reactions leading to future assembly platforms for large-area nanodevices.

  6. Kinetic calorimetry in the study of the mechanism of low-temperature chemical reactions

    Science.gov (United States)

    Barkalov, I. M.; Kiryukhin, D. P.

    Chemical reactions are always followed by a change in the reacting system enthalpy, hence, calorimetry as a method of enthalpy and heat capacity measuring is a universal and, sometimes, even the only possible way of studying chemical reaction kinetics. Throughout its long history, the calorimeter, having preserved the positions of the main method of thermodynamic studies, has conquered a new field of application: that of kinetic study of chemical reactions. The advantages and disadvantages of the kinetic calorimeter are now obvious. First, the advantages are: (1) the possibility of measuring the rate of a chemical reaction without any special requirements being imposed on the reaction medium (solid, viscous, multicomponent systems); (2) the high efficiency: a large volume of kinetic information in one experiment and a non-destructive character of changes; (3) the possibility of measuring directly in the field of ionizing radiation (γ-radiation, accelerated electrons) and light; and (4) recording of the chemical conversion directly at the time of its occurrence. The disadvantages of this method are: (1) the high inertia of standard calorimeter systems (τC⋍102-103S), which restricts the possibilities of studying fast processes; and (2) the complexity of the correct organization of the calorimeter experiment when the parameters of the process are changed (overheating in the sample, conversion of the process to explosive and auto wave regimens). One of the oldest and most universal methods of studying the mechanism of chemical reactions, calorimetry, is now passing through a period of turbulent development due to the advances in electronics and computerization. The wide variety of types of calorimeter set-ups and the large assortment of measurement schemes in the currently described methods complicate the experimental selection of the necessary instrument rather than facilitate it. The basic principles of the method, the types of calorimeters, and the measuring

  7. Fusion reaction yield in focused discharges with variable energy and plasma fine structure

    International Nuclear Information System (INIS)

    Bortolotti, A.; Brzosko, J.S.; Chiara, P. De; Kilic, H.; Mezzetti, F.; Nardi, V.; Powell, C.; Wang, J.

    1992-01-01

    The same linear correlation between the distribution parameters (ΔT and Max ΔV) of the radial current density J between electrodes and the fusion reaction yield per pulse, Y, in the plasma focus (PF) pinch was quantitatively determined from different PF machines. Contact prints of current-sheath fragments (CSF) ejected from the pinch are obtained from 2.5-MeV-D + ions. CSF's show the same submillimetric fine structure of the pinch. (author) 3 refs., 2 tabs

  8. Effect of chemical and mechanical weed control on cassava yield, soil quality and erosion under cassava cropping system

    Science.gov (United States)

    Islami, Titiek; Wisnubroto, Erwin; Utomo, Wani

    2016-04-01

    Three years field experiments were conducted to study the effect of chemical and mechanical weed control on soil quality and erosion under cassava cropping system. The experiment were conducted at University Brawijaya field experimental station, Jatikerto, Malang, Indonesia. The experiments were carried out from 2011 - 2014. The treatments consist of three cropping system (cassava mono culture; cassava + maize intercropping and cassava + peanut intercropping), and two weed control method (chemical and mechanical methods). The experimental result showed that the yield of cassava first year and second year did not influenced by weed control method and cropping system. However, the third year yield of cassava was influence by weed control method and cropping system. The cassava yield planted in cassava + maize intercropping system with chemical weed control methods was only 24 t/ha, which lower compared to other treatments, even with that of the same cropping system used mechanical weed control. The highest cassava yield in third year was obtained by cassava + peanuts cropping system with mechanical weed control method. After three years experiment, the soil of cassava monoculture system with chemical weed control method possessed the lowest soil organic matter, and soil aggregate stability. During three years of cropping soil erosion in chemical weed control method, especially on cassava monoculture, was higher compared to mechanical weed control method. The soil loss from chemical control method were 40 t/ha, 44 t/ha and 54 t/ha for the first, second and third year crop. The soil loss from mechanical weed control method for the same years was: 36 t/ha, 36 t/ha and 38 t/ha. Key words: herbicide, intercropping, soil organic matter, aggregate stability.

  9. Investigation of Yield and Yield Components of Canary Seed Forage (Phalaris canariensis L. in Response to Different Levels of Irrigation, Organic and Chemical Fertilizers and their integration

    Directory of Open Access Journals (Sweden)

    V Varnaseri Ghandali

    2016-12-01

    Full Text Available Introduction Canary seed (Phalaris canariensis L. is a forage plant from Poaceae family. This plant is drought tolerant. Canary seed is originally a native to Mediterranean region, which can be grown commercially in several parts of the word, especially in semi-arid conditions. Increasing growth of population and lack of ability of pastures to satisfy the food requirement of animal has led to more interest in cultivating forage plants. In this regard, Canary seed having properties such as high yield per unit area, high tillering power, very fast growth and appropriate nutritional value, is of considerable importance and its cultivation development especially in arid and semi-arid regions can be effective in providing part of the country forage needs. Optimum water requirement is considered as one the important factors to obtain a high growth and yield of the product. On the other hand, Iran is located in arid and semi-arid climate region of the world . Therefore, determination of appropriate amount of irrigation water can lead to the improvement of water use efficiency and preventing the water loss. In order to achieve a high yield and desirable quality in plants one of the important requirements in agricultural planning is the evaluation of different systems of plant feeding. By applying an appropriate method in soil productivity, in addition to protecting the environment, optimization of water usage, reduction of erosion and protection of biodiversity can be increased. Therefore, gradually replacing chemical fertilizers with biological and organic fertilizers will result in providing feed requirements of plants, improvement of physical, chemical and biological conditions of soil and reduction of adverse environmental effects resulting from application of chemical inputs. The aim of this research was to study the effects of deficit irrigation and fertilizer management based on sole chemical and organic fertilizers or their integrated

  10. A mathematical model for chemical reactions with actinide elements in the aqueous nitric acid solution: REACT

    International Nuclear Information System (INIS)

    Tachimori, Shoichi

    1990-02-01

    A mathematical model of chemical reactions with actinide elements: REACT code, was developed to simulate change of valency states of U, Pu and Np in the aqueous nitric acid solution. Twenty seven rate equations for the redox reactions involving some reductants, disproportionation reactions, and radiolytic growth and decay reaction of nitrous acid were programmed in the code . Eight numerical solution methods such as Porsing method to solve the rate equations were incorporated parallel as options depending on the characteristics of the reaction systems. The present report gives a description of the REACT code, e.g., chemical reactions and their rate equations, numerical solution methods, and some examples of the calculation results. A manual and a source file of the program was attached to the appendix. (author)

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

    Directory of Open Access Journals (Sweden)

    Qingkai Zhao

    2017-01-01

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

  12. Yield of Peas Treated with Compost and Chemical Fertilizer Using 15N Technique

    International Nuclear Information System (INIS)

    El-Degwy, S.M.A.

    2011-01-01

    A field experiment was carried out to evaluate the yield of peas treated with organic compost and mineral N fertilizer under sandy soil conditions. The obtained results showed that all the tested vegetative growth parameters, i.e. fresh and dry weight of leaves, root and pods of pea plants, were significantly increased with increasing the levels of mineral N fertilizer from 20 up to 50 kg N ha-1 either solely or in combination with compost. Nitrogen, phosphorus and potassium uptake by pea plants were ranked as follow: chemical N fertilize > compost + chemical N fertilize > compost. Organic additives either alone or in combination with chemical fertilizer had enhanced Ndff uptake by pods over aerial parts and roots while reversible trend was noticed with sole application of chemical fertilizer. Nitrogen derived from compost (Ndfc) and uptake by aerial parts followed by pods were enhanced by addition of organic plus chemical fertilizers comparable to sole addition of organic compost. In other term, chemical fertilizer had enhanced the portion of N derived from organic compost

  13. On the chemical reaction of matter with antimatter.

    Science.gov (United States)

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

    2007-06-04

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

  14. 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.

  15. 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.

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

    International Nuclear Information System (INIS)

    Muramatsu, Y.; Grush, M.; Callcott, T.A.

    1997-01-01

    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

  17. Investigation of the pp{yields}K{sup +}n{sigma}{sup +} reaction at the magnetic spectrometer ANKE-COSY

    Energy Technology Data Exchange (ETDEWEB)

    Valdau, Yury

    2009-10-20

    This thesis describes measurements of the pp{yields}K{sup +}n{sigma}{sup +} reaction near threshold. The work was largely motivated by the lack of data for {sigma}{sup +} hyperon production in pp collisions and, in particular, by recent measurements of pp{yields}K{sup +}n{sigma}{sup +} by the COSY11 collaboration. The experiment performed by this group using a neutron detector reported surprisingly high {sigma}{sup +} cross sections that are hard to reconcile with isospin considerations. The experiment discussed in the thesis has been performed at the ANKE-COSY facility at four close-to-threshold energies. It relies on the almost background-free K{sup +} identification using the delayed-veto technique and the fact that below the threshold for pp{yields}K{sup +}n{lambda}{pi}{sup +} there is no source of the K{sup +}{pi}{sup +} correlations other than the {sigma}{sup +}{yields}n{pi}{sup +} decay. Thus, the detection of K{sup +}{pi}{sup +} pairs allows one to identify the pp{yields}K{sup +}n{sigma}{sup +} reaction without the need for a neutron detector. The analysis of three simultaneously measured spectra has been carried out, searching for any signal from a possible high {sigma}{sup +} cross section. All the K{sup +} production channels allowed at the energy of the experiment contribute to the K{sup +} inclusive and K{sup +}p correlation spectra. In the K{sup +} inclusive distributions, signals from the different production channels are summed and can only be isolated using theoretical models. In the K{sup +}p correlation spectra, there are not only signals from the direct reaction protons but also protons from hyperon decays can be observed. Thus, the signal from {sigma}{sup +}{yields}p{pi}{sup 0} decay contributes to the K{sup +}p missing mass. The study of the K{sup +}{pi}{sup +} correlations allows one to identify the {sigma}{sup +} reaction channels and to estimate the total production cross section. This method has been successfully applied to existing ANKE

  18. Do high school chemistry examinations inhibit deeper level understanding of dynamic reversible chemical reactions?

    Science.gov (United States)

    Wheeldon, R.; Atkinson, R.; Dawes, A.; Levinson, R.

    2012-07-01

    Background and purpose : Chemistry examinations can favour the deployment of algorithmic procedures like Le Chatelier's Principle (LCP) rather than reasoning using chemical principles. This study investigated the explanatory resources which high school students use to answer equilibrium problems and whether the marks given for examination answers require students to use approaches beyond direct application of LCP. Sample : The questionnaire was administered to 162 students studying their first year of advanced chemistry (age 16/17) in three high achieving London high schools. Design and methods : The students' explanations of reversible chemical systems were inductively coded to identify the explanatory approaches used and interviews with 13 students were used to check for consistency. AS level examination questions on reversible reactions were analysed to identify the types of explanations sought and the students' performance in these examinations was compared to questionnaire answers. Results : 19% of students used a holistic explanatory approach: when the rates of forward and reverse reactions are correctly described, recognising their simultaneous and mutually dependent nature. 36% used a mirrored reactions approach when the connected nature of the forward and reverse reactions is identified, but not their mutual dependency. 42% failed to recognize the interdependence of forward and reverse reactions (reactions not connected approach). Only 4% of marks for AS examination questions on reversible chemical systems asked for responses which went beyond either direct application of LCP or recall of equilibrium knowledge. 37% of students attained an A grade in their AS national examinations. Conclusions : Examinations favour the application of LCP making it possible to obtain the highest grade with little understanding of reversible chemical systems beyond a direct application of this algorithm. Therefore students' understanding may be attenuated so that they are

  19. Computational studies of atmospherically-relevant chemical reactions in water clusters and on liquid water and ice surfaces.

    Science.gov (United States)

    Gerber, R Benny; Varner, Mychel E; Hammerich, Audrey D; Riikonen, Sampsa; Murdachaew, Garold; Shemesh, Dorit; Finlayson-Pitts, Barbara J

    2015-02-17

    isolated defects where it involves formation of H3O(+)-acid anion contact ion pairs. This behavior is found in simulations of a model of the ice quasi-liquid layer corresponding to large defect concentrations in crystalline ice. The results are in accord with experiments. (iv) Ionization of acids on wet quartz. A monolayer of water on hydroxylated silica is ordered even at room temperature, but the surface lattice constant differs significantly from that of crystalline ice. The ionization processes of HCl and H2SO4 are of high yield and occur in a few picoseconds. The results are in accord with experimental spectroscopy. (v) Photochemical reactions on water and ice. These simulations require excited state quantum chemical methods. The electronic absorption spectrum of methyl hydroperoxide adsorbed on a large ice cluster is strongly blue-shifted relative to the isolated molecule. The measured and calculated adsorption band low-frequency tails are in agreement. A simple model of photodynamics assumes prompt electronic relaxation of the excited peroxide due to the ice surface. SEMD simulations support this, with the important finding that the photochemistry takes place mainly on the ground state. In conclusion, dynamics simulations using quantum chemical potentials are a useful tool in atmospheric chemistry of water media, capable of comparison with experiment.

  20. Evaluation of Effect of Chemical and Organic Fertilizers on Growth Characteristics, Yield and Yield components of three Sesame Ecotypes (Sesamum indicum L.

    Directory of Open Access Journals (Sweden)

    M Goldani

    2014-07-01

    Full Text Available Using organic fertilizers is cause increase soil fertility, improving crop growth and production. For this purpose a greenhouse experiment was carried out in factorial arrangement based on a completely randomized design with three replications during 2011 year. First factor included: three sesame ecotype (MSC3, MSC6, MSC7 and second factor was 6 fertilizer treatments that included: Incorporation manure and chemical fertilizer (216 g manure and 1 gram chemical fertilizer NPK, Chemical fertilizer (2 g NPK, Vermicompost (192 g, Manure ( 228 g, Compost Sulfur granules (192 g per vase and Control (without any manure or fertilizer. Results indicated that different manure treatments had significant effect on morphological and yield components traits, as the most number and length branch per plant was obtained from incorporation manure and chemical fertilizer treatment. Appling incorporation manure and chemical fertilizer treatment had the most biomass in MSC3 ecotype that in comparison of control treatment was increased almost 73 percent. Consuming incorporation manure and chemical fertilizer treatment in MSC3 ecotype was also obtained the most capsule per plant (21.2, number seed per capsule (54.4, 100-seed weight (0.257 g and seed per plant with (1.95 g. The least seed weight per plant with 0.450 g was observed in MSC7 ecotype from application of control treatment. Response of three sesame ecotype (MSC3, MSC6, MSC7 to applied vermin-compost manure was similar; as the amount of seed weight per plant was increased more than 1 g per plant in all these ecotypes and in others fertilizer treatments was not observed this trend. There was significant positive correlation between seed weight per plant and number of capsule per plant (r=0.83**, height (r=0.68** and biomass (r=0.51**. The results showed that incorporation manure and chemical fertilizer was improved on growth and yield characteristics of sesame plant.

  1. EXPLORING THE DESIGN AND USE OF MOLECULAR ANIMATIONS THAT CONFLICT FOR UNDERSTANDING CHEMICAL REACTIONS

    Directory of Open Access Journals (Sweden)

    Resa M. Kelly

    Full Text Available Understanding chemical reactions conceptually involves recognizing characteristics of observable phenomena and envisioning how atoms, ions and molecules move and interact to cause the macroscopic changes. Our research focuses on the development of effective strategies for designing and presenting visualizations (videos and animations to assist students with making connections between macroscopic and molecular level behaviors of chemical reactions. Specifically, we study how students, who view videos of a redox reaction that exhibits obvious signs of macroscopic chemical change, can determine which molecular animation of a set of contrasting animations is best supported by its fit with experimental evidence. Herein we describe how we develop our videos and animations, and how students are learning from this animation task. Students who select inaccurate animation models are often enticed by a model that is easier to explain and fits with their understanding of reaction equations. We note that even though students indicate a preference for one animation over another, they often revise their drawn representations to fit with features from multiple animations. With the assistance of eye tracking research, we are gaining a better understanding of what students view and how they make sense of it.

  2. Chemical reaction on solid surface observed through isotope tracer technique

    International Nuclear Information System (INIS)

    Tanaka, Ken-ichi

    1983-01-01

    In order to know the role of atoms and ions on solid surfaces as the partners participating in elementary processes, the literatures related to the isomerization and hydrogen exchanging reaction of olefines, the hydrogenation of olefines, the metathesis reaction and homologation of olefines based on solid catalysts were reviewed. Various olefines, of which the hydrogen atoms were substituted with deuterium at desired positions, were reacted using various solid catalysts such as ZnO, K 2 CO 3 on C, MoS 2 (single crystal and powder) and molybdenum oxide (with various carriers), and the infra-red spectra of adsorbed olefines on catalysts, the isotope composition of reaction products and the production rate of the reaction products were measured. From the results, the bonding mode of reactant with the atoms and ions on solid surfaces, and the mechanism of the elementary process were considered. The author emphasized that the mechanism of the chemical reaction on solid surfaces and the role of active points or catalysts can be made clear to the considerable extent by combining isotopes suitably. (Yoshitake, I.)

  3. Boosting Chemical Stability, Catalytic Activity, and Enantioselectivity of Metal-Organic Frameworks for Batch and Flow Reactions.

    Science.gov (United States)

    Chen, Xu; Jiang, Hong; Hou, Bang; Gong, Wei; Liu, Yan; Cui, Yong

    2017-09-27

    A key challenge in heterogeneous catalysis is the design and synthesis of heterogeneous catalysts featuring high catalytic activity, selectivity, and recyclability. Here we demonstrate that high-performance heterogeneous asymmetric catalysts can be engineered from a metal-organic framework (MOF) platform by using a ligand design strategy. Three porous chiral MOFs with the framework formula [Mn 2 L(H 2 O) 2 ] are prepared from enantiopure phosphono-carboxylate ligands of 1,1'-biphenol that are functionalized with 3,5-bis(trifluoromethyl)-, bismethyl-, and bisfluoro-phenyl substituents at the 3,3'-position. For the first time, we show that not only chemical stability but also catalytic activity and stereoselectivity of the MOFs can be tuned by modifying the ligand structures. Particularly, the MOF incorporated with -CF 3 groups on the pore walls exhibits enhanced tolerance to water, weak acid, and base compared with the MOFs with -F and -Me groups. Under both batch and flow reaction systems, the CF 3 -containing MOF demonstrated excellent reactivity, selectivity, and recyclability, affording high yields and enantioselectivities for alkylations of indoles and pyrrole with a range of ketoesters or nitroalkenes. In contrast, the corresponding homogeneous catalysts gave low enantioselectivity in catalyzing the tested reactions.

  4. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-11-01

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

  6. 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.

  7. The influence of the "cage effect" on the mechanism of reversible bimolecular multistage chemical reactions in solutions.

    Science.gov (United States)

    Doktorov, Alexander B

    2015-08-21

    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.

  8. Influence of urea application on growth, yield and mineral uptake in ...

    African Journals Online (AJOL)

    A pot experiment was conducted in a wire netting green house in order to assess the beneficial effect of urea on corn cultivars (C-20 and C-79) differing in yield production. Corn plants were grown in loam soil with alkaline in reaction. Application of varying urea levels did not change the physico-chemical properties of soil.

  9. Application of radioanalytical techniques in the study of the products of heavy-ion reactions

    International Nuclear Information System (INIS)

    Hoffman, D.C.

    1989-01-01

    The use of heavy ions to induce nuclear reactions was reported as early as 1950. Since then it has been one of the most active areas of nuclear research. Intense beams of ions as heavy as uranium with energies high enough to overcome the Coulomb barriers of even the heaviest elements are available. The large variety of possible reactions gives rise to a multitude of products, which have been studied by many chemical and physical techniques. Chemical techniques have been of special value for the separation and unequivocal identification of low-yield species from the plethora of other nuclides present. Heavy-ion reactions have been essential for the production of the transmendelevium elements and a host of new isotopes. The systematics of compound nucleus reactions, transfer reactions and deeply inelastic reactions have been elucidated using chemical techniques. The variety of chemical procedures and techniques which have been developed for the study of heavy-ion reactions and their products has been examined. The determination of the chemical properties of the transmendelevium elements, which are very short-lived and can only be produced an ''atom at a time'' via heavy-ion reactions, is discussed. (author)

  10. Rare gas isotope yields in bremsstrahlung-induced nuclear reactions of 41K, 87Rb, 127I, 133Cs, and 139La

    International Nuclear Information System (INIS)

    Oura, Y.; Yazawa, A.; Sarkar, S.R.; Sakamoto, K.; Shibata, S.; Fujiwara, I.; Furukawa, M.

    1994-05-01

    Radiochemical yield measurements have been reported for 41 K(γ, π + ) 41 Ar, 87 Rb(γ, π + ) 87 Kr, 133 Cs(γ, π + ) 133m,133g Xe, 127 I(γ, π - xn) 127-x Xe (x=0,2,4,5, and 6), 133 Cs(γ, pxn) 132-x Xe (x=1,3,5,7,9,10, and 11), and 139 La(γ, 3pxn) 136- xXe (x=7,9,11,13,14, and 15) at bremsstrahlung end-point energies(E 0 ) of 50-1200 MeV. For photopion reactions it has been confirmed that the both yields of (γ, π - ) and (γ, π + ) reactions are independent of target mass (A t ) and the yield ratios of (γ, π - ) to (γ, π + ) reactions are about 5 over the studied ranges of E 0 and A t . The profile of 127 I(γ, π - xn) yields as a function of x is similar to that of 133 Cs but quite different from that of 51 V when compared at the same E 0 , suggesting a strong A t dependence. It is also found that the photospallogenic Xe isotope yields from 133 Cs and 139 La are consistent with the reported mass yield pattems of the other radionuclides produced from the same targets. These results are discussed by referring to the previous literature values and to a cascade-evaporation calculation based on the PICA code by Gabriel and Alsmiller. (author)

  11. Chemical methods and techniques to monitor early Maillard reaction in milk products; A review.

    Science.gov (United States)

    Aalaei, Kataneh; Rayner, Marilyn; Sjöholm, Ingegerd

    2018-01-23

    Maillard reaction is an extensively studied, yet unresolved chemical reaction that occurs as a result of application of the heat and during the storage of foods. The formation of advanced glycation end products (AGEs) has been the focus of several investigations recently. These molecules which are formed at the advanced stage of the Maillard reaction, are suspected to be involved in autoimmune diseases in humans. Therefore, understanding to which extent this reaction occurs in foods, is of vital significance. Because of their composition, milk products are ideal media for this reaction, especially when application of heat and prolonged storage are considered. Thus, in this work several chemical approaches to monitor this reaction in an early stage are reviewed. This is mostly done regarding available lysine blockage which takes place in the very beginning of the reaction. The most popular methods and their applications to various products are reviewed. The methods including their modifications are described in detail and their findings are discussed. The present paper provides an insight into the history of the most frequently-used methods and provides an overview on the indicators of the Maillard reaction in the early stage with its focus on milk products and especially milk powders.

  12. CHEMSIMUL - A program package for numerical simulation of chemical reaction systems

    International Nuclear Information System (INIS)

    Lang Rasmussen, O.; Bjergbakke, E.

    1984-01-01

    A description is given of a program package, CHEMSIMUL, for numerical simulation of chemical reaction systems. The main components in the package are a translator of chemical equations to differential equations, a balance equation program, a differential equation solver, EPISODE, and an input/output program. The performance of the program is demonstrated by four examples. A manual for the input file and the complete program text with comments are given in Appendices I and II. (author)

  13. Chemical aspects of radiation damage processes: radiolysis

    International Nuclear Information System (INIS)

    Asmus, K.D.

    1975-01-01

    The formation of primary species and radiation chemical yields are discussed. In a section on chemical scavenging of primary species the author considers scavenging kinetics and competition reactions and gives a brief outline of some experimental methods. The radiation chemistry of aqueous solutions is discussed as an example for polar solvents. Cyclohexane is used as an example for non-polar solvents. The importance of excited states and energy transfer is considered. Reactions in the solid state are discussed and results on linear energy transfer and average ion pair formation for various kinds of radiation are surveyed. (B.R.H.)

  14. Yields of the rare-earth neutron-deficient isotopes in the reactions of Mo isotopes with 40Ca ions

    International Nuclear Information System (INIS)

    Adam, J.; Chaloun, P.; Gangrskij, Yu.P.

    1999-01-01

    The results of the joint Russian-Chinese experiment on the measurements of the reaction cross sections of the rare-earth neutron-deficient isotopes production and the study of their decay scheme are presented. The studied nuclides were obtained in the reactions 92 Mo + 40 Ca and 97 Mo + 40 Ca on the 4-meter cyclotron of the Flerov Laboratory of Nuclear Reactions, JINR. The recoil nuclei were stopped in the inert gas and transported by the gas flow to the detectors. The single and coincidence spectra of γ-, x-rays and delayed protons were measured. The enhanced yield of the reactions with the charge particle evaporation was observed

  15. Computer Controlled Chemical Micro-Reactor

    International Nuclear Information System (INIS)

    Mechtilde, Schaefer; Eduard, Stach; Adreas, Foitzik

    2006-01-01

    Chemical reactions or chemical equilibria can be influenced and controlled by several parameters. The ratio of two liquid ingredients, the so called reactants or educts, plays an important role in determining the end product and its yield. The reactants must be weighed and accordingly mixed with the conventional batch mode. If the reaction is done in a microreactor or in several parallel working micro-reactors, units for allotting the educts in appropriate quantities are required. In this report we present a novel micro-reactor that allows the constant monitoring of the chemical reaction via Raman spectroscopy. Such monitoring enables an appropriate feedback on the steering parameters for the PC controlled micro-pumps for the appropriate educt flow rate of both liquids to get optimised ratios of ingredients at an optimised total flow rate. The micro-reactors are the core pieces of the design and are easily removable and can therefore be changed at any time to adapt the requirements of the chemical reaction. One type of reactor consists of a stainless steel base containing small scale milled channels covered with anodically bonded Pyrex glass. Another type of reactor has a base of anisotropically etched silicon, and is also covered with anodically bonded Pyrex glass. The glass window allows visual observation of the initial phase interface of the two educts in the reaction channels by optical microscopy and does not affect, in contrast to infrared spectroscopy, the Raman spectroscopic signal for detection of the reaction kinetics. On the basis of a test reaction, we present non-invasive and spatially highly resolved in-situ reaction analysis using Raman spectroscopy measured along the reaction channel at different locations

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

    International Nuclear Information System (INIS)

    Luo, Y.; Mora-Hernández, J.M.; Estudillo-Wong, L.A.; Arce-Estrada, E.M.; Alonso-Vante, N.

    2015-01-01

    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

  17. Rate Constants and H-Atom Product Yields for the Reactions of O(1D) Atoms with Ethane and Acetylene from 50 to 296 K.

    Science.gov (United States)

    Nunez-Reyes, Dianailys; Hickson, Kevin M

    2018-05-01

    The gas phase reactions of atomic oxygen in its first excited state with ethane and acetylene have been investigated in a continuous supersonic flow reactor over the temperature range 50 K to 296 K. O(1D) atoms were produced by pulsed laser photolysis of ozone at 266 nm. Two different types of experiments, kinetics measurements and H-atom product yield determinations, were performed by detecting O(1D) atoms and H(2S) atoms respectively by vacuum ultraviolet laser induced fluorescence. The measured rate constants are in agreement with previous work at room temperature and little or no temperature dependence was observed as the temperature is decreased to 50 K. H-atoms yields were found to be independent of temperature for the reaction of O(1D) with ethane. These product yields are discussed in the context of earlier dynamics measurements at higher temperature. Due to the influence of secondary reactions, no H-atom yields could be obtained for the reaction of O(1D) with acetylene.

  18. A transformation theory of stochastic evolution in Red Moon methodology to time evolution of chemical reaction process in the full atomistic system.

    Science.gov (United States)

    Suzuki, Yuichi; Nagaoka, Masataka

    2017-05-28

    Atomistic information of a whole chemical reaction system, e.g., instantaneous microscopic molecular structures and orientations, offers important and deeper insight into clearly understanding unknown chemical phenomena. In accordance with the progress of a number of simultaneous chemical reactions, the Red Moon method (a hybrid Monte Carlo/molecular dynamics reaction method) is capable of simulating atomistically the chemical reaction process from an initial state to the final one of complex chemical reaction systems. In the present study, we have proposed a transformation theory to interpret the chemical reaction process of the Red Moon methodology as the time evolution process in harmony with the chemical kinetics. For the demonstration of the theory, we have chosen the gas reaction system in which the reversible second-order reaction H 2 + I 2  ⇌ 2HI occurs. First, the chemical reaction process was simulated from the initial configurational arrangement containing a number of H 2 and I 2 molecules, each at 300 K, 500 K, and 700 K. To reproduce the chemical equilibrium for the system, the collision frequencies for the reactions were taken into consideration in the theoretical treatment. As a result, the calculated equilibrium concentrations [H 2 ] eq and equilibrium constants K eq at all the temperatures were in good agreement with their corresponding experimental values. Further, we applied the theoretical treatment for the time transformation to the system and have shown that the calculated half-life τ's of [H 2 ] reproduce very well the analytical ones at all the temperatures. It is, therefore, concluded that the application of the present theoretical treatment with the Red Moon method makes it possible to analyze reasonably the time evolution of complex chemical reaction systems to chemical equilibrium at the atomistic level.

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

    Science.gov (United States)

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

    2006-09-01

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

  20. Development of a quantum chemical molecular dynamics tribochemical simulator and its application to tribochemical reaction dynamics of lubricant additives

    International Nuclear Information System (INIS)

    Onodera, T; Tsuboi, H; Hatakeyama, N; Endou, A; Miyamoto, A; Miura, R; Takaba, H; Suzuki, A; Kubo, M

    2010-01-01

    Tribology at the atomistic and molecular levels has been theoretically studied by a classical molecular dynamics (MD) method. However, this method inherently cannot simulate the tribochemical reaction dynamics because it does not consider the electrons in nature. Although the first-principles based MD method has recently been used for understanding the chemical reaction dynamics of several molecules in the tribology field, the method cannot simulate the tribochemical reaction dynamics of a large complex system including solid surfaces and interfaces due to its huge computation costs. On the other hand, we have developed a quantum chemical MD tribochemical simulator on the basis of a hybrid tight-binding quantum chemical/classical MD method. In the simulator, the central part of the chemical reaction dynamics is calculated by the tight-binding quantum chemical MD method, and the remaining part is calculated by the classical MD method. Therefore, the developed tribochemical simulator realizes the study on tribochemical reaction dynamics of a large complex system, which cannot be treated by using the conventional classical MD or the first-principles MD methods. In this paper, we review our developed quantum chemical MD tribochemical simulator and its application to the tribochemical reaction dynamics of a few lubricant additives

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

    NARCIS (Netherlands)

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

    2013-01-01

    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

  2. The yields of 1P and 1D resonances in the He(e,2e)He+ reaction

    International Nuclear Information System (INIS)

    Lhagva, O.; Badamdamdin, R.; Strakhova, S.I.; Hehnmedeh, L.

    1991-01-01

    In the first Born approximation the dependence of the yields of the 1 P and 1 D resonances in the He(e,2e)He + reaction on the momentum transfer in the recoil peak region at incident energies E 0 =1000 eV is studied. It is shown that in a certain range of the ejection angle and for the large momentum transfer the yield of the 1 D resonance dominates over the 1 P resonance one. 12 refs.; 4 figs

  3. Effect of Non-chemical Procedures of Weed Management on Growth Characteristics and Yield of Cumin (Cuminnum cyminum L.

    Directory of Open Access Journals (Sweden)

    Surur Khorramdel

    2018-02-01

    Full Text Available Introduction Medicinal and aromatic plants are major crops of domestic and industrial interest. The essential oil yield, seed yield and biomass of medicinal and aromatic plants are seriously affected by interspecific competition, meaning proper weed management becomes crucial. Competition with weeds is detrimental for medicinal and aromatic plants production for two main reasons. The first reason is that, in acting as an important stress factor, the interference of weeds is supposed to generate variations in photosynthesis rate and direction, pushing plants to allocate more carbon to roots (competition for nutrients or water or shoots (competition for light. These plants are increasingly organically grown to improve profitability. However, the presence of weeds may lead to a decline in both yield and quality. Therefore, nonchemical methods of weed management are needed. More attention has been paid worldwide about the technical means for weeding, generally addressed to a removal of weeds as complete as possible, and sometimes to the effects of weeds on medicinal and aromatic plants yields and quality.Cumin (Cuminum cyminum L. is an herbaceous and annual plant belonging to Apiaceae family which is planted in arid and semi-arid regions of Iran as medicinal plant. About 26% of the total area under cultivation of medicinal plants in Iran is allocated to cumin cultivation. This paper studied the methods of non-chemical weed control on yield components and quantitative and qualitative yield of cumin. Materials and Methods In order to study weed management methods, an experiment was conducted based on a randomized complete block design with nine treatments and three replications at the Agricultural Research Station, Ferdowsi University of Mashhad during growing season 2012-2013. Treatments included tillage at night, false seed bed, three cover crops such as hairy vetch, chuckling vetch and fenugreek, crop residues of sunflower, barley and garlic and

  4. Biochemical methane potential, biodegradability, alkali treatment and influence of chemical composition on methane yield of yard wastes.

    Science.gov (United States)

    Gunaseelan, Victor Nallathambi

    2016-03-01

    In this study, the biochemical CH4 potential, rate, biodegradability, NaOH treatment and the influence of chemical composition on CH4 yield of yard wastes generated from seven trees were examined. All the plant parts were sampled for their chemical composition and subjected to the biochemical CH4 potential assay. The component parts exhibited significant variation in biochemical CH4 potential, which was reflected in their ultimate CH4 yields that ranged from 109 to 382 ml g(-1) volatile solids added and their rate constants that ranged from 0.042 to 0.173 d(-1). The biodegradability of the yard wastes ranged from 0.26 to 0.86. Variation in the biochemical CH4 potential of the yard wastes could be attributed to variation in the chemical composition of the different fractions. In the Thespesia yellow withered leaf, Tamarindus fruit pericarp and Albizia pod husk, NaOH treatment enhanced the ultimate CH4 yields by 17%, 77% and 63%, respectively, and biodegradability by 15%, 77% and 61%, respectively, compared with the untreated samples. The effectiveness of NaOH treatment varied for different yard wastes, depending on the amounts of acid detergent fibre content. Gliricidia petals, Prosopis leaf, inflorescence and immature pod, Tamarindus seeds, Albizia seeds, Cassia seeds and Delonix seeds exhibited CH4 yields higher than 300 ml g(-1) volatile solids added. Multiple linear regression models for predicting the ultimate CH4 yield and biodegradability of yard wastes were designed from the results of this work. © The Author(s) 2016.

  5. 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…

  6. Prediction of biomass-generated syngas using extents of major reactions in a continuous stirred-tank reactor

    International Nuclear Information System (INIS)

    Sharma, Ashokkumar M.; Kumar, Ajay; Madihally, Sundararajan; Whiteley, James R.; Huhnke, Raymond L.

    2014-01-01

    Syngas, the main gasification product, is a well-known intermediate for making fuels, chemicals and power. The objective of this study was to develop and validate reaction kinetics-based gasification model using extents of major reactions in a CSTR (continuous stirred-tank reactor) to predict syngas composition and yield. The model was studied by varying biomass and air flowrates from 2.9 to 4.2 dry kg/h and 4.5–10 kg/h, respectively, with temperature from 801 to 907 °C. Results showed significant improvement in the predictions of syngas composition and yield, and gasification efficiency. The extents of gasification reactions indicated that at ERs (equivalence ratios) below 0.32, the water gas reaction contributed the most to the syngas CO and H 2 yields. The char oxidation reaction was also the dominating reaction contributing to CO yield at ERs below 0.40. At ERs above 0.29, the Boudouard and methane oxidation reactions were the most dominating reactions contributing to the CO yield while the water gas shift reaction contributed to the H 2 yield. The developed model corrected one of the key underlying assumptions that biomass decomposes into elemental forms (C, H, O, N and S), however, gasification temperature, carbon conversion efficiency and tar yield were assumed to be given. - Highlights: • Modeled gasification using extent of reaction in a continuous stirred-tank reactor. • Extents of major reactions during gasification were predicted. • Model greatly improved prediction of biomass-generated gas composition and yield. • Water gas, Boudouard and methane oxidation reactions contributed to CO production. • Water gas and water gas shift were the dominating reactions for H 2 production

  7. 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.

  8. The rate coefficient for the reaction NO2 + NO3 yielding NO + NO2 + O2 from 273 to 313 K

    Science.gov (United States)

    Cantrell, Chris A.; Shetter, Richard E.; Mcdaniel, Anthony H.; Calvert, Jack G.

    1990-01-01

    The ratio of rate constants for the reaction NO3 + NO yielding 2 NO2 (k3) and the reaction NO2 + NO3 yielding NO + NO2 + O2 (k4) were determined by measuring of NO and NO2 concentrations of NO and NO2 in an N2O5/NO2/N2 mixture over the temperature range 273-313 K. The measured ratio was found to be expressed by the equation k3/k4 = 387 exp(-1375/T). The results are consistent with those of Hammer et al. (1986).

  9. Exploring chemical reaction mechanisms through harmonic Fourier beads path optimization.

    Science.gov (United States)

    Khavrutskii, Ilja V; Smith, Jason B; Wallqvist, Anders

    2013-10-28

    Here, we apply the harmonic Fourier beads (HFB) path optimization method to study chemical reactions involving covalent bond breaking and forming on quantum mechanical (QM) and hybrid QM∕molecular mechanical (QM∕MM) potential energy surfaces. To improve efficiency of the path optimization on such computationally demanding potentials, we combined HFB with conjugate gradient (CG) optimization. The combined CG-HFB method was used to study two biologically relevant reactions, namely, L- to D-alanine amino acid inversion and alcohol acylation by amides. The optimized paths revealed several unexpected reaction steps in the gas phase. For example, on the B3LYP∕6-31G(d,p) potential, we found that alanine inversion proceeded via previously unknown intermediates, 2-iminopropane-1,1-diol and 3-amino-3-methyloxiran-2-ol. The CG-HFB method accurately located transition states, aiding in the interpretation of complex reaction mechanisms. Thus, on the B3LYP∕6-31G(d,p) potential, the gas phase activation barriers for the inversion and acylation reactions were 50.5 and 39.9 kcal∕mol, respectively. These barriers determine the spontaneous loss of amino acid chirality and cleavage of peptide bonds in proteins. We conclude that the combined CG-HFB method further advances QM and QM∕MM studies of reaction mechanisms.

  10. Laser-enhanced chemical reactions and the liquid state. II. Possible applications to nuclear fuel reprocessing

    International Nuclear Information System (INIS)

    DePoorter, G.L.; Rofer-DePoorter, C.K.

    1976-01-01

    Laser photochemistry is surveyed as a possible improvement upon the Purex process for reprocessing spent nuclear fuel. Most of the components of spent nuclear fuel are photochemically active, and lasers can be used to selectively excite individual chemical species. The great variety of chemical species present and the degree of separation that must be achieved present difficulties in reprocessing. Lasers may be able to improve the necessary separations by photochemical reaction or effects on rates and equilibria of reactions

  11. Photo- and radiation chemical studies of intermediates involved in excited-state electron-transfer reactions

    International Nuclear Information System (INIS)

    Hoffman, M.Z.

    1985-01-01

    Excited-state inter- and intramolecular electron-transfer reactions lie at the heart of the most photochemical solar energy conversion schemes. The authors research, which has utilized the techniques of continuous and pulsed photolysis and radiolysis, has focused on three general aspects of these reactions involving transition metal coordination complexes and electron donor-acceptor complexes: i) the effect of solution medium on the properties and quenching of the excited states; ii) the control of the quantum yields of formation of redox products; iii) the mechanism by which reduced species interact with water to yield H 2 homogeneously and heterogeneously. EDTA is among the most popular sacrificial electron donors used in model systems. Its role is to scavenge the oxidized form of the photosensitizer in order to prevent its rapid reaction with the reduced form of the electron relay species that results from the electron-transfer quenching of the excited photosensitizer. In systems involving MV 2+ , the radicals resulting from the oxidation of EDTA can eventually lead to the generation of a second equivalent of MV + ; the reducing agent is believed to be a radical localized on the carbon atom alpha to the carboxylate group. The reaction of radiolytically-generated OH/H with EDTA produces this radical directly via H-abstraction or indirectly via deprotonation of the carbon atom adjacent to the nitrogen radical site in the oxidized amine moiety; it reduces MV 2+ with rate constants of 2.8 x 10 9 , 7.6 x 10 9 , and 8.5 x 10 6 M -1 s -1 at pH 12.5, 8.3, and 4.7, respectively. Degradative decarboxylation of EDTA-radicals and their back electron-transfer reactions are enhanced in acidic solution causing the yield of MV + to be severely diminished

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

    Science.gov (United States)

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

    2012-08-01

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

  13. Processing yield and chemical composition of rainbow trout (Oncorhynchus mykiss with regard to body weight

    Directory of Open Access Journals (Sweden)

    Maria Luiza Rodrigues de Souza

    2015-05-01

    Full Text Available The influence of weight (W category of the rainbow trout on processing yield and chemical composition of the entire eviscerated fish and fish fillet was analyzed. A completely randomized design was employed for processing variables (W1 = 300 to 370 g and W2 = 371 to 440 coupled to a 2 x 2 factorial scheme for the chemical composition (W1 and W2 and forms of presentation: fillet and whole eviscerated fish. W1 showed higher yield for entire eviscerated fish (83.00% and head (13.27%, but a lower yield for the viscera (17.00%, when compared to W2. We did not affect abdominal muscle yield, fillet with or without skin, skin percentage and residues. There were significant differences between W for moisture (W1 = 72.30% and W2 = 71.15% and lipids (CP1 = 7.96% and CP2 = 9.04% rates. Fillet moisture contents (73.74% and crude protein (19.05% were higher (p < 0.01 than for entire eviscerated fish (69.71% and 17.81%, respectively. Ash (2.15% and lipid (10.48% rates were higher (p < 0.01 for entire fish when compared to those of fillets (1.16% and 6.52%, respectively. The slaughter of fish weighing between 300 and 370 g and their fillets are more adequate for the market.

  14. Chemical Reaction Engineering Applications in Non-traditional Technologies. A Textbook Supplement.

    Science.gov (United States)

    Savage, Phillip E.; Blaine, Steven

    1991-01-01

    A set of educational materials that have been developed which deal with chemical engineering applications in emerging technologies is described. The organization and the content of the supplemental textbook materials and how they can be integrated into an undergraduate reaction engineering course are discussed. (KR)

  15. Chemical equilibrium and reaction modeling of arsenic and selenium in soils

    Science.gov (United States)

    The chemical processes and soil factors that affect the concentrations of As and Se in soil solution were discussed. Both elements occur in two redox states differing in toxicity and reactivity. Methylation and volatilization reactions occur in soils and can act as detoxification pathways. Precip...

  16. 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…

  17. Magnetic isotope effect and theory of atomic orbital hybridization to predict a mechanism of chemical exchange reactions.

    Science.gov (United States)

    Epov, Vladimir N

    2011-08-07

    A novel approach is suggested to investigate the mechanisms of chemical complexation reactions based on the results of Fujii with co-workers; they have experimentally observed that several metals and metalloids demonstrate mass-independent isotope fractionation during the reactions with the DC18C6 crown ether using solvent-solvent extraction. In this manuscript, the isotope fractionation caused by the magnetic isotope effect is used to understand the mechanisms of chemical exchange reactions. Due to the rule that reactions are allowed for certain electron spin states, and forbidden for others, magnetic isotopes show chemical anomalies during these reactions. Mass-independent fractionation is suggested to take place due to the hyperfine interaction of the nuclear spin with the electron spin of the intermediate product. Moreover, the sign of the mass-independent fractionation is found to be dependent on the element and its species, which is also explained by the magnetic isotope effect. For example, highly negative mass-independent isotope fractionation of magnetic isotopes was observed for reactions of DC18C6 with SnCl(2) species and with several Ru(III) chloro-species, and highly positive for reactions of this ether with TeCl(6)(2-), and with several Cd(II) and Pd(II) species. The atomic radius of an element is also a critical parameter for the reaction with crown ether, particularly the element ions with [Kr]4d(n)5s(m) electron shell fits the best with the DC18C6 crown ring. It is demonstrated that the magnetic isotope effect in combination with the theory of orbital hybridization can help to understand the mechanism of complexation reactions. The suggested approach is also applied to explain previously published mass-independent fractionation of Hg isotopes in other types of chemical exchange reactions. This journal is © the Owner Societies 2011

  18. A Study of Interactions between Mixing and Chemical Reaction Using the Rate-Controlled Constrained-Equilibrium Method

    Science.gov (United States)

    Hadi, Fatemeh; Janbozorgi, Mohammad; Sheikhi, M. Reza H.; Metghalchi, Hameed

    2016-10-01

    The rate-controlled constrained-equilibrium (RCCE) method is employed to study the interactions between mixing and chemical reaction. Considering that mixing can influence the RCCE state, the key objective is to assess the accuracy and numerical performance of the method in simulations involving both reaction and mixing. The RCCE formulation includes rate equations for constraint potentials, density and temperature, which allows taking account of mixing alongside chemical reaction without splitting. The RCCE is a dimension reduction method for chemical kinetics based on thermodynamics laws. It describes the time evolution of reacting systems using a series of constrained-equilibrium states determined by RCCE constraints. The full chemical composition at each state is obtained by maximizing the entropy subject to the instantaneous values of the constraints. The RCCE is applied to a spatially homogeneous constant pressure partially stirred reactor (PaSR) involving methane combustion in oxygen. Simulations are carried out over a wide range of initial temperatures and equivalence ratios. The chemical kinetics, comprised of 29 species and 133 reaction steps, is represented by 12 RCCE constraints. The RCCE predictions are compared with those obtained by direct integration of the same kinetics, termed detailed kinetics model (DKM). The RCCE shows accurate prediction of combustion in PaSR with different mixing intensities. The method also demonstrates reduced numerical stiffness and overall computational cost compared to DKM.

  19. Automated Discovery of New Chemical Reactions and Accurate Calculation of Their Rates

    Science.gov (United States)

    2015-06-02

    chemistry calculations are run. The product matrices P are obtained and converted to block structure by simple linear algebra operations...in the system, i.e. 0 , =∑ ji ija Usually in elementary reactions |aij|ɛ since the change by two implies a significant chemical process, for...instance, formation or rupture of a double bond in a single elementary step. After applying the reaction matrix A, the product matrix P can then be

  20. Isotope effects in gas-phase chemical reactions and photodissociation processes: Overview

    International Nuclear Information System (INIS)

    Kaye, J.A.

    1992-01-01

    The origins of isotope effects in equilibrium and non-equilibrium chemical processes are reviewed. In non-equilibrium processes, attention is given to isotope effects in simple bimolecular reactions, symmetry-related reactions, and photodissociation processes. Recent examples of isotope effects in these areas are reviewed. Some indication of other scientific areas for which measurements and/or calculations of isotope effects are used is also given. Examples presented focus on neutral molecule chemistry and in many cases complement examples considered in greater detail in the other chapters of this volume

  1. Nuclear reactions excited by recoil protons on a nuclear reactor

    International Nuclear Information System (INIS)

    Mukhammedov, S.; Khaydarov, A.; Barsukova, E.G.

    2006-01-01

    The nuclear reactions excited by recoil protons and of the detection possibility of the various chemical elements with the use of these secondary nucleus reactions were investigated. The recoil protons are produced on a nuclear reactor in the result of (n, p) inelastic and elastic scattering interaction of fast neutrons with nuclei of hydrogen. It is well known that the share of fast neutrons in energetic spectrum of reactor's neutrons in comparison with the share of thermal neutrons is small. . Consequently, the share of recoil protons produced in the result of fast neutron interaction with nuclei of light elements, capable to cause the nuclear reactions, is also small, des, due to Coulomb barrier of nuclei the recoil protons can cause the nuclear reactions only on nuclei of light and some middle elements. Our studies show that observable yields have radio nuclides excited in the result of nuclear reactions on Li, B, O, V and Cu. Our experimental results have demonstrated that the proton activation analysis based on the application of secondary nuclear reactions is useful technique to determine large contents of various light and medium chemical elements. Detection limits for studied chemical elements are estimated better than 10 ppm

  2. Precise measurements of the thick target neutron yields of the 7Li(p,n) reaction

    International Nuclear Information System (INIS)

    Matysiak, W.; Prestwich, W.V.; Byun, S.H.

    2011-01-01

    Thick target neutron yield of the 7 Li(p,n) 7 Be reaction was measured in the proton energy range from 1.95 to 2.3 MeV by determining induced activity of the 7 Be. A HPGe detector was used to detect the 478 keV gamma-rays emitted through 7 Be decay. A series of irradiations with nominal proton energies of 1.95, 2.0, 2.1, 2.2, and 2.3 MeV were carried out. In an independent experiment, raw neutron spectra were collected by a 3 He ion chamber for the same series of proton energies. From the raw neutron spectra, it was noted, that the effective proton energies were lower than the nominal by 50-58 keV. After corrections for the proton energy offsets were applied, the measured neutron yields matched the analytically calculated yields within 20%. Long term stability of neutron yield was tested at two nominal proton energies, 2.1 and 1.95 MeV over an experimental period of one year. The results show that the yield at 2.1 MeV was stable within rmse variation coefficient of 4.7% and remained consistent even when the lithium target was replaced, whereas at 1.95 MeV, the maximum fluctuations reached a factor of 10.

  3. Helicity dependence of the {gamma}d{yields} {pi}NN reactions in the {delta}-resonance region

    Energy Technology Data Exchange (ETDEWEB)

    Ahrens, J.; Arends, H.J.; Beck, R.; Heid, E.; Jahn, O.; Lang, M.; Martinez-Fabregate, M.; Schwamb, M.; Tamas, G.; Thomas, A. [Universitaet Mainz, Institut fuer Kernphysik, Mainz (Germany); Altieri, S.; Panzeri, A.; Pinelli, T. [INFN, Pavia (Italy); Universita di Pavia, Dipartimento di Fisica Nucleare e Teorica, Pavia (Italy); Annand, J.R.M.; McGeorge, J.C.; Protopopescu, D.; Rosner, G. [University of Glasgow, Department of Physics and Astronomy, Glasgow (United Kingdom); Blackston, M.A.; Weller, H.R. [Duke University, Department of Physics, Durham, NC (United States); Bradtke, C.; Dutz, H.; Klein, F.; Rohlof, C. [Universitaet Bonn, Physikalisches Institut, Bonn (Germany); Braghieri, A.; Pedroni, P. [INFN, Sezione di Pavia, Pavia (Italy); Hose, N. d' [DSM/DAPNIA/SPhN, CEA Saclay, Gif-sur-Yvette Cedex (France); Fix, A. [Tomsk Polytechnic University, Laboratory of Mathematical Physics, Tomsk (Russian Federation); Kondratiev, R.; Lisin, V. [Academy of Science, INR, Moscow (Russian Federation); Meyer, W.; Reicherz, G. [Ruhr-Universitaet Bochum, Insitut fuer Experimentalphysik, Bochum (Germany); Rostomyan, T. [Universiteit Gent, Subatomaire en Stralingsfysica, Gent (Belgium); INFN, Pavia (Italy); Ryckbosch, D. [Universiteit Gent, Subatomaire en Stralingsfysica, Gent (Belgium)

    2010-05-15

    The helicity dependence of the differential cross-section for the {gamma}d{yields}{pi}NN reactions has been measured for the first time in the {delta} -resonance region. The measurement was performed with the large-acceptance detector DAPHNE at the tagged photon beam facility of the MAMI accelerator in Mainz. The data show that the main reaction mechanisms for the {pi}{sup {+-}} NN channels are the quasi-free N {pi} processes on one bound nucleon with nuclear dynamics playing a minor role. On the contrary, for the {pi}{sup 0}np channel nuclear mechanisms involving the reabsorption of the photoproduced {pi}{sup 0} by the np pair have to be taken into account to reproduce the experimental data. (orig.)

  4. Radiation induced chemical changes in foodstuffs model reaction systems and strawberries

    International Nuclear Information System (INIS)

    Breitfellner, F.

    1999-10-01

    In the first part of this work 4-hydroxybenzoic acid (4-HBA) and 4-hydroxybenzoic acid ethyl ester (4-HBAEE) were investigated in order to elucidate the reaction mechanisms leading to final products after reaction with OH-radicals (N 2 O-saturated and aerated aqueous solutions) at various pH. Irradiation of 5*10 -4 mol l -1 solutions of 4-HBA at pH 6.0 leads to formation of 3,4-dihydroxybenzoic acid and hydroquinone. In case of the ester neither hydroxylation nor decarboxylation products are observable. By means of pulse radiolysis it could be shown that water splitting from the ester OH-adducts is 17 times faster than from that of the acid. Therefore the main transients are phenoxyl radicals in case of the ester. At pH 10, where base catalyzed water elimination takes place, no hydroxylation products are observable either. In aerated solutions dihydroxy-compounds are formed with both substrates. In the case of 4-HBA 68 % of the OH-radicals result in 3,4-dihydroxyderivate, for 4-HBAEE these are only 25 %. Comparison of the initial degradation yields demonstrates 4-HBAEE to be 1.6-times more stable towards radiation. The second part of this work deals with radiation induced chemical changes in strawberries. Dose/concentration relationships could be obtained for 7 components, i.e. gallic acid, 4-hydroxybenzoic acid, cinnamic acid, 4-hydroxycinnamic acid, 3,4-dihydroxy-cinnamic acid, (-)-epicatechin and (+)-catechin. Linear dose relationships have been found for 4-HBA (formation) and (+)-catechin (degradation). In addition a specific radiolytically formed compound which can be used as marker for irradiation treatment of strawberries could be detected. There are strong indications that it is a radiolytic product of kaempferol, however, it could not yet be identified exactly. (author)

  5. Catalytic Conversion of Renewable Resources into Bulk and Fine Chemicals.

    Science.gov (United States)

    de Vries, Johannes G

    2016-12-01

    Several strategies can be chosen to convert renewable resources into chemicals. In this account, I exemplify the route that starts with so-called platform chemicals; these are relatively simple chemicals that can be produced in high yield, directly from renewable resources, either via fermentation or via chemical routes. They can be converted into the existing bulk chemicals in a very efficient manner using multistep catalytic conversions. Two examples are given of the conversion of sugars into nylon intermediates. 5-Hydroxymethylfurfural (HMF) can be prepared in good yield from fructose. Two hydrogenation steps convert HMF into 1,6-hexanediol. Oppenauer oxidation converts this product into caprolactone, which in the past, has been converted into caprolactam in a large-scale industrial process by reaction with ammonia. An even more interesting platform chemical is levulinic acid (LA), which can be obtained directly from lignocellulose in good yield by treatment with dilute sulfuric acid at 200°C. Hydrogenation converts LA into gamma-valerolactone, which is ring-opened and esterified in a gas-phase process to a mixture of isomeric methyl pentenoates in excellent selectivity. In a remarkable selective palladium-catalysed isomerising methoxycarbonylation, this mixture is converted in to dimethyl adipate, which is finally hydrolysed to adipic acid. Overall selectivities of both processes are extremely high. The conversion of lignin into chemicals is a much more complicated task in view of the complex nature of lignin. It was discovered that breakage of the most prevalent β-O-4 bond in lignin occurs not only via the well-documented C3 pathway, but also via a C2 pathway, leading to the formation of highly reactive phenylacetaldehydes. These compounds went largely unnoticed as they immediately recondense on lignin. We have now found that it is possible to prevent this by converting these aldehydes in a tandem reaction, as they are formed. For this purpose, we have used

  6. Recent searches for superheavy elements in deep-inelastic reactions

    International Nuclear Information System (INIS)

    Hulet, E.K.; Lougheed, R.W.; Nitschke, J.M.

    1980-10-01

    New attempts have been made to synthesize superheavy elements (SHE) by nuclear reactions that may possibly form the products at low excitation energies. Survival of the superheavy elements would then be enhanced because of reduced losses from prompt fission. Classical and diffusion-model calculations of deep-inelastic reactions indicate there should be detectable yields of SHE formed with less than 30 MeV of excitation energy. Accordingly, superheavy elements have been sought in such reactions where targets of 248 Cm and 238 U have been irradiated with 136 Xe and 238 U ions. In the most recent experiments, targets of 248 Cm metal (3.5 to 7 mg-cm -2 ) were bombarded with 1.8-GeV 238 U ions from the UNILAC accelerator. The longer-lived SHE and actinides near the target Z were chemically separated, and the yields of a number of isotopes of Bk, Cf, Es, and Fm were measured. An upper limit of 30 nb was obtained for the formation of 1-h 259 No. In addition to the off-line chemical recovery and search for SHE, an on-line experiment was performed to detect volatile SHE with half-lives of a minute or more. All experiments to produce and detect superheavy elements were much less than optimum because of premature failures in the Cm-metal targets. The outcome and status of these experiments and the implications of the actinide yields in estimating the chances for forming superheavy elements in the 248 Cm + 238 U reactions are discussed. 5 figures, 1 table

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

    International Nuclear Information System (INIS)

    Doktorov, Alexander B.

    2015-01-01

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Doktorov, Alexander B., E-mail: doktorov@kinetics.nsc.ru [Voevodsky Institute of Chemical Kinetics & Combustion, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia and Novosibirsk State University, Novosibirsk 630090 (Russian Federation)

    2015-08-21

    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.

  9. Chemical reactions induced and probed by positive muons

    International Nuclear Information System (INIS)

    Ito, Yasuo

    1990-01-01

    The application of μ + science, collectively called μSR, but encompassing a variety of methods including muon spin rotation, muon spin relaxation, muon spin repolarization, muon spin resonance and level-crossing resonance, to chemistry is introduced emphasizing the special aspects of processes which are 'induced and probed' by the μ + itself. After giving a general introduction to the nature and methods of muon science and a short history of muon chemistry, selected topics are given. One concerns the usefulness of muonium as hydrogen-like probes of chemical reactions taking polymerization of vinyl monomers and reaction with thiosulphate as examples. Probing solitons in polyacetylene induced and probed by μ + is also an important example which shows the unique nature of muonium. Another important topic is 'lost polarization'. Although this term is particular to muonium. Another important topic is 'lost polarization'. Although this term is particular to muon chemistry, the chemistry underlining the phenomenon of lost polarization has an importance to both radiation and hot atom chemistries. (orig.)

  10. Non-empirical analysis of the chemical reaction of cesium with steam; Cs+H{sub 2}O {yields} CsOH+H, in severe light water reactor accidents

    Energy Technology Data Exchange (ETDEWEB)

    Inada, Yasuzi [Fuji Research Inst. Corp., Tokyo (Japan). Computational Engineering Div.

    1998-04-01

    The elementary chemical reaction of cesium which is a volatile fission product with steam (water) shown in the title are analyzed from the first principle. The activation energies for both reactions of the forward and the backward are calculated for the first time with a computer program Gamess, which is based on the non-empirical molecular orbital theory. The calculated values are expected to agree with those of experiments within an accuracy of several tens of kJ/mol. Using the values obtained above, the rate constants are also calculated in the framework of the transition state theory. The derived rate constants will allow us to predict the orders of magnitude of experimental values under high temperature conditions (1,000 K or higher). Thus these rate constants are available as input data for the kinetic (non-equilibrium state) study of cesium in severe light water reactor accidents. (author)

  11. Effects of Single and Combined Application of Organic, Biological and Chemical Fertilizers on Quantitative and Qualitative Yield of Coriander (Coriandrum sativum

    Directory of Open Access Journals (Sweden)

    M. Aghhavani Shajari

    2016-07-01

    Full Text Available Introduction: Medicinal plants were one of the main natural resources of Iran from ancient times. Coriander (Coriandrum sativum L. is from Apiaceae family that it has cultivated extensively in the world. Management and environmental factors such as nutritional management has a significant impact on the quantity and quality of plants. Application of organic fertilizers in conventional farming systems is not common and most of the nutritional need of plants supply through chemical fertilizers for short period. Excessive and unbalanced use of fertilizers in the long period, reduce crop yield and soil biological activity, accumulation of nitrates and heavy metals, and finally cause negative environmental effects and increase the cost of production. The use of bio-fertilizers and organic matter are taken into consideration to reduce the use of chemical fertilizers and increase the quality of most crops. Stability and soil fertility through the use of organic fertilizers are important due to having most of the elements required by plants and beneficial effects on physical, chemical, biological and soil fertility. Therefore, the aim of this research was to evaluate the effects of organic, biological and chemical fertilizers on quality and quantity characteristics of coriander. Materials and Methods: In order to study the effects of single and combined applications of organic, biological and chemical fertilizers on quantitative and qualitative characteristics of Coriander (Coriandrum sativum, an experiment was conducted based on a randomized complete block design with three replications and 12 treatments at Research Station, Faculty of Agriculture, Ferdowsi University of Mashhad, Iran, in - 2011. Treatments included: (1 mycorrhizae (Glomus mosseae (2 biosulfur (Thiobacillus sp., (3 chemical fertilizer (NPK, (4 cow manure, 5( vermin compost, 6( mycorrhizae + chemical fertilizer, 7( mycorrhizae + cow manure, 8( mycorrhizae + vermicompost, 9( biosulfur

  12. Fast preparation of Na0.44MnO2 nanorods via a high NaOH concentration hydrothermal soft chemical reaction and their lithium storage properties

    International Nuclear Information System (INIS)

    Liu, Cai; Li, Jiangang; Zhao, Pengxiang; Guo, Wenli; Yang, Xiaoping

    2015-01-01

    This paper describes a high NaOH concentration hydrothermal soft chemical reaction to prepare Na 0.44 MnO 2 nanorods. In this process, Na-birnessite precursors and concentrated NaOH solution are introduced into the hydrothermal reaction. As a result, the hydrothermal time can be significantly shortened from 96 to 24 h, the hydrothermal temperature can be reduced from 205 to 180 °C and the yield of Na 0.44 MnO 2 can be increased from about 0.6 to about 2.4 g/(mL . day), respectively. Furthermore, the obtained Na 0.44 MnO 2 nanorods with one-dimensional tunnel structures exhibit favorable electrochemical lithium storage properties, which make them promising for the cathode materials of lithium-ion batteries

  13. 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.

  14. 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 - others: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

  15. Potential of commodity chemicals to become bio-based according to maximum yields and petrochemical prices

    NARCIS (Netherlands)

    Straathof, Adrie J.J.; Bampouli, A.

    2017-01-01

    Carbohydrates are the prevailing biomass components available for bio-based production. The most direct way to convert carbohydrates into commodity chemicals is by one-step conversion at maximum theoretical yield, such as by anaerobic fermentation without side product formation. Considering these

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

    International Nuclear Information System (INIS)

    Saripalli, Prasad; Meyer, P D.; Parker, Kent E.; Lindberg, Michael J.

    2005-01-01

    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

  17. In silico prediction of potential chemical reactions mediated by human enzymes.

    Science.gov (United States)

    Yu, Myeong-Sang; Lee, Hyang-Mi; Park, Aaron; Park, Chungoo; Ceong, Hyithaek; Rhee, Ki-Hyeong; Na, Dokyun

    2018-06-13

    Administered drugs are often converted into an ineffective or activated form by enzymes in our body. Conventional in silico prediction approaches focused on therapeutically important enzymes such as CYP450. However, there are more than thousands of different cellular enzymes that potentially convert administered drug into other forms. We developed an in silico model to predict which of human enzymes including metabolic enzymes as well as CYP450 family can catalyze a given chemical compound. The prediction is based on the chemical and physical similarity between known enzyme substrates and a query chemical compound. Our in silico model was developed using multiple linear regression and the model showed high performance (AUC = 0.896) despite of the large number of enzymes. When evaluated on a test dataset, it also showed significantly high performance (AUC = 0.746). Interestingly, evaluation with literature data showed that our model can be used to predict not only enzymatic reactions but also drug conversion and enzyme inhibition. Our model was able to predict enzymatic reactions of a query molecule with a high accuracy. This may foster to discover new metabolic routes and to accelerate the computational development of drug candidates by enabling the prediction of the potential conversion of administered drugs into active or inactive forms.

  18. High resolution studies of the effects of magnetic fields on chemical reactions

    OpenAIRE

    Hamilton, C. A.; Hewitt, J. P.; McLauchlan, Keith A.; Steiner, Ulrich

    1988-01-01

    A simple and inexpensive experiment is described which detects magnetic field effects on chemical reactions with high signal-to-noise ratio and high resolution. It consists in applying a small modulation field to the sample, whilst the main field it experiences is varied, with optical detection at the modulation frequency. It consequently measures the derivative of the normal MARY spectrum. It is shown by theoretical analysis that when using this method it is better to monitor reaction interm...

  19. Determination of the Rate Coefficients of the SO2 plus O plus M yields SO3 plus M Reaction

    Science.gov (United States)

    Hwang, S. M.; Cooke, J. A.; De Witt, K. J.; Rabinowitz, M. J.

    2010-01-01

    Rate coefficients of the title reaction R(sub 31) (SO2 +O+M yields SO3 +M) and R(sub 56) (SO2 + HO2 yields SO3 +OH), important in the conversion of S(IV) to S(VI),were obtained at T =970-1150 K and rho (sub ave) = 16.2 micro mol/cubic cm behind reflected shock waves by a perturbation method. Shock-heated H2/ O2/Ar mixtures were perturbed by adding small amounts of SO2 (1%, 2%, and 3%) and the OH temporal profiles were then measured using laser absorption spectroscopy. Reaction rate coefficients were elucidated by matching the characteristic reaction times acquired from the individual experimental absorption profiles via simultaneous optimization of k(sub 31) and k(sub 56) values in the reaction modeling (for satisfactory matches to the observed characteristic times, it was necessary to take into account R(sub 56)). In the experimental conditions of this study, R(sub 31) is in the low-pressure limit. The rate coefficient expressions fitted using the combined data of this study and the previous experimental results are k(sub 31,0)/[Ar] = 2.9 10(exp 35) T(exp ?6.0) exp(?4780 K/T ) + 6.1 10(exp 24) T(exp ?3.0) exp(?1980 K/T ) cm(sup 6) mol(exp ?2)/ s at T = 300-2500 K; k(sub 56) = 1.36 10(exp 11) exp(?3420 K/T ) cm(exp 3)/mol/s at T = 970-1150 K. Computer simulations of typical aircraft engine environments, using the reaction mechanism with the above k(sub 31,0) and k(sub 56) expressions, gave the maximum S(IV) to S(VI) conversion yield of ca. 3.5% and 2.5% for the constant density and constant pressure flow condition, respectively. Moreover, maximum conversions occur at rather higher temperatures (?1200 K) than that where the maximum k(sub 31,0) value is located (approximately 800 K). This is because the conversion yield is dependent upon not only the k(sup 31,0) and k(sup 56) values (production flux) but also the availability of H, O, and HO2 in the system (consumption flux).

  20. MULTICOMPONENT DETERMINATION OF CHLORINATED HYDROCARBONS USING A REACTION-BASED CHEMICAL SENSOR .2. CHEMICAL SPECIATION USING MULTIVARIATE CURVE RESOLUTION

    NARCIS (Netherlands)

    Tauler, R.; Smilde, A. K.; HENSHAW, J. M.; BURGESS, L. W.; KOWALSKI, B. R.

    1994-01-01

    A new multivariate curve resolution method that can extract analytical information from UV/visible spectroscopic data collected from a reaction-based chemical sensor is proposed. The method is demonstrated with the determination of mixtures of chlorinated hydrocarbons by estimating the kinetic and

  1. Remarkable nanoconfinement effects on chemical equilibrium manifested in nucleotide dimerization and H-D exchange reactions.

    Science.gov (United States)

    Polak, Micha; Rubinovich, Leonid

    2011-10-06

    Nanoconfinement entropic effects on chemical equilibrium involving a small number of molecules, which we term NCECE, are revealed by two widely diverse types of reactions. Employing statistical-mechanical principles, we show how the NCECE effect stabilizes nucleotide dimerization observed within self-assembled molecular cages. Furthermore, the effect provides the basis for dimerization even under an aqueous environment inside the nanocage. Likewise, the NCECE effect is pertinent to a longstanding issue in astrochemistry, namely the extra deuteration commonly observed for molecules reacting on interstellar dust grain surfaces. The origin of the NCECE effect is elucidated by means of the probability distributions of the reaction extent and related variations in the reactant-product mixing entropy. Theoretical modelling beyond our previous preliminary work highlights the role of the nanospace size in addition to that of the nanosystem size, namely the limited amount of molecules in the reaction mixture. Furthermore, the NCECE effect can depend also on the reaction mechanism, and on deviations from stoichiometry. The NCECE effect, leading to enhanced, greatly variable equilibrium "constants", constitutes a unique physical-chemical phenomenon, distinguished from the usual thermodynamical properties of macroscopically large systems. Being significant particularly for weakly exothermic reactions, the effects should stabilize products in other closed nanoscale structures, and thus can have notable implications for the growing nanotechnological utilization of chemical syntheses conducted within confined nanoreactors.

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

    International Nuclear Information System (INIS)

    Li, Tiejun; Lin, Feng

    2016-01-01

    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. (paper)

  3. Laser thermal effect on silicon nitride ceramic based on thermo-chemical reaction with temperature-dependent thermo-physical parameters

    International Nuclear Information System (INIS)

    Pan, A.F.; Wang, W.J.; Mei, X.S.; Wang, K.D.; Zhao, W.Q.; Li, T.Q.

    2016-01-01

    Highlights: • A two-dimensional thermo-chemical reaction model is creatively built. • Thermal conductivity and heat capacity of β-Si_3N_4 are computed accurately. • The appropriate thermo-chemical reaction rate is fitted and reaction element length is set to assure the constringency. • The deepest ablated position was not the center of the ablated area due to plasma absorption. • The simulation results demonstrate the thermo-chemical process cant be simplified to be physical phase transition. - Abstract: In this study, a two-dimensional thermo-chemical reaction model with temperature-dependent thermo-physical parameters on Si_3N_4 with 10 ns laser was developed to investigate the ablated size, volume and surface morphology after single pulse. For model parameters, thermal conductivity and heat capacity of β-Si_3N_4 were obtained from first-principles calculations. Thermal-chemical reaction rate was fitted by collision theory, and then, reaction element length was deduced using the relationship between reaction rate and temperature distribution. Furthermore, plasma absorption related to energy loss was approximated as a function of electron concentration in Si_3N_4. It turned out that theoretical ablated volume and radius increased and then remained constant with increasing laser energy, and the maximum ablated depth was not in the center of the ablated zone. Moreover, the surface maximum temperature of Si_3N_4 was verified to be above 3000 K within pulse duration, and it was much higher than its thermal decomposition temperature of 1800 K, which indicated that Si_3N_4 was not ablated directly above the thermal decomposition temperature. Meanwhile, the single pulse ablation of Si_3N_4 was performed at different powers using a TEM_0_0 10 ns pulse Nd:YAG laser to validate the model. The model showed a satisfactory consistence between the experimental data and numerical predictions, presenting a new modeling technology that may significantly increase the

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

    Science.gov (United States)

    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.

  5. Single-Molecule Sensing with Nanopore Confinement: from Chemical Reactions to Biological Interactions.

    Science.gov (United States)

    Lin, Yao; Ying, Yi-Lun; Gao, Rui; Long, Yi-Tao

    2018-03-25

    The nanopore can generate an electrochemical confinement for single-molecule sensing which help understand the fundamental chemical principle in nanoscale dimensions. By observing the generated ionic current, individual bond-making and bond-breaking steps, single biomolecule dynamic conformational changes and electron transfer processes that occur within pore can be monitored with high temporal and current resolution. These single-molecule studies in nanopore confinement are revealing information about the fundamental chemical and biological processes that cannot be extracted from ensemble measurements. In this concept, we introduce and discuss the electrochemical confinement effects on single-molecule covalent reactions, conformational dynamics of individual molecules and host-guest interactions in protein nanopores. Then, we extend the concept of nanopore confinement effects to confine electrochemical redox reactions in solid-state nanopores for developing new sensing mechanisms. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. 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.

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

    Directory of Open Access Journals (Sweden)

    Abdolhossein Naseri

    2016-12-01

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

  8. Looking for chemical reaction networks exhibiting a drift along a manifold of marginally stable states.

    Science.gov (United States)

    Brogioli, Doriano

    2013-02-07

    I recently reported some examples of mass-action equations that have a continuous manifold of marginally stable stationary states [Brogioli, D., 2010. Marginally stable chemical systems as precursors of life. Phys. Rev. Lett. 105, 058102; Brogioli, D., 2011. Marginal stability in chemical systems and its relevance in the origin of life. Phys. Rev. E 84, 031931]. The corresponding chemical reaction networks show nonclassical effects, i.e. a violation of the mass-action equations, under the effect of the concentration fluctuations: the chemical system drifts along the marginally stable states. I proposed that this effect is potentially involved in abiogenesis. In the present paper, I analyze the mathematical properties of mass-action equations of marginally stable chemical reaction networks. The marginal stability implies that the mass-action equations obey some conservation law; I show that the mathematical properties of the conserved quantity characterize the motion along the marginally stable stationary state manifold, i.e. they allow to predict if the fluctuations give rise to a random walk or a drift under the effect of concentration fluctuations. Moreover, I show that the presence of the drift along the manifold of marginally stable stationary-states is a critical property, i.e. at least one of the reaction constants must be fine tuned in order to obtain the drift. Copyright © 2012 Elsevier Ltd. All rights reserved.

  9. Study of the production of {sup 177}Lu through {sup 176}Yb (n, {gamma}) {sup 177}Yb {yields} {sup 177}Lu nuclear reaction

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Giovana Pasqualini da; Osso Junior, Joao Alberto [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)]. E-mail: gpsilva@ipen.br; jaosso@ipen.br

    2007-07-01

    The beta minus emitter {sup 177}Lu is a promising therapeutic radioisotope for the curative treatment of cancer using labelled proteins. It has a half - life of T{sub 1/2} = 6.71 day and maximum and average {beta}{sup -} energies of 421 and 133 keV, resulting in a short range of radiation in tissue. The decay is accompanied by the emission of low energy {gamma}-radiation with 208.3 keV (11%) and 113 keV (6.4%) suitable for simultaneous imaging, {sup 177}Lu can be produced by two different routes, namely, by irradiation of natural Lu{sub 2}O{sub 3} target ({sup 176}Lu, 2.6%) or enriched (in {sup 176}Lu) Lu{sub 2}O{sub 3} target, as also by irradiation of Yb target (Yb{sub 2}O{sub 3}) followed by radiochemical separation of {sup 177}Lu from Yb isotopes. The objective of this work is to study the production of {sup 177}Lu through the indirect {sup 176}Yb(n,{gamma}){sup 177}Yb {yields} {sup 177}Lu nuclear reaction. The results of the production yield of {sup 177}Lu will be shown and compared with the direct reaction. The method of choice for the chemical separation between Lu and Yb was the ion exchange, using an cation exchange resin in Cl{sup -} form and {alpha}-HIBA as eluent. Preliminary results showed a good separation of {sup 177}Lu from Yb{sub 2}O{sub 3} indirect targets. (author)

  10. Method and apparatus for obtaining enhanced production rate of thermal chemical reactions

    Science.gov (United States)

    Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Wegeng, Robert S [Richland, WA; Gao, Yufei [Kennewick, WA

    2003-04-01

    The present invention is a method and apparatus (vessel) for providing a heat transfer rate from a reaction chamber through a wall to a heat transfer chamber substantially matching a local heat transfer rate of a catalytic thermal chemical reaction. The key to the invention is a thermal distance defined on a cross sectional plane through the vessel inclusive of a heat transfer chamber, reaction chamber and a wall between the chambers. The cross sectional plane is perpendicular to a bulk flow direction of the reactant stream, and the thermal distance is a distance between a coolest position and a hottest position on the cross sectional plane. The thermal distance is of a length wherein the heat transfer rate from the reaction chamber to the heat transfer chamber substantially matches the local heat transfer rate.

  11. Development of a novel fingerprint for chemical reactions and its application to large-scale reaction classification and similarity.

    Science.gov (United States)

    Schneider, Nadine; Lowe, Daniel M; Sayle, Roger A; Landrum, Gregory A

    2015-01-26

    Fingerprint methods applied to molecules have proven to be useful for similarity determination and as inputs to machine-learning models. Here, we present the development of a new fingerprint for chemical reactions and validate its usefulness in building machine-learning models and in similarity assessment. Our final fingerprint is constructed as the difference of the atom-pair fingerprints of products and reactants and includes agents via calculated physicochemical properties. We validated the fingerprints on a large data set of reactions text-mined from granted United States patents from the last 40 years that have been classified using a substructure-based expert system. We applied machine learning to build a 50-class predictive model for reaction-type classification that correctly predicts 97% of the reactions in an external test set. Impressive accuracies were also observed when applying the classifier to reactions from an in-house electronic laboratory notebook. The performance of the novel fingerprint for assessing reaction similarity was evaluated by a cluster analysis that recovered 48 out of 50 of the reaction classes with a median F-score of 0.63 for the clusters. The data sets used for training and primary validation as well as all python scripts required to reproduce the analysis are provided in the Supporting Information.

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

    International Nuclear Information System (INIS)

    Zabka, J.; Roithova, J.; Dolejsek, Z.; Herman, Z.

    2002-01-01

    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 (C 12 -hydrocarbon SAM, C 11 -perfluorohydrocarbon SAM, and C 11 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, C 2 H 5 O + , CD 5 + ) and about 10 - 10 2 times lower for radical ions (like ethanol and benzene molecular ions, CD 4 + ). 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

  13. Anomalous Hall effect assisted by interfacial chemical reaction in perpendicular Co/Pt multilayers

    Science.gov (United States)

    Liu, Qian; Jiang, Shaolong; Teng, Jiao

    2018-05-01

    To uncover the underlying mechanism of Mg effect on the improved anomalous Hall effect (AHE) of perpendicular [Pt/Co]3/Mg/HfO2 multilayers, the X-ray photoelectron spectroscopy analysis has been carried out. It is found that Mg interlayer at the Co/HfO2 interface could prevent the Co oxidation to some extent via interfacial chemical reaction. As a result, A large anomalous Hall resistivity (ρAH) is obtained in perpendicular [Pt/Co]3/Mg/HfO2 multilayers, with a maximum ρAH of 3.02 μΩ cm, which is 59% larger than that in Co/Pt multilayers without Mg insertion. This effective modification of the AHE based on interfacial chemical reaction provides a promising pathway for spintronic applications.

  14. 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

  15. A coupled mechanical-chemical model for reflecting the influence of stress on oxidation reactions in thermal barrier coating

    Science.gov (United States)

    Chen, Lin; Yueming, Li

    2018-06-01

    In this paper, a coupled mechanical-chemical model is established based on the thermodynamic framework, in which the contribution of chemical expansion to free energy is introduced. The stress-dependent chemical potential equilibrium at the gas-solid interface and the stress gradient-dependent diffusion equation as well as a so-called generalized force which is conjugate to the oxidation rate are derived from the proposed model, which could reflect the influence of stresses on the oxidation reaction. Based on the proposed coupled mechanical-chemical model, a user element subroutine is developed in ABAQUS. The numerical simulation of the high temperature oxidation in the thermal barrier coating is carried out to verify the accuracy of the proposed model, and then the influence of stresses on the oxidation reaction is investigated. In thermally grown oxide, the considerable stresses would be induced by permanent volumetric swelling during the oxidation. The stresses play an important role in the chemical potential equilibrium at the gas-solid interface and strongly affect the oxidation reaction. The gradient of the stresses, however, only occurs in the extremely thin oxidation front layer, which plays a very limited role in the oxidation reaction. The generalized force could be divided into the stress-dependent and the stress-independent parts. Comparing with the stress-independent part, the stress-dependent part is smaller, which has little influence on oxidation reaction.

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

    Directory of Open Access Journals (Sweden)

    T. B. Demissie

    2017-01-01

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

  17. Understanding and Improvement of an Experiment Measuring Chemical Reaction Rates by Monitoring Volume Change of a Gas: On the Reaction between HCl(aq) and Mg(s)

    International Nuclear Information System (INIS)

    Bang, Jeong Ah; Yoon, Hee Sook; Jeong, Dae Hong; Choi, Won Ho

    2006-01-01

    In this study we analyzed and improved an experiment measuring chemical reaction rates introduced in the high school science textbooks through an understanding of the phenomena observed in carrying out the experiment. For this purpose, the contents of textbooks related to the experiment were analyzed, and the problems observed in carrying out the experiment were addressed through experimental analysis. When the experiment was carried out by the method of aquatic transposition presented in textbooks, the observed volume change of H 2 gas was delayed and chemical reaction rate was increased in the early stage of reaction period. To resolve these problems, an improved method for measuring the reaction rates was suggested. In the improved experiment the reaction rate was measured to be constant on time, which was interpreted in terms of the concentration of H + and the surface area of magnesium

  18. College Chemistry Students' Use of Memorized Algorithms in Chemical Reactions

    Science.gov (United States)

    Nyachwaya, James M.; Warfa, Abdi-Rizak M; Roehrig, Gillian H.; Schneider, Jamie L.

    2014-01-01

    This study sought to uncover memorized algorithms and procedures that students relied on in responding to questions based on the particulate nature of matter (PNM). We describe various memorized algorithms or processes used by students. In the study, students were asked to balance three equations of chemical reaction and then draw particulate…

  19. In Situ Environmental TEM in Imaging Gas and Liquid Phase Chemical Reactions for Materials Research.

    Science.gov (United States)

    Wu, Jianbo; Shan, Hao; Chen, Wenlong; Gu, Xin; Tao, Peng; Song, Chengyi; Shang, Wen; Deng, Tao

    2016-11-01

    Gas and liquid phase chemical reactions cover a broad range of research areas in materials science and engineering, including the synthesis of nanomaterials and application of nanomaterials, for example, in the areas of sensing, energy storage and conversion, catalysis, and bio-related applications. Environmental transmission electron microscopy (ETEM) provides a unique opportunity for monitoring gas and liquid phase reactions because it enables the observation of those reactions at the ultra-high spatial resolution, which is not achievable through other techniques. Here, the fundamental science and technology developments of gas and liquid phase TEM that facilitate the mechanistic study of the gas and liquid phase chemical reactions are discussed. Combined with other characterization tools integrated in TEM, unprecedented material behaviors and reaction mechanisms are observed through the use of the in situ gas and liquid phase TEM. These observations and also the recent applications in this emerging area are described. The current challenges in the imaging process are also discussed, including the imaging speed, imaging resolution, and data management. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Rock-fluid chemical interactions at reservoir conditions: The influence of brine chemistry and extent of reaction

    Science.gov (United States)

    Anabaraonye, B. U.; Crawshaw, J.; Trusler, J. P. M.

    2016-12-01

    Following carbon dioxide injection in deep saline aquifers, CO2 dissolves in the formation brines forming acidic solutions that can subsequently react with host reservoir minerals, altering both porosity and permeability. The direction and rates of these reactions are influenced by several factors including properties that are associated with the brine system. Consequently, understanding and quantifying the impacts of the chemical and physical properties of the reacting fluids on overall reaction kinetics is fundamental to predicting the fate of the injected CO2. In this work, we present a comprehensive experimental study of the kinetics of carbonate-mineral dissolution in different brine systems including sodium chloride, sodium sulphate and sodium bicarbonate of varying ionic strengths. The impacts of the brine chemistry on rock-fluid chemical reactions at different extent of reactions are also investigated. Using a rotating disk technique, we have investigated the chemical interactions between the CO2-saturated brines and carbonate minerals at conditions of pressure (up to 10 MPa) and temperature (up to 373 K) pertinent to carbon storage. The changes in surface textures due to dissolution reaction were studied by means of optical microscopy and vertical scanning interferometry. Experimental results are compared to previously derived models.

  1. Recent Trends in Quantum Chemical Modeling of Enzymatic Reactions.

    Science.gov (United States)

    Himo, Fahmi

    2017-05-24

    The quantum chemical cluster approach is a powerful method for investigating enzymatic reactions. Over the past two decades, a large number of highly diverse systems have been studied and a great wealth of mechanistic insight has been developed using this technique. This Perspective reviews the current status of the methodology. The latest technical developments are highlighted, and challenges are discussed. Some recent applications are presented to illustrate the capabilities and progress of this approach, and likely future directions are outlined.

  2. One- and two-dimensional chemical exchange nuclear magnetic resonance studies of the creatine kinase catalyzed reaction

    International Nuclear Information System (INIS)

    Gober, J.R.

    1988-01-01

    The equilibrium chemical exchange dynamics of the creatine kinase enzyme system were studied by one- and two-dimensional 31 P NMR techniques. Pseudo-first-order reaction rate constants were measured by the saturation transfer method under an array of experimental conditions of pH and temperature. Quantitative one-dimensional spectra were collected under the same conditions in order to calculate the forward and reverse reaction rates, the K eq , the hydrogen ion stoichiometry, and the standard thermodynamic functions. The pure absorption mode in four quadrant two-dimensional chemical exchange experiment was employed so that the complete kinetic matrix showing all of the chemical exchange process could be realized

  3. CH3CO + O2 + M (M = He, N2) Reaction Rate Coefficient Measurements and Implications for the OH Radical Product Yield.

    Science.gov (United States)

    Papadimitriou, Vassileios C; Karafas, Emmanuel S; Gierczak, Tomasz; Burkholder, James B

    2015-07-16

    The gas-phase CH3CO + O2 reaction is known to proceed via a chemical activation mechanism leading to the formation of OH and CH3C(O)OO radicals via bimolecular and termolecular reactive channels, respectively. In this work, rate coefficients, k, for the CH3CO + O2 reaction were measured over a range of temperature (241-373 K) and pressure (0.009-600 Torr) with He and N2 as the bath gas and used to characterize the bi- and ter-molecular reaction channels. Three independent experimental methods (pulsed laser photolysis-laser-induced fluorescence (PLP-LIF), pulsed laser photolysis-cavity ring-down spectroscopy (PLP-CRDS), and a very low-pressure reactor (VLPR)) were used to characterize k(T,M). PLP-LIF was the primary method used to measure k(T,M) in the high-pressure regime under pseudo-first-order conditions. CH3CO was produced by PLP, and LIF was used to monitor the OH radical bimolecular channel reaction product. CRDS, a complementary high-pressure method, measured k(295 K,M) over the pressure range 25-600 Torr (He) by monitoring the temporal CH3CO radical absorption following its production via PLP in the presence of excess O2. The VLPR technique was used in a relative rate mode to measure k(296 K,M) in the low-pressure regime (9-32 mTorr) with CH3CO + Cl2 used as the reference reaction. A kinetic mechanism analysis of the combined kinetic data set yielded a zero pressure limit rate coefficient, kint(T), of (6.4 ± 4) × 10(-14) exp((820 ± 150)/T) cm(3) molecule(-1) s(-1) (with kint(296 K) measured to be (9.94 ± 1.3) × 10(-13) cm(3) molecule(-1) s(-1)), k0(T) = (7.39 ± 0.3) × 10(-30) (T/300)(-2.2±0.3) cm(6) molecule(-2) s(-1), and k∞(T) = (4.88 ± 0.05) × 10(-12) (T/300)(-0.85±0.07) cm(3) molecule(-1) s(-1) with Fc = 0.8 and M = N2. A He/N2 collision efficiency ratio of 0.60 ± 0.05 was determined. The phenomenological kinetic results were used to define the pressure and temperature dependence of the OH radical yield in the CH3CO + O2 reaction. The

  4. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 128; Issue 1 ... Ruthenium(II) complexes (1-3) bearing bis-phenolate--heterocyclic carbene ligand were synthesized in good yields by the reaction of imidazolinium proligand (HL) with ... Department of Chemistry, Periyar University, Salem 636 011, Tamil Nadu, India ...

  5. 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.

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

    International Nuclear Information System (INIS)

    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 2 /minus/> DH + H and the substitution reaction D + C 2 H 2 /minus/> C 2 HD + H. Recent advances in uv laser and pulsed molecular beam techniques have made the detailed study of hydrogen atom reactions under single collision conditions possible. 18 refs., 9 figs

  7. Control of chemical reactions with electron beams; Kontrolle chemischer Reaktionen mit Elektronenstrahlung

    Energy Technology Data Exchange (ETDEWEB)

    Boehler, Esther

    2014-03-18

    Interaction between low-energy electrons and molecules can lead to dissociative electron attachment (DEA) or dissociative ionization (DI). In condensed matter, the resulting reactive fragments can attack adjacent molecules to yield larger products. In this thesis, reactions initiated by DEA to acetonitrile in condensed phase have been compared to the known gas phase fragmentation channels. Also, gas phase DEA experiments have been performed on chlorosilanes to study the effect of a variation of the organic ligands on the energy of their molecular orbitals and reactivity in DEA processes. Furthermore, hydroamination reactions induced by DI for different alkenes and amines have been investigated. A similar reaction of ammonia and carbon monoxide was shown to produce formamide (HCONH2), which is the smallest molecule to contain a peptide bond and thus represents an important building block of biologically relevant substances.

  8. Theoretical and experimental study on solid chemical reaction between BaCO3 and TiO2 in microwave field

    International Nuclear Information System (INIS)

    Liu Hanxing; Guo, Liling; Zou Long; Cao Minhe; Zhou Jian; Ouyang Shixi

    2004-01-01

    Solid-state chemical reaction mechanism for the reaction between BaCO 3 and TiO 2 in microwave field was investigated based on X-ray power diffraction (XRD) data and theory of diffusion. The compositions of the resultant after reaction under different conditions were studied by employing XRD. The quantitative analyses based on XRD data showed the reaction in microwave field was quite different from that in the conventional method. A model was proposed to explain the change of the ratio between the reactant BaCO 3 , TiO 2 and the resultant BaTiO 3 for the chemical reaction. The formation kinetic of BaTiO 3 from the BaCO 3 and TiO 2 was calculated by employing this theoretical model. The reaction rate between BaCO 3 and TiO 2 in microwave field was much higher than that in conventional method. The activation energy of the atomic diffusions in this solid chemical reaction is only 58 kJ/mol, which was only about 1/4 of 232 kJ/mol in the conventional value. The result suggests that the microwave field enhance atomic diffusion during the reaction

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

    NARCIS (Netherlands)

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

    1995-01-01

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

  10. Vibrational state-resolved differential cross sections for the D + H sub 2 yields DH + H reaction

    Energy Technology Data Exchange (ETDEWEB)

    Continetti, R.E.

    1989-11-01

    In this thesis, crossed-molecular-beams studies of the reaction D + H{sub 2} {yields} DH + H at collision energies of 0.53 and 1.01 eV are reported. Chapter 1 provides a survey of important experimental and theoretical studies on the dynamics of the hydrogen exchange reaction. Chapter 2 discusses the development of the excimer-laser photolysis D atom beam source that was used in these studies and preliminary experiments on the D + H{sub 2} reaction. In Chapter 3, the differential cross section measurements are presented and compared to recent theoretical predictions. The measured differential cross sections for rotationally excited DH products showed significant deviations from recent quantum scattering calculations, in the first detailed comparison of experimental and theoretical differential cross sections. These results indicate that further work on the H{sub 3} potential energy surface, particularly the bending potential, is in order.

  11. Ab initio chemical kinetics for SiH3 reactions with Si(x)H2x+2 (x = 1-4).

    Science.gov (United States)

    Raghunath, P; Lin, M C

    2010-12-30

    Gas-phase kinetics and mechanisms of SiH(3) reactions with SiH(4), Si(2)H(6), Si(3)H(8), and Si(4)H(10), processes of relevance to a-Si thin-film deposition, have been investigated by ab initio molecular orbital and transition-state theory (TST) calculations. Geometric parameters of all the species involved in the title reactions were optimized by density functional theory at the B3LYP and BH&HLYP levels with the 6-311++G(3df,2p) basis set. The potential energy surface of each reaction was refined at the CCSD(T)/6-311++G(3df,2p) level of theory. The results show that the most favorable low energy pathways in the SiH(3) reactions with these silanes occur by H abstraction, leading to the formation of SiH(4) + Si(x)H(2x+1) (silanyl) radicals. For both Si(3)H(8) and n-Si(4)H(10) reactions, the lowest energy barrier channels take place by secondary Si-H abstraction, yielding SiH(4) + s-Si(3)H(7) and SiH(4) + s-Si(4)H(9), respectively. In the i-Si(4)H(10) reaction, tertiary Si-H abstraction has the lowest barrier producing SiH(4) + t-Si(4)H(9). In addition, direct SiH(3)-for-X substitution reactions forming Si(2)H(6) + X (X = H or silanyls) can also occur, but with significantly higher reaction barriers. A comparison of the SiH(3) reactions with the analogous CH(3) reactions with alkanes has been made. The rate constants for low-energy product channels have been calculated for the temperature range 300-2500 K by TST with Eckart tunneling corrections. These results, together with predicted heats of formation of various silanyl radicals and Si(4)H(10) isomers, have been tabulated for modeling of a-Si:H film growth by chemical vapor deposition.

  12. Evaluation of Yield and Chemical Characteristics of some Peanut Mutants Induced by Gamma Irradiation

    International Nuclear Information System (INIS)

    Abd El-daem, G.A.; Anwar, M.M.

    2013-01-01

    This study was conducted to evaluate some promising mutants in peanut for yielding ability over three generation (M5, M6 and M7) and to evaluate yield attributes as will as chemical characteristics of these mutants in M7 generation induced by 100 Gy gamma radiation. The obtained results showed that the increase of yield / plot over three generation as a percentage of control was 5% for mutant 7, 10.2 % for mutant 10; 22% for mutant 9 and 22.9% for mutant 8. This increase in yield may be due to increase of one or more of yield attributes for most mutant lines. The significant increase for. No .of pods and seeds/ plant, weight of pods and seeds/ plant and 100- seed weight in M7 as compared to the control. For saturated fatty acid composition, results revealed that total saturated fatty acids ranged from 17.79% for mutant 8 to 21.75 for mutant 2 compared to 24.21% for control. Reduction of total saturated fatty acid was noticed for different mutants compared to that of the original variety. However, for total unsaturated fatty acids, results indicated that total unsaturated fatty acid composition ranged from 77.95% for mutant 9 to 82.09% for mutant 8 compared to 75.49% for control. Higher total unsaturated fatty acids for all mutant lines were obtained than that of the control, however, total saturated (TS)/ total unsaturated (TU) ratio was decreased for all mutants compared to control. The physical and chemical contents of Peanut oils showed that the refractive indices were ranged from 1.4620 to 1.4718 specific gravity were in range of 0.9146 to 0.9177. Acid value was range from 0.54 to 0.89% lodine value was ranged from 94.56 to 101.85. Saponification value was ranged from 185.2 to 190.7 and unsaponifiable matter was ranged from 0.98 to 1.33. The peroxide values ranged from 1.15 to 2.33 meq/kg oil. Also, fortified yoghurt made with replaced mutant peanut oil by 50% as milk fat substitute. Data showed that chemical composition and organolyptic properties had the

  13. Association of total-mixed-ration chemical composition with milk, fat, and protein yield lactation curves at the individual level

    NARCIS (Netherlands)

    Caccamo, M.; Veerkamp, R.F.; Licitra, G.; Petriglieri, R.; Terra, La F.; Pozzebon, A.; Ferguson, J.D.

    2012-01-01

    The objective of this study was to examine the effect of the chemical composition of a total mixed ration (TMR) tested quarterly from March 2006 through December 2008 for milk, fat, and protein yield curves for 27 herds in Ragusa, Sicily. Before this study, standard yield curves were generated on

  14. Fast pyrolysis of Miscanthus sinensis in fluidized bed reactors: Characteristics of product yields and biocrude oil quality

    International Nuclear Information System (INIS)

    Bok, Jin Pil; Choi, Hang Seok; Choi, Joon Weon; Choi, Yeon Seok

    2013-01-01

    In the present work, fast pyrolysis of Miscanthus sinensis was performed and the product yields and properties of the resulting biocrude oil were determined for varying reactor configurations and pyrolysis temperatures. Two types of reactors (rectangular and cylindrical fluidized beds) were adopted, and pyrolysis temperature was increased from 400 °C to 550 °C. Based on the results, it was found that the reaction temperature greatly influenced the product yield and the characteristics of biocrude oil. The highest yield of biocrude oil for the rectangular reactor was 48.9 wt.%, produced at 500 °C, and the highest yield for the cylindrical reactor was 50.01 wt.%, produced at 450 °C. Additionally, the biocrude oil yield in the rectangular reactor sharply decreased when reaction temperature was increased to 550 °C, while only a slight decrease was observed in the cylindrical reactor. From GC/MS analysis, biocrude oil was found to contain various chemical components, such as nonaromatic ketones, furans, sugars, lignin-derived phenols, guaiacols and syringols. In particular, the sugar content of the biocrude oil produced in rectangular reactor (2.11–9.35 wt.%) was generally lower than that produced in the cylindrical reactor (7.93–10.79 wt.%). - Highlights: • Fast pyrolysis of Miscanthus sinensis was performed in two fluidized bed reactors to obtain biocrude oil. • The yield and characteristics of the biocrude oil were scrutinized with changing reaction temperature and reactor type. • The reaction temperature was found to be the most influencing parameter for the fast pyrolysis reaction. • The different heating rate caused by reactor type has an effect on the final product yield and characteristics

  15. Barrierless Reactions with Loose Transition States Govern the Yields and Lifetimes of Organic Nitrates Derived from Isoprene

    Science.gov (United States)

    The chemical reaction mechanism of NO addition to two β and δ isoprene hydroxy–peroxy radical isomers is examined in detail using density functional theory, coupled cluster methods, and the energy resolved master equation formalism to provide estimates of rate co...

  16. Novel catalysts for valorization of biomass to value-added chemicals ...

    Indian Academy of Sciences (India)

    The catalysts used for each transformation were subjected to detailed characterization using XRD, BET surface area, temperature-programmed desorption and transmission electron microscopy. The effect of various reaction parameters was also investigated for obtaining high yields of desired chemical intermediates.

  17. Surface Reaction Kinetics of Ga(1-x)In(x)P Growth During Pulsed Chemical Beam Epitaxy

    National Research Council Canada - National Science Library

    Dietz, N; Beeler, S. C; Schmidt, J. W; Tran, H. T

    2000-01-01

    ... into the surface reaction kinetics during an organometallic deposition process. These insights will allow us to move the control point closer to the point where the growth occurs, which in a chemical been epitaxy process is a surface reaction layer (SRL...

  18. Ionic Diffusion and Kinetic Homogeneous Chemical Reactions in the Pore Solution of Porous Materials with Moisture Transport

    DEFF Research Database (Denmark)

    Johannesson, Björn

    2009-01-01

    Results from a systematic continuum mixture theory will be used to establish the governing equations for ionic diffusion and chemical reactions in the pore solution of a porous material subjected to moisture transport. The theory in use is the hybrid mixture theory (HMT), which in its general form......’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...

  19. O efeito do ultra-som em reações químicas The ultrasound effect on chemistry reactions

    Directory of Open Access Journals (Sweden)

    Marco Antonio Utrera Martines

    2000-04-01

    Full Text Available Unusual chemical phenomenon associated with ultrasound is on account of cavitation effect. The ultrasound increase the rate and yield of chemical reaction on account of its ability to emulsify liquids. When the ultrasound is used in metallic catalyst reaction the activity of catalyst is increased because the ultrasound clean the surface of catalyst. Sonogels have a fine porosity and large specific surface improving different properties. This paper deals with ultrasound phenomenon and gives some examples of reactions and properties where this radiation takes an important role.

  20. Influence of reaction time on the structure of polyaniline synthesized on a pre-pilot scale

    Directory of Open Access Journals (Sweden)

    Maria Alice Carvalho Mazzeu

    Full Text Available Abstract The aim of this work is to follow the structural variations of polyaniline (PAni obtained by chemical oxidation on a pre-pilot scale, with different reaction times. Synthesis of PAni is well known, but when it is carried out on a pre-pilot scale, several factors can lead to structural changes and understanding these changes is important to improve controls on the synthesis process. The polymers formed were characterized by spectroscopic techniques (Raman spectroscopy, Fourier Transform Infrared - FTIR and UV-Visible. Degree of oxidation and yield were calculated for each reaction time. The analysis by FTIR, the calculated degree of oxidation and the yield showed significant changes in polymer structure at reaction times of 65 and 80 min. This result was attributed to the excessive oxidation of PAni, with the breaking of its polymer chain. The changes observed in the structure of PAni gave subsidies to the optimization of the process of obtaining polyaniline by chemical synthesis.

  1. Olive oil pilot-production assisted by pulsed electric field: impact on extraction yield, chemical parameters and sensory properties.

    Science.gov (United States)

    Puértolas, Eduardo; Martínez de Marañón, Iñigo

    2015-01-15

    The impact of the use of pulsed electric field (PEF) technology on Arroniz olive oil production in terms of extraction yield and chemical and sensory quality has been studied at pilot scale in an industrial oil mill. The application of a PEF treatment (2 kV/cm; 11.25 kJ/kg) to the olive paste significantly increased the extraction yield by 13.3%, with respect to a control. Furthermore, olive oil obtained by PEF showed total phenolic content, total phytosterols and total tocopherols significantly higher than control (11.5%, 9.9% and 15.0%, respectively). The use of PEF had no negative effects on general chemical and sensory characteristics of the olive oil, maintaining the highest quality according to EU legal standards (EVOO; extra virgin olive oil). Therefore, PEF could be an appropriate technology to improve olive oil yield and produce EVOO enriched in human-health-related compounds, such as polyphenols, phytosterols and tocopherols. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Recurrence Relations for the Equilibrium Means of Distributions Arising in Chemical Reactions

    Directory of Open Access Journals (Sweden)

    E.K. Elsheikh

    1997-12-01

    Full Text Available In this paper we derive recurrence relations that describe how the equilibrium mean of the number molecules of a reactant varies with each of the parameters defining the initial state for four basic reversible chemical reactions. In essence, the relations provide a rationale for updating the equilibrium mean following the addition (or removal of a molecule of one of the types involved in the reaction, there being a relation for each type. With a new parameterization introduced for each reaction, the relations provide a convenient means of evaluating the means, variances and other important moments without any need to work out the underlying distributions. As an application, the relations are used to numerically assess-approximate expressions for the means and variances.

  3. Effect of Organic and Chemical Fertilizers on Yield and Essential Oil of Two Ecotypes of Savory (Satureja hortensis L. under Normal and Drought Stress Conditions

    Directory of Open Access Journals (Sweden)

    O Akrami nejad

    2016-02-01

    Full Text Available Introduction Savory (Satureja hortensis L. is an annual and aromatic plant from Labiatae family, which has plenty of essential oil and is important in medicinal, food, health and beauty industries (6. In comparison with chemical fertilizers, organic fertilizers especially manure have lots of organic material sources, and can be used as nutrients, especially Nitrogen, Phosphor and Potassium. Organic fertilizers also keeps more water in the soil (14. Water deficit is one of the most important boundaries of production in arid and semi-arid regions. Drought stress reduces water content, limits plant growth and changes some physiological and metabolic activities (31. This experiment was conducted as there is a global interest for production of medicinal plants with sustainable agriculture system, and with low input and shortage of information about Savory reaction to fertilization in drought stress condition. The objective of this research was to compare the effects of chemical fertilizers and different organic fertilizers on quantitative and qualitative characteristics of two ecotypes of savory under drought stress condition. Materials and Methods In order to study the effects of organic and mineral (N, P and K fertilizers on quantitative and qualitative characteristics of savory in drought stress condition, two separate split plot designs with three replications were carried out in 2012-2013 year, at the research field of Shahid Bahonar University of Kerman, Iran. In each design fertilizers including cow manure (30 ton per hectare, poultry manure (10 ton per hectare, chemical fertilizers (used equally with macro elements existing in both poultry and cow manure and control (no fertilizer were used as main factor. Kerman and Khuzestan ecotypes were sub-factor. One of the experiments was irrigated to 100% and the other to 50% of field capacity. Two experiments were analyzed as a combined design. The important characteristics of Savory such as plant

  4. FORAGE YIELD, CHEMICAL COMPOSITION AND IN VITRO GAS PRODUCTION OF YELLOW HYBRID MAIZE GROWN IN MEXICO

    Directory of Open Access Journals (Sweden)

    Lizbeth Esmeralda Roblez Jimenez

    2017-12-01

    Full Text Available Maize is the most important forage in feed cattle, due to its higher energy content, however, it is characterized by its wide range of varieties and the possibility of generating a large quantity of final products. The objective of the present study was to evaluate and compare the forage yield, chemical composition and in vitro gas production as fresh and hay of a local yellow criollo maize and six varieties of yellow hybrid maize (HIT13, CML460, PIONER, COPPER, CDMO80001 and CLO80902. Fresh and dry yield did not show differences between treatments (P>0.05, their chemical composition (g / kg DM showed differences (P ˂ 0.05 for the protein content by various storage methods ranging from 59.87 to 59.61 g kg-1 DM per conservation method, NDF ranged from 591 to 686 g kg-1 DM by variety and by the method ranged from 619 to 639 g kg -1 DM, ADF ranged from 298 to 345 g kg-1 DM by variety and 317 to 340 g kg-1 DM by conservation method; ADL ranged from 58 to 41 g kg-1 DM by variety and 41 to 57 g kg-1 DM by conservation method, in vitro gas production  there were no differences (P>0.05 between varieties and conservation method. It is concluded that according to the results obtained, the varieties studied show the same forage yields in both hay and fresh, chemical composition, and in vitro gas production.

  5. Chemical reactions of recoil atoms and thermal atoms of tritium with haloid benzenes

    International Nuclear Information System (INIS)

    Simirskij, Yu.N.; Firsova, L.P.

    1978-01-01

    Radiochemical yields have been determined for the products of substitution of hydrogen atoms and halides in Cl-, Br-, and I-benzenes with tritium atoms obtained during thermal dissociation of T 2 and with recoil atoms T arising in nuclear reaction 6 Li(n, P)T. It is shown that in the series of Cl-, Br-, and I-benzenes yields of the products of substitution of halides atoms with tritium grow, whereas those of hydrogen atom substitution change only little. The correlation nature of the yields of substitution products of halide atoms with tritium remains constant in a wide range of the initial kinetic energies of T atoms for the recoil atoms with E 0 =2.7 MeV and for the completely thermolized atoms during thermal dissociation of T 2

  6. Reactivity and selectivity of arenes in reactions with ozone

    International Nuclear Information System (INIS)

    Vysotskii, Yu.B.; Mestechkin, M.M.; Sivyakova, L.N.; Tyupalo, N.F.

    1987-01-01

    The reactions of arenes with ozone, distinguished by the variety of products (quinones, aldehydes, acids), are of interest not only from the theoretical standpoint but also are of preparative value in the case of polycyclic hydrocarbons. In this work a quantitative treatment of this reaction is given on the basis of direct kinetic measurements and simple quantum chemical means, permitting its rate constants and the yield of the products to be related to the elements of electronic structure readily subject to quantum mechanical calculation

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

    NARCIS (Netherlands)

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

    2006-01-01

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

  8. Mathematical modeling of the radiation-chemical oxidation of U(IV) in HClO4

    International Nuclear Information System (INIS)

    Vladimirova, M.V.

    1995-01-01

    Mathematical modeling of U(IV) oxidation in 0.5-12 M HClO 4 upon α, γ-radiolysis, based on the proposed scheme of radiation-chemical reactions, has been performed. The rate constants of the U(VI) + HO 2 , U(IV) + HO 2 , U(IV) + ClO 2 , and U(IV) + ClO 2 - reactions have been determined by the comparison of the calculated and experimental kinetic and dose curves and radiation-chemical yields of U(IV) oxidation or U(VI) formation. General equations for uranium (IV) oxidation constants at various HClO 4 concentrations, based on the analysis of the rates of particular radiation-chemical reactions composing oxidation process, have been obtained

  9. Use of the nonsteady monotonic heating method for complex determination of thermophysical properties of chemically reacting mixture in the case of non-equilibrium proceeding of the chemical reaction

    International Nuclear Information System (INIS)

    Serebryanyj, G.Z.

    1984-01-01

    Theoretical analysis is made for the monotonic heating method as applied for complex determination of thermophysical properties of chemically reacting gases. The possibility is shown of simultaneous determination of frozen and equilibrium heat capacity, frozen and equilibrium heat conduction provided non-equilibrium occuring of the reaction in the wide range of temperatures and pressures. The monotonic heating method can be used for complex determination of thermophysical properties of chemically reacting systems in case of non-equilibrium proceeding of the chemical reaction

  10. The correlation schemes in calculations of the rate constants of some radiation chemical reactions

    International Nuclear Information System (INIS)

    Zagorets, P.A.; Shostenko, A.G.; Kim, V.

    1983-01-01

    The various correlation relationships of the evaluation of the rate constants of radiation chemical reactions of addition, abstraction and isomerization were considered. It was shown that neglection of the influence of solvent can result in errors in calculations of rate constants equalling two orders in magnitude. Several examples of isokinetic relationship are given. The methods of calculation of transmission coefficient of reaction addition have been discussed. (author)

  11. 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: 2.183, year: 2015

  12. 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

  13. 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

  14. Chemical reaction at ferromagnet/oxide interface and its influence on anomalous Hall effect

    International Nuclear Information System (INIS)

    Liu, Yi-Wei; Teng, Jiao; Zhang, Jing-Yan; Liu, Yang; Chen, Xi; Li, Xu-Jing; Feng, Chun; Wang, Hai-Cheng; Li, Ming-Hua; Yu, Guang-Hua; Wu, Zheng-Long

    2014-01-01

    Chemical reactions at the ferromagnet/oxide interface in [Pt/Fe] 3 /MgO and [Pt/Fe] 3 /SiO 2 multilayers before and after annealing were investigated by X-ray photoelectron spectroscopy. The results show that Fe atoms at the Fe/MgO interface were completely oxidized in the as-grown state and significantly deoxidized after vacuum annealing. However, only some of the Fe atoms at the Fe/SiO 2 interface were oxidized and rarely deoxidized after annealing. The anomalous Hall effect was modified by this interfacial chemical reaction. The saturation anomalous Hall resistance (R xy ) was greatly increased in the [Pt/Fe] 3 /MgO multilayers after annealing and was 350% higher than that in the as-deposited film, while R xy of the [Pt/Fe] 3 /SiO 2 multilayer only increased 10% after annealing.

  15. Mass transfer rate through liquid membranes: interfacial chemical reactions and diffusion as simultaneous permeability controlling factors

    International Nuclear Information System (INIS)

    Danesi, P.R.; Horwitz, E.P.; Vandegrift, G.F.; Chiarizia, R.

    1981-01-01

    Equations describing the permeability of a liquid membrane to metal cations have been derived taking into account aqueous diffusion, membrane diffusion, and interfacial chemical reactions as simultaneous permeability controlling factors. Diffusion and chemical reactions have been coupled by a simple model analogous to the one previously described by us to represent liquid-liquid extraction kinetics. The derived equations, which make use of experimentally determined interfacial reaction mechanisms, qualitatively fit unexplained literature data regarding Cu 2+ transfer through liquid membranes. Their use to predict and optimize membrane permeability in practical separation processes by setting the appropriate concentration of the membrane carrier [LIX 64 (General Mills), a commercial β-hydroxy-oxime] and the pH of the aqueous copper feed solution is briefly discussed. 4 figures

  16. HELP: a model for evaluating the feasibility of using various chemical reaction systems as electronic lasers

    Energy Technology Data Exchange (ETDEWEB)

    Herbelin, J M; Cohen, N

    1975-09-01

    An analytical model for estimating the minimum requirements of a chemically pumped electronic laser is developed. From a knowledge of the basic spectroscopic and thermodynamic properties of a particular reaction, the model can quickly classify the system in accordance with the feasibility of generating stimulated emission at different possible wavelengths. Sample calculations of the reactions of barium atoms with nitrous oxide and nitrogen dioxide indicate that the model is sufficiently sensitive to distinguish between very similar systems and, therefore, should be useful in providing classification criteria in the search for a chemically pumped electronic laser.

  17. Crossed-beam reaction of carbon atoms with hydrocarbon molecules. IV. Chemical dynamics of methylpropargyl radical formation, C4H5, from reaction of C(3Pj) with propylene, C3H6 (X1A)

    International Nuclear Information System (INIS)

    Kaiser, R.I.; Stranges, D.; Bevsek, H.M.; Lee, Y.T.; Suits, A.G.

    1997-01-01

    The reaction between ground state carbon atoms and propylene, C 3 H 6 , was studied at average collision energies of 23.3 and 45.0 kJmol -1 using the crossed molecular beam technique. Product angular distributions and time-of-flight spectra of C 4 H 5 at m/e=53 were recorded. Forward-convolution fitting of the data yields a maximum energy release as well as angular distributions consistent with the formation of methylpropargyl radicals. Reaction dynamics inferred from the experimental results suggest that the reaction proceeds on the lowest 3 A surface via an initial addition of the carbon atom to the π-orbital to form a triplet methylcyclopropylidene collision complex followed by ring opening to triplet 1,2-butadiene. Within 0.3 endash 0.6 ps, 1,2-butadiene decomposes through carbon endash hydrogen bond rupture to atomic hydrogen and methylpropargyl radicals. The explicit identification of C 4 H 5 under single collision conditions represents a further example of a carbon endash hydrogen exchange in reactions of ground state carbon with unsaturated hydrocarbons. This versatile machine represents an alternative pathway to build up unsaturated hydrocarbon chains in combustion processes, chemical vapor deposition, and in the interstellar medium. copyright 1997 American Institute of Physics

  18. Substrate-Directed Catalytic Selective Chemical Reactions.

    Science.gov (United States)

    Sawano, Takahiro; Yamamoto, Hisashi

    2018-05-04

    The development of highly efficient reactions at only the desired position is one of the most important subjects in organic chemistry. Most of the reactions in current organic chemistry are reagent- or catalyst-controlled reactions, and the regio- and stereoselectivity of the reactions are determined by the inherent nature of the reagent or catalyst. In sharp contrast, substrate-directed reaction determines the selectivity of the reactions by the functional group on the substrate and can strictly distinguish sterically and electronically similar multiple reaction sites in the substrate. In this Perspective, three topics of substrate-directed reaction are mainly reviewed: (1) directing group-assisted epoxidation of alkenes, (2) ring-opening reactions of epoxides by various nucleophiles, and (3) catalytic peptide synthesis. Our newly developed synthetic methods with new ligands including hydroxamic acid derived ligands realized not only highly efficient reactions but also pinpointed reactions at the expected position, demonstrating the substrate-directed reaction as a powerful method to achieve the desired regio- and stereoselective functionalization of molecules from different viewpoints of reagent- or catalyst-controlled reactions.

  19. Computed potential energy surfaces for chemical reactions

    Science.gov (United States)

    Walch, Stephen P.

    1988-01-01

    The minimum energy path for the addition of a hydrogen atom to N2 is characterized in CASSCF/CCI calculations using the (4s3p2d1f/3s2p1d) basis set, with additional single point calculations at the stationary points of the potential energy surface using the (5s4p3d2f/4s3p2d) basis set. These calculations represent the most extensive set of ab initio calculations completed to date, yielding a zero point corrected barrier for HN2 dissociation of approx. 8.5 kcal mol/1. The lifetime of the HN2 species is estimated from the calculated geometries and energetics using both conventional Transition State Theory and a method which utilizes an Eckart barrier to compute one dimensional quantum mechanical tunneling effects. It is concluded that the lifetime of the HN2 species is very short, greatly limiting its role in both termolecular recombination reactions and combustion processes.

  20. yield and yield componemts of extra early maize (zea mays l.)

    African Journals Online (AJOL)

    SHARIFAI

    maize crop and improve the soil structures and chemical nutrients of the soil. The significant interaction between intra-row spacing and poultry manure on cob diameter, 100 grain weight and grain yield showed the importance of poultry manure on yield and yield components of maize crop. Poultry manure increases both ...