Sample records for chemical reaction thermal

  1. Thermal Coefficients and Heat Capacities in Systems with Chemical Reaction

    E-print Network

    Matías, Manuel A.

    Thermal Coefficients and Heat Capacities in Systems with Chemical Reaction The Le Chatelier of the study of the equilib- rium states in chemical reactions is based much on the for- mulation of empirical and rigorous basis for the effect of external pertur- bations on a chemical reaction. Namely, the basis

  2. Femtosecond Chemically Activated Reactions: Concept of Nonstatistical Activation at High Thermal Energies

    E-print Network

    Kim, Sang Kyu

    Femtosecond Chemically Activated Reactions: Concept of Nonstatistical Activation at High Thermal Femtosecond chemical activation of reactions at very high thermal energies, much above the bond energy of reactions have been central to chemical kinetics and dynamics. Ideally, with lasers, one wishes to deposit

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

    NASA Technical Reports Server (NTRS)

    Grodzka, P. G.

    1975-01-01

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

  4. A combined quantum-classical dynamics method for calculating thermal rate constants of chemical reactions in solution

    E-print Network

    Truong, Thanh N.

    -flux correlation function for calculating the thermal rate constants of chemical reactions in solution in this study would provide a complete tool for studying the quantum dynamics of chemical reactions the thermal chemical reaction rate constants. Furthermore, we also employ an efficient and accurate quantum

  5. Chemical Reactions

    NSDL National Science Digital Library

    National Science Teachers Association (NSTA)

    2009-05-01

    We don't often stop to think about it, but underlying many of our everyday activities are chemical reactions. From the cooking of an egg to the growth of a child, chemical reactions make things happen. Although many of the reactions that support our lives

  6. Chemical Reactions

    NSDL National Science Digital Library

    Mrs. Hicken

    2009-05-04

    We are going go over a general view of reactions to prepare us for our unit on Chemical Reactions! Have fun learning! WARNING: If you are caught looking at ANY other site, without permission, you will be sent to the ALC, and you will not participate in any other computer activities for the rest of the year. Get your worksheet and begin! Overview Take this quiz and have me come over and sign off on your worksheet when you have completed the quiz! Overview Quiz Next let's take a look at what effect the rate of a chemical reaction. Rates of Reactions Another quiz, another check off by me! Rates of Reactions Quiz Now how do we measure how fast a ...

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

    PubMed

    Craven, Galen T; Bartsch, Thomas; Hernandez, Rigoberto

    2015-02-21

    Chemical reaction rates must increasingly be determined in systems that evolve under the control of external stimuli. In these systems, when a reactant population is induced to cross an energy barrier through forcing from a temporally varying external field, the transition state that the reaction must pass through during the transformation from reactant to product is no longer a fixed geometric structure, but is instead time-dependent. For a periodically forced model reaction, we develop a recrossing-free dividing surface that is attached to a transition state trajectory [T. Bartsch, R. Hernandez, and T. Uzer, Phys. Rev. Lett. 95, 058301 (2005)]. We have previously shown that for single-mode sinusoidal driving, the stability of the time-varying transition state directly determines the reaction rate [G. T. Craven, T. Bartsch, and R. Hernandez, J. Chem. Phys. 141, 041106 (2014)]. Here, we extend our previous work to the case of multi-mode driving waveforms. Excellent agreement is observed between the rates predicted by stability analysis and rates obtained through numerical calculation of the reactive flux. We also show that the optimal dividing surface and the resulting reaction rate for a reactive system driven by weak thermal noise can be approximated well using the transition state geometry of the underlying deterministic system. This agreement persists as long as the thermal driving strength is less than the order of that of the periodic driving. The power of this result is its simplicity. The surprising accuracy of the time-dependent noise-free geometry for obtaining transition state theory rates in chemical reactions driven by periodic fields reveals the dynamics without requiring the cost of brute-force calculations. PMID:25702003

  8. Chemical and thermal stability of N-heterocyclic ionic liquids in catalytic C-H activation reactions.

    PubMed

    Chen, Guanyi; Kang, Shujuan; Ma, Qisheng; Chen, Weiqun; Tang, Yongchun

    2014-11-01

    (1)H-NMR spectrum analyses are applied to study the chemical and thermal stability of selected N-heterocyclic ionic liquids within the reaction system that can highly efficiently activate a C-H bond of methane and convert it into the C-O bond in methanol. Our results indicate that under such reaction conditions involving using a powerful Pt-based catalyst and strong acidic solvent, the aromatic ring of an imidazolium cation becomes unstable generating an ammonium ion (NH(4)(+)). Our results also suggest that the instability of the imidazolium ring is more chemically (participation in reactions) than thermally based. Modifications of the aromatic ring structure such as pyrazolium and triazolium cations can increase the chemical/thermal stability of ionic liquids under these reaction conditions. PMID:24942984

  9. Correlation of shock initiated and thermally initiated chemical reactions in a 1:1 atomic ratio nickel-silicon mixture

    NASA Astrophysics Data System (ADS)

    Krueger, Barry R.; Mutz, Andrew H.; Vreeland, Thad, Jr.

    1991-11-01

    Shock initiated chemical reaction experiments have been performed on a 1:1 atomic ratio mixture of 20- to 45-?m nickel and -325 mesh crystalline silicon powders. It has been observed that no detectable or only minor surface reactions occur between the constituents until a thermal energy threshold is reached, above which the reaction goes to completion. The experiments show the energy difference between virtually no and full reaction is on the order of 5 percent. Differential scanning calorimetery (DSC) of statically pressed powders shows an exothermic reaction beginning at a temperature which decreases with decreasing porosity. Powder, shock compressed to just below the threshold energy, starts to react in the DSC at 621 °C while powder statically pressed to 23% porosity starts to react at about 30 °C higher. Tap density powder starts to react at 891 °C. The DSC reaction initiation temperature of the shock compressed but unreacted powder corresponds to a thermal energy in the powder of 382 J/g which agrees well with the thermal energy produced by a shock wave with the threshold energy (between 384 and 396 J/g). (Thermal energies referenced to 20 °C.) A sharp energy threshold and a direct correlation with DSC results indicates that the mean thermal energy determines whether or not the reaction will propagate in the elemental Ni+Si powder mixture rather than local, particle level conditions. From this it may be concluded that the reaction occurs on a time scale greater than the time constant for thermal diffusion into the particle interiors.

  10. Application of a reversible chemical reaction system to solar thermal power plants

    Microsoft Academic Search

    E. J. Hanseth; Y. S. Won; L. P. Seibowitz

    1980-01-01

    Three distributed dish solar thermal power systems using various applications of SO2\\/SO3 chemical energy storage and transport technology were comparatively assessed. Each system features various roles for the chemical system: (1) energy storage only, (2) energy transport, or (3) energy transport and storage. These three systems were also compared with the dish-Stirling, using electrical transport and battery storage, and the

  11. Application of a reversible chemical reaction system to solar thermal power plants

    NASA Technical Reports Server (NTRS)

    Hanseth, E. J.; Won, Y. S.; Seibowitz, L. P.

    1980-01-01

    Three distributed dish solar thermal power systems using various applications of SO2/SO3 chemical energy storage and transport technology were comparatively assessed. Each system features various roles for the chemical system: (1) energy storage only, (2) energy transport, or (3) energy transport and storage. These three systems were also compared with the dish-Stirling, using electrical transport and battery storage, and the central receiver Rankine system, with thermal storage, to determine the relative merit of plants employing a thermochemical system. As an assessment criterion, the busbar energy costs were compared. Separate but comparable solar energy cost computer codes were used for distributed receiver and central receiver systems. Calculations were performed for capacity factors ranging from 0.4 to 0.8. The results indicate that SO2/SO3 technology has the potential to be more cost effective in transporting the collected energy than in storing the energy for the storage capacity range studied (2-15 hours)

  12. Application of a reversible chemical reaction system to solar thermal power plants

    NASA Astrophysics Data System (ADS)

    Hanseth, E. J.; Won, Y. S.; Seibowitz, L. P.

    1980-08-01

    Three distributed dish solar thermal power systems using various applications of SO2/SO3 chemical energy storage and transport technology were comparatively assessed. Each system features various roles for the chemical system: (1) energy storage only, (2) energy transport, or (3) energy transport and storage. These three systems were also compared with the dish-Stirling, using electrical transport and battery storage, and the central receiver Rankine system, with thermal storage, to determine the relative merit of plants employing a thermochemical system. As an assessment criterion, the busbar energy costs were compared. Separate but comparable solar energy cost computer codes were used for distributed receiver and central receiver systems. Calculations were performed for capacity factors ranging from 0.4 to 0.8. The results indicate that SO2/SO3 technology has the potential to be more cost effective in transporting the collected energy than in storing the energy for the storage capacity range studied (2-15 hours)

  13. Chemical Reactions and Stoichiometry

    NSDL National Science Digital Library

    2012-07-31

    In this activity, students explore reactions in which chemical bonds are formed and broken. Students experiment with changing the temperature and the concentration of the atoms in order to see how these affect reaction rates. They also learn how to communicate what happens during a chemical reaction by writing the ratios of reactants and products, known as stoichiometry.

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

    E-print Network

    Craven, Galen T; Hernandez, Rigoberto

    2015-01-01

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

  15. Thermal-diffusion effects on mixed convection flow in a heat absorbing fluid with Newtonian heating and chemical reaction

    NASA Astrophysics Data System (ADS)

    Hussanan, Abid; Salleh, Mohd Zuki; Tahar, Razman Mat; Khan, Ilyas

    2015-02-01

    Thermal-diffusion and chemical reaction effects on mixed convection heat and mass transfer flow past an infinite oscillating vertical plate with Newtonian heating is investigated. The governing equations are transformed to a system of linear partial differential equations using appropriate non-dimensional variables. Using Laplace transform method the resulting equations are solved analytically and the expression for velocity, temperature and concentration are obtained. They satisfy all imposed initial and boundary conditions. Numerical results for temperature and concentration are shown in various graphs for embedded flow parameters and discussed in details.

  16. General Biology 1, Reactions 1 CHEMICAL REACTIONS *

    E-print Network

    Prestwich, Ken

    General Biology 1, Reactions 1 CHEMICAL REACTIONS * Note: This is the first of a two-part set of notes. This set will review chemical reactions and the next will overview enzymes. What you learn and ribozymes. At their heart, organisms are complex chemical engines. However, many of the chemical reactions

  17. Intro Biology, Reactions 1 CHEMICAL REACTIONS *

    E-print Network

    Prestwich, Ken

    Intro Biology, Reactions 1 CHEMICAL REACTIONS * Note: This is the first of a two-part set of notes. This set will review chemical reactions and the next will overview enzymes. What you learn in these two and ribozymes. At their heart, organisms are complex chemical engines. However, many of the chemical reactions

  18. Multimass thermal desorption spectroscopy as a monitoring device for chemical reaction products

    Microsoft Academic Search

    G. Zagatta; U. Heinzmann

    1994-01-01

    To observe the products of surface reaction mechanisms we combined a standard quadrupole mass spectrometer featuring high-speed scanning options with fast data acquisition and a computer-controlled sample heating system. This combination served to obtain a general view (like a ‘‘fingerprint’’) of the reaction occurring on a Pt(100) crystal upon heating the adsorbate covered surface, as well as to allow for

  19. Chemical ReactionsChemical Reactions between the Componentsbetween the Components

    E-print Network

    Beauchamp, Jack

    1 Chemical ReactionsChemical Reactions between the Componentsbetween the Components of MolecularMethodology We induce chemical reactions in molecular aggregates by collisionally activating the clusters of AMP to ATP by CID: Julian, RJ and J.L. Beauchamp IJMS 2003, 227(1), 147-159. Reaction of Gas

  20. Categorizing Chemical Reactions

    NSDL National Science Digital Library

    National Science Teachers Association (NSTA)

    2009-07-10

    Science Objects are two hour on-line interactive inquiry-based content modules that help teachers better understand the science content they teach. This Science Object is the second of four Science Objects in the Chemical Reactions SciPack. It provides an

  1. Rates of Chemical Reactions

    NSDL National Science Digital Library

    National Science Teachers Association (NSTA)

    1900-01-01

    Science Objects are two hour on-line interactive inquiry-based content modules that help teachers better understand the science content they teach. This Science Object is the third of four Science Objects in the Chemical Reactions SciPack. It demonstrates

  2. Reaction Kinetics Analysis of Chemical Changes in Pressure-Assisted Thermal Processing

    Microsoft Academic Search

    Rosario Ramirez; Jorge Saraiva; Concepción Pérez Lamela; J. Antonio Torres

    2009-01-01

    Pressure-assisted thermal processing (PATP) at T < 100°C can be used when enzyme inactivation and pasteurization by high pressure processing (HPP) is not feasible due to\\u000a long processing times while PATP at T > 100°C can be used when bacterial spores inactivation is necessary. In PATP, the adiabatic compression\\/decompression heat\\u000a increases\\/decreases temperature almost instantaneously, and the simultaneous application of high pressure (~600–700 MPa) and\\u000a temperature

  3. Chemical Reactions at Surfaces

    SciTech Connect

    Michael Henderson and Nancy Ryan Gray

    2010-04-14

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

  4. Ultrafast Laser Spectroscopyof Chemical Reactions

    E-print Network

    Zewail, Ahmed

    Ultrafast Laser Spectroscopyof Chemical Reactions - Joseph L. Kneeand AhmedH. Zewail California of chemical physics is to understand how chemi- cal reactions complete their journey from reactants to prod at the molecular level. The making of new bonds (and the breaking of old ones) in elementary chemical reactions

  5. Chemical Reactions in DSMC

    NASA Astrophysics Data System (ADS)

    Bird, G. A.

    2011-05-01

    DSMC simulations of chemically reacting gas flows have generally employed procedures that convert the macroscopic chemical rate equations to reaction cross-sections at the microscopic level. They therefore depend on the availability of experimental data that has been fitted to equations of the Arrhenius form. This paper presents a physical model for dissociation and recombination reactions and a phenomenological model for exchange and chain reactions. These are based on the vibrational states of the colliding molecules and do not require any experimentally-based data. The simplicity of the models allows the corresponding rate equations to be written down and, while these are not required for the implementation of the models, they facilitate their validation. The model is applied to a typical hypersonic atmospheric entry problem and the results are compared with the corresponding results from the traditional method. It is also used to investigate both spontaneous and forced ignition as well as the structure of a deflagration wave in an oxygen-hydrogen mixture.

  6. Concordant Chemical Reaction Networks

    E-print Network

    Shinar, Guy

    2011-01-01

    We describe a large class of chemical reaction networks, those endowed with a subtle structural property called concordance. We show that the class of concordant networks coincides precisely with the class of networks which, when taken with any weakly monotonic kinetics, invariably give rise to kinetic systems that are injective --- a quality that, among other things, precludes the possibility of switch-like transitions between distinct positive steady states. We also provide persistence characteristics of concordant networks, instability implications of discordance, and consequences of stronger variants of concordance. Some of our results are in the spirit of recent ones by Banaji and Craciun, but here we do not require that every species suffer a degradation reaction. This is especially important in studying biochemical networks, for which it is rare to have all species degrade.

  7. A preliminary study on numerical simulation of microwave heating process for chemical reaction and discussion of hotspot and thermal runaway phenomenon

    Microsoft Academic Search

    Xiang Zhao; Kama Huang; Liping Yan; Yuan Yao

    2009-01-01

    The nonlinear process of microwave heating chemical reaction is studied by means of numerical simulation. Especially, the\\u000a variation of temperature in terms of space and time, as well as the hotspot and thermal runaway phenomena are discussed. Suppose\\u000a the heated object is a cylinder and the incident electromagnetic (EM) wave is plane wave, the problem turns out to be a

  8. A review of reaction rates and thermodynamic and transport properties for the 11-species air model for chemical and thermal nonequilibrium calculations to 30000 K

    NASA Technical Reports Server (NTRS)

    Gupta, Roop N.; Yos, Jerrold M.; Thompson, Richard A.

    1989-01-01

    Reaction rate coefficients and thermodynamic and transport properties are provided for the 11-species air model which can be used for analyzing flows in chemical and thermal nonequilibrium. Such flows will likely occur around currently planned and future hypersonic vehicles. Guidelines for determining the state of the surrounding environment are provided. Approximate and more exact formulas are provided for computing the properties of partially ionized air mixtures in such environments.

  9. Magnetic Effects in Chemical Reactions

    Microsoft Academic Search

    Anatolii L Buchachenko

    1976-01-01

    The Review discusses in what elementary chemical reactions the intrinsic angular momentum of electrons and nuclei is conserved and in what reactions it is not conserved, how weak electron-nuclear magnetic interaction and an external magnetic field influence the conservation of angular momentum and what are the consequences of this effect, and what magnetic effects occur in chemical reactions, as well

  10. Chemical Master versus Chemical Langevin for First-Order Reaction Networks

    E-print Network

    Mottram, Nigel

    Chemical Master versus Chemical Langevin for First-Order Reaction Networks Desmond J. Higham Raya;1 Motivation A system of chemical reactions at thermal equilibrium is traditionally modelled as a collection in typical chemical reactions, the RRE is a per- fectly adequate model. However, there are some application

  11. Computed potential energy surfaces for chemical reactions

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1994-01-01

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

  12. First Order Chemical Reaction Effects on Exponentially Accelerated Vertical Plate with Variable Mass Diffusion in the Presence of Thermal Radiation

    NASA Astrophysics Data System (ADS)

    Muthucumaraswamy, R.; Lakshmi, C. S.

    2015-05-01

    Effects of transfer of mass and free convection on the flow field of an incompressible viscous fluid past an exponentially accelerated vertical plate with variable surface temperature and mass diffusion are studied. Results for velocity, concentration, temperature are obtained by solving governing equations using the Laplace transform technique. It is observed that the velocity increases with decreasing values of the chemical reaction parameter or radiation parameter. But the trend is just reversed with respect to the time parameter. The skin friction is also studied.

  13. Temperature and Concentration Stratification Effects in Mixed Convection Flow of an Oldroyd-B Fluid with Thermal Radiation and Chemical Reaction

    PubMed Central

    Hayat, Tasawar; Muhammad, Taseer; Shehzad, Sabir Ali; Alsaedi, Ahmed

    2015-01-01

    This research addresses the mixed convection flow of an Oldroyd-B fluid in a doubly stratified surface. Both temperature and concentration stratification effects are considered. Thermal radiation and chemical reaction effects are accounted. The governing nonlinear boundary layer equations are converted to coupled nonlinear ordinary differential equations using appropriate transformations. Resulting nonlinear systems are solved for the convergent series solutions. Graphs are plotted to examine the impacts of physical parameters on the non-dimensional temperature and concentration distributions. The local Nusselt number and the local Sherwood number are computed and analyzed numerically. PMID:26102200

  14. Quantum chemical investigation of the primary thermal pyrolysis reactions of the sodium carboxylate group in a brown coal model.

    PubMed

    Li, Jian; Zhang, Baisheng; Zhang, Zhiqiang; Yan, Kefeng; Kang, Lixun

    2014-12-01

    The primary pyrolysis mechanisms of the sodium carboxylate group in sodium benzoate-used as a model compound of brown coal-were studied by performing quantum chemical computations using B3LYP and the CBS method. Various possible reaction pathways involving reactions such as unimolecular and bimolecular decarboxylation and decarbonylation, crosslinking, and radical attack in the brown coal matrix were explored. Without the participation of reactive radicals, unimolecular decarboxylation to release CO2 was calculated to be the most energetically favorable primary reaction pathway at the B3LYP/6-311+G (d, p) level of theory, and was also found to be more energetically favorable than decarboxylation of an carboxylic acid group. When CBS-QBS results were included, crosslinking between the sodium carboxylate group and the carboxylic acid and the decarboxylation of the sodium carboxylate group (catalyzed by the phenolic hydroxyl group) were found to be possible; this pathway competes with unimolecular decarboxylation of the sodium carboxylate group. Provided that H and CH3 radicals are present in the brown coal matrix and can access the sodium carboxylate group, accelerated pyrolysis of the sodium carboxylate group becomes feasible, leading to the release of an Na atom or an NaCO2 radical at the B3LYP/6-311+G (d, p) or CBS-QB3 level of theory, respectively. PMID:25451141

  15. International chemical identifier for chemical reactions

    E-print Network

    Grethe, Guenter; Goodman, Jonathan; Allen, Chad

    2013-03-22

    ORAL PRESENTATION Open Access International chemical identifier for chemical reactions Guenter Grethe1*, Jonathan Goodman2, Chad Allen2 From 8th German Conference on Chemoinformatics: 26 CIC-Workshop Goslar, Germany. 11-13 November 2012 An open... -access software for creating a unique, text-based identifier for reactions (RInChI) was developed by the Goodman group at the University of Cambridge, based on the IUPAC International Chemical Identifier (InChI) stan- dard. RInChIs describe the substances...

  16. Speeding chemical reactions by focusing

    E-print Network

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

    2012-12-13

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

  17. Speeding chemical reactions by focusing

    E-print Network

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

    2012-01-01

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

  18. Geometric description of chemical reactions

    E-print Network

    Hernando Quevedo; Diego Tapias

    2013-01-02

    We use the formalism of Geometrothermodynamics to describe chemical reactions in the context of equilibrium thermodynamics. Any chemical reaction in a closed system is shown to be described by a geodesic in a $2-$dimensional manifold that can be interpreted as the equilibrium space of the reaction. We first show this in the particular cases of a reaction with only two species corresponding to either two ideal gases or two van der Waals gases. We then consider the case of a reaction with an arbitrary number of species. The initial equilibrium state of the geodesic is determined by the initial conditions of the reaction. The final equilibrium state, which follows from a thermodynamic analysis of the reaction, is shown to correspond to a coordinate singularity of the thermodynamic metric which describes the equilibrium manifold.

  19. Geometric description of chemical reactions

    E-print Network

    Quevedo, Hernando

    2013-01-01

    We use the formalism of Geometrothermodynamics to describe chemical reactions in the context of equilibrium thermodynamics. Any chemical reaction in a closed system is shown to be described by a geodesic in a $2-$dimensional manifold that can be interpreted as the equilibrium space of the reaction. We first show this in the particular cases of a reaction with only two species corresponding to either two ideal gases or two van der Waals gases. We then consider the case of a reaction with an arbitrary number of species. The initial equilibrium state of the geodesic is determined by the initial conditions of the reaction. The final equilibrium state, which follows from a thermodynamic analysis of the reaction, is shown to correspond to a coordinate singularity of the thermodynamic metric which describes the equilibrium manifold.

  20. Chemical burn or reaction

    MedlinePLUS

    ... the skin has come in contact with the toxic substance Rash , blisters , burns on the skin Unconsciousness ... locked cabinet. Avoid mixing different products that contain toxic chemicals such as ammonia and bleach. The mixture ...

  1. Chemical and Thermal Analysis

    NASA Technical Reports Server (NTRS)

    Bulluck, J. W.; Rushing, R. A.

    1994-01-01

    Thermal decomposition activation energies have been determined using two methods of Thermogravimetric Analysis (TGA), with good correlation being obtained between the two techniques. Initial heating curves indicated a two-component system for Coflon (i.e. polymer plus placticizer) but a single component system for Tefzel. Two widely differing activation energies were for Coflon supported this view, 15 kcl/mol being associated with plasticizer, and 40 kcal/mol with polymer degradation. With Tefzel, values were 40-45 kcal/mol, the former perhaps being associated with a low molecular weight fraction. Appropriate acceleration factors have been determined. Thermomechanical Analysis (TMA) has shown considerable dimensional change during temperature cycles. For unaged pipe sections heating to 100 C and then holding the temperature resulted in a stable thickness increase of 2%, whereas the Coflon thickness decreased continuously, reaching -4% in 2.7 weeks. Previously strained tensile bars of Tefzel expanded on cooling during TMA. SEM performed on H2S-aged Coflon samples showed significant changes in both physical and chemical nature. The first may have resulted from explosive decompression after part of the aging process. Chemically extensive dehydrofluorination was indicated, and sulfur was present as a result of the aging. These observations indicate that chemical attack of PVDF can occur in some circumstances.

  2. Solar-thermal reaction processing

    DOEpatents

    Weimer, Alan W; Dahl, Jaimee K; Lewandowski, Allan A; Bingham, Carl; Raska Buechler, Karen J; Grothe, Willy

    2014-03-18

    In an embodiment, a method of conducting a high temperature chemical reaction that produces hydrogen or synthesis gas is described. The high temperature chemical reaction is conducted in a reactor having at least two reactor shells, including an inner shell and an outer shell. Heat absorbing particles are included in a gas stream flowing in the inner shell. The reactor is heated at least in part by a source of concentrated sunlight. The inner shell is heated by the concentrated sunlight. The inner shell re-radiates from the inner wall and heats the heat absorbing particles in the gas stream flowing through the inner shell, and heat transfers from the heat absorbing particles to the first gas stream, thereby heating the reactants in the gas stream to a sufficiently high temperature so that the first gas stream undergoes the desired reaction(s), thereby producing hydrogen or synthesis gas in the gas stream.

  3. LEGO® Chemical Reactions

    NSDL National Science Digital Library

    Kathleen M. Vandiver, Ph.D.

    2009-01-01

    This activity uses LEGO® bricks to represent atoms bonding into molecules and crystals. The lesson plan is for a 2.5 hour workshop (or four 45-minute classes). There is a "wet lab" chemistry experiment (mixing baking soda and calcium chloride with phenol red indicator), followed by a "LEGO lab" modeling phase that includes writing formulas using chemical notation. This lesson is also offered as a 2.5 hour field trip lesson at the MIT Edgerton Center.

  4. A review of reaction rates and thermodynamic and transport properties for an 11-species air model for chemical and thermal nonequilibrium calculations to 30000 K

    NASA Technical Reports Server (NTRS)

    Gupta, Roop N.; Yos, Jerrold M.; Thompson, Richard A.; Lee, Kam-Pui

    1990-01-01

    Reaction rate coefficients and thermodynamic and transport properties are reviewed and supplemented for the 11-species air model which can be used for analyzing flows in chemical and thermal nonequilibrium up to temperatures of 3000 K. Such flows will likely occur around currently planned and future hypersonic vehicles. Guidelines for determining the state of the surrounding environment are provided. Curve fits are given for the various species properties for their efficient computation in flowfield codes. Approximate and more exact formulas are provided for computing the properties of partially ionized air mixtures in a high energy environment. Limitations of the approximate mixing laws are discussed for a mixture of ionized species. An electron number-density correction for the transport properties of the charged species is obtained. This correction has been generally ignored in the literature.

  5. Experimental Demonstrations in Teaching Chemical Reactions.

    ERIC Educational Resources Information Center

    Hugerat, Muhamad; Basheer, Sobhi

    2001-01-01

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

  6. Application of Reversible Chemical Reactions for Temperature Amplification 

    E-print Network

    Ally, M. R.; Rebello, W. J.; Suciu, D. F.

    1985-01-01

    temperature thermal energy, mechanical and absorption type heat pumps have been proposed and developed so far. This paper addresses itself to the concept of a heat reaction chemical heat pump (HRCHP). The HRCHP concept is aimed to upgrade low temperature...

  7. Application of Reversible Chemical Reactions for Temperature Amplification

    E-print Network

    Ally, M. R.; Rebello, W. J.; Suciu, D. F.

    temperature thermal energy, mechanical and absorption type heat pumps have been proposed and developed so far. This paper addresses itself to the concept of a heat reaction chemical heat pump (HRCHP). The HRCHP concept is aimed to upgrade low temperature...

  8. Homeostasis in Chemical Reaction Pathways

    E-print Network

    Malyshev, V A; Zamyatin, A A

    2011-01-01

    We consider stochastic models of chemical reaction networks with time dependent input rates and several types of molecules. We prove that, in despite of strong time dependence of input rates, there is a kind of homeostasis phenomenon: far away from input nodes the mean numbers of molecules of each type become approximately constant (do not depend on time).

  9. Homeostasis in Chemical Reaction Pathways

    E-print Network

    V. A. Malyshev; A. D. Manita; A. A. Zamyatin

    2011-12-25

    We consider stochastic models of chemical reaction networks with time dependent input rates and several types of molecules. We prove that, in despite of strong time dependence of input rates, there is a kind of homeostasis phenomenon: far away from input nodes the mean numbers of molecules of each type become approximately constant (do not depend on time).

  10. Nanomotors Propelled by Chemical Reactions

    NASA Astrophysics Data System (ADS)

    Kapral, Raymond

    2013-12-01

    Molecular motors, like their macroscopic counterparts, consume energy and convert it to work; however, unlike macroscopic motors, they are subject to strong fluctuations and do not rely on inertia for their operation. In this chapter, the dynamics of synthetic chemically-powered nanomotors and mechanisms by which they operate are described. The focus is on motors that propel themselves by utilizing fuel in the environment to generate their own concentration gradients through chemical reactions. Macroscopic diffusiophoretic mechanisms for such motions are discussed, as well as microscopic and mesoscopic descriptions of motor dynamics.

  11. Chemical energy storage system for SEGS solar thermal power plant

    Microsoft Academic Search

    D. R. Brown; J. L. Lamarche; G. E. Spanner

    1991-01-01

    In October 1988, a symposium was held in Helendale, California, to discuss thermal energy storage (TES) concepts applicable to medium temperature (200 to 400 C) solar thermal electric power plants, in general, and the solar electric generating system (SEGS) plants developed by Luz International, in particular. Chemical reaction energy storage based on the reversible reaction between metal oxides and metal

  12. THEORY OF CHEMICAL REACTION ANTONIO LAGANA

    E-print Network

    Auzinsh, Marcis

    THEORY OF CHEMICAL REACTION DYNAMICS Edited by: ANTONIO LAGANA Department of Chemistry University Theoretical treatment of the dynamics of chemical reactions has undergone a spectacular development during the NATO Advanced Research Work- shop on the Theory of the Dynamics of Chemical Reactions in Balatonf

  13. GENERALIZED TOPOLOGIES: HYPERGRAPHS, CHEMICAL REACTIONS, AND

    E-print Network

    Flamm, Christoph

    GENERALIZED TOPOLOGIES: HYPERGRAPHS, CHEMICAL REACTIONS, AND BIOLOGICAL EVOLUTION Christoph Flamm1;INTRODUCTION Investigations into general principles underlying chemical reaction networks, molecular [21, 66, 62, 31, 59, 56, 22, 60]. Chemical Reaction Networks. We start from a fixed set X of molecular

  14. Leaderless deterministic chemical reaction networks Monir Hajiaghayi

    E-print Network

    Doty, David

    Leaderless deterministic chemical reaction networks David Doty Monir Hajiaghayi Abstract This paper is deterministically computable by a stochastic chemical reaction network (CRN) if and only if the graph of f in a well-mixed solution, the language of chemical reaction networks (CRNs) is an attractive choice. A CRN

  15. Collisions, Chemical Reactions, and Transport Chemistry 223

    E-print Network

    Ronis, David M.

    Collisions, Chemical Reactions, and Transport Chemistry 223 David Ronis McGill University 1 for a number of practical con- siderations; e.g., if a chemical reaction takes place every time a molecule hits, introduced earlier. Aside from the previously mentioned example of chemical reaction on a surface, another

  16. Physics 112 Equilibrium in Chemical Reactions

    E-print Network

    Young, A. Peter

    Physics 112 Equilibrium in Chemical Reactions Peter Young I. FORMALISM This is a considerably that it is indeed a minimum. In this handout we discuss chemical reactions, which take place not at constant volume next give some examples of chemical reactions which we will use to illustrate the theory in what

  17. Theory of chemical reaction dynamics. Volume 4

    SciTech Connect

    Baer, M.

    1985-01-01

    This book examines some of the basic principles behind chemical reaction kinetics. Topics considered include generalized transition state theory, statistical dynamics, the theory of reactions at a solid surface, and the theory of reactions in solution.

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

    Microsoft Academic Search

    James R. Skorpik; Michael G. Dodson

    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

  19. Holographic Thermalization with Chemical Potential

    E-print Network

    Elena Caceres; Arnab Kundu

    2012-05-25

    We study the thermalization of a strongly coupled quantum field theory in the presence of a chemical potential. More precisely, using the holographic prescription, we calculate non- local operators such as two point function, Wilson loop and entanglement entropy in a time- dependent background that interpolates between AdSd+1 and AdSd+1 -Reissner-Nordstr\\"om for d = 3, 4. We find that it is the entanglement entropy that thermalizes the latest and thus sets a time-scale for equilibration in the field theory. We study the dependence of the thermalization time on the probe length and the chemical potential. We find an interesting non-monotonic behavior. For a fixed small value of T l and small values of \\mu/T the thermalization time decreases as we increase \\mu/T, thus the plasma thermalizes faster. For large values of \\mu/T the dependence changes and the thermalization time increases with increasing \\mu/T . On the other hand, if we increase the value of T l this non-monotonic behavior becomes less pronounced and eventually disappears indicating two different regimes for the physics of thermalization: non-monotonic dependence of the thermalization time on the chemical potential for T l > 1.

  20. M. Bahrami ENSC 461 (S 11) Chemical Reactions 1 Chemical Reactions

    E-print Network

    Bahrami, Majid

    M. Bahrami ENSC 461 (S 11) Chemical Reactions 1 Chemical Reactions When analyzing reacting systemsHm. For example octane is C8H18. Combustion: is a chemical reaction during which a fuel is oxidized and a large.28 #12;M. Bahrami ENSC 461 (S 11) Chemical Reactions 2 Where N is the number of moles and M is the molar

  1. A Method for IncorporatingA Method for Incorporating Chemical Reactions intoChemical Reactions into

    E-print Network

    Politècnica de Catalunya, Universitat

    A Method for IncorporatingA Method for Incorporating Chemical Reactions intoChemical Reactions Vilarrasa, Francesca De Gaspari, Orlando Silva, Jesús Carrera #12;Introduction "Chemical reactions" in CODE), CO3 2-, OH- 5 Chemical reactions: CaCO3(s) + H+ = Ca2+ + HCO3 - CO2(aq) = CO2(g) H+ + HCO3 - = H2

  2. Timing in chemical reaction networks Chemical reaction networks (CRNs) formally model chem-

    E-print Network

    Doty, David

    Timing in chemical reaction networks David Doty Abstract Chemical reaction networks (CRNs) formally the interactions of molecular species in a well-mixed solution is that of (fi- nite) chemical reaction networks (CRNs), i.e., finite sets of chemical reactions such as A+B A+C. When the behavior of individual

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

    NASA Astrophysics Data System (ADS)

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

    2011-09-01

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

  4. A reversible nanoconfined chemical reaction.

    PubMed

    Nielsen, Thomas K; Bösenberg, Ulrike; Gosalawit, Rapee; Dornheim, Martin; Cerenius, Yngve; Besenbacher, Flemming; Jensen, Torben R

    2010-07-27

    Hydrogen is recognized as a potential, extremely interesting energy carrier system, which can facilitate efficient utilization of unevenly distributed renewable energy. A major challenge in a future "hydrogen economy" is the development of a safe, compact, robust, and efficient means of hydrogen storage, in particular, for mobile applications. Here we report on a new concept for hydrogen storage using nanoconfined reversible chemical reactions. LiBH4 and MgH2 nanoparticles are embedded in a nanoporous carbon aerogel scaffold with pore size Dmax approximately 21 nm and react during release of hydrogen and form MgB2. The hydrogen desorption kinetics is significantly improved compared to bulk conditions, and the nanoconfined system has a high degree of reversibility and stability and possibly also improved thermodynamic properties. This new scheme of nanoconfined chemistry may have a wide range of interesting applications in the future, for example, within the merging area of chemical storage of renewable energy. PMID:20533850

  5. Learning to Predict Chemical Reactions

    PubMed Central

    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 is generalizable, making reasonable predictions over reactants and conditions which the rule-based expert does not handle. A web interface to the machine learning based mechanistic reaction predictor is accessible through our chemoinformatics portal (http://cdb.ics.uci.edu) under the Toolkits section. PMID:21819139

  6. Classes of Chemical Reactions Reactions in aqueous media

    E-print Network

    Zakarian, Armen

    Classes of Chemical Reactions Reactions in aqueous media · Precipitation reactions · Acid + electrolytes: a substance that conducts an electric current when dissolved in water Acids are donors of H+ (this is a definition) HBr ! H3O+ + Br¯ or HBr ! H+ + Br¯ Equations for Aqueous Ionic Reactions

  7. Chemical reactions at aqueous interfaces

    NASA Astrophysics Data System (ADS)

    Vecitis, Chad David

    2009-12-01

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

  8. Invited Review Biologically Relevant Chemical Reactions of

    E-print Network

    Gates, Kent. S.

    Invited Review Biologically Relevant Chemical Reactions of N7-Alkylguanine Residues in DNA Kent S set out here to provide an overview of the biologically relevant chemical reactions of N7-alkylgua-Catalyzed Depurination 841 3.2. Chemical Mechanism for the Depurination of N7-Alkylguanine Residues 842 3.3. Overview

  9. Chemical and Thermal Analysis

    NASA Technical Reports Server (NTRS)

    Bulluck, J. W.; Rushing, R. A.

    1995-01-01

    During the past six months we have conducted significant research in several domains in order to clarify and understanding the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) for pipes. We organized numerous analytical studies with methods including Fourier Transform Infrared Spectroscopy, Dynamic Mechanical Analysis, Differential Scanning Calorimetry, and Stress Relaxation experiments. In addition we have reanalyzed previous thermogravimetric data concerning the rate of deplasticization of Coflon pipe. We investigated a number of aged samples of both Tefzel and Coflon that were forwarded from MERL. We conducted stress relaxation experiments of Coflon pipe at several temperatures and determined an activation energy. We also examined the dynamic mechanical response PVDF during deplasticization and during methanol plasticization. We performed numerous DSC analyses to research the changing crystalline morphology. We have noted significant changes in crystallinity upon aging for both PVDF and Tefzel. Little variation in elemental composition was noted for many of the aged Coflon and Tefzel samples tested.

  10. Reaction efficiency effects on binary chemical reactions.

    PubMed

    Lazaridis, Filippos; Savara, Aditya; Argyrakis, Panos

    2014-09-14

    We study the effect of the variation of reaction efficiency in binary reactions. We use the well-known A + B ? 0 model, which has been extensively studied in the past. We perform simulations on this model where we vary the efficiency of reaction, i.e., when two particles meet they do not instantly react, as has been assumed in previous studies, but they react with a probability ?, where ? is in the range 0 < ? < 1. Our results show that at small ? values the system is reaction limited, but as ? increases it crosses over to a diffusion limited behavior. At early times, for small ? values, the particle density falls slower than for larger ? values. This fall-off goes over a crossover point, around the value of ? = 0.50 for high initial densities. Under a variety of conditions simulated, we find that the crossover point was dependent on the initial concentration but not on the lattice size. For intermediate and long times simulations, all ? values (in the depleted reciprocal density versus time plot) converge to the same behavior. These theoretical results are useful in models of epidemic reactions and epidemic spreading, where a contagion from one neighbor to the next is not always successful but proceeds with a certain probability, an analogous effect with the reaction probability examined in the current work. PMID:25217900

  11. The 1st Law of Thermodynamics in Chemical Reactions

    E-print Network

    I. A. Stepanov

    2000-11-10

    In the previous papers of the author it has been shown that the 1st law of thermodynamics in chemical reactions is the following one: dU=dQ+PdV+SUM In the present paper this theory was developed and it has been shown that the 1st law of thermodynamics in chemical reactions has the following form: dC=-dU+dA and -dU=dQ where dC is the change in the chemical energy, dU is the change in the internal energy. Internal energy is the energy of thermal motion of molecules.

  12. Thermodynamic performance for a chemical reactions model

    NASA Astrophysics Data System (ADS)

    Gonzalez-Narvaez, R. E.; Sánchez-Salas, N.; Chimal-Eguía, J. C.

    2015-01-01

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

  13. 2005 Chemical Reactions at Surfaces

    SciTech Connect

    Cynthia M. Friend

    2006-03-14

    The Gordon Research Conference (GRC) on 2005 Chemical Reactions at Surfaces was held at Ventura Beach Marriott, Ventura California from February 13, 2005 through February 18, 2005. The Conference was well-attended with 124 participants (attendees list attached). The attendees represented the spectrum of endeavor in this field coming from academia, industry, and government laboratories, both U.S. and foreign scientists, senior researchers, young investigators, and students. In designing the formal speakers program, emphasis was placed on current unpublished research and discussion of the future target areas in this field. There was a conscious effort to stimulate lively discussion about the key issues in the field today. Time for formal presentations was limited in the interest of group discussions. In order that more scientists could communicate their most recent results, poster presentation time was scheduled. Attached is a copy of the formal schedule and speaker program and the poster program. In addition to these formal interactions, 'free time' was scheduled to allow informal discussions. Such discussions are fostering new collaborations and joint efforts in the field.

  14. Chemical reactions in low-g

    NASA Technical Reports Server (NTRS)

    Grodzka, P. G.; Facemire, B. R.

    1978-01-01

    The Apollo-Soyuz flight experiment, 'Chemical Foams' demonstrated that foams and air/liquid dispersions are much more stable in low-gravity than on the ground. It thus should be possible to conduct unique chemical reactions in space foams. The low-g results and subsequent ground work on the formaldehyde clock reaction indicate that the reaction is strongly influenced by (1) dissociated and undissociated solution species being adsorbed at solid/liquid and gas/liquid surfaces and (2) chemical reaction rates apparently being affected by long-range forces determined by the liquid mass and the extent and nature of all surface interfaces.

  15. 'GREENER' CHEMICAL SYNTHESES USING ALTERNATE REACTION CONDITIONS

    EPA Science Inventory

    Microwave (MW) irradiation in conjunction with water as reaction media has proven to be a greener chemical approach for expeditious N-alkylation reactions of amines and hydrazines wherein the reactions under mildly basic conditions afford tertiary amines and double N-alkylation t...

  16. A Unified Theory of Chemical Reactions

    E-print Network

    Aubry, S

    2014-01-01

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

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

    DOEpatents

    Skorpik, J.R.; Dodson, M.G.

    1999-05-25

    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. 8 figs.

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

    DOEpatents

    Skorpik, James R. (Kennewick, WA); Dodson, Michael G. (Richland, WA)

    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. Thermal, chemical, and mechanical cookoff modeling

    SciTech Connect

    Hobbs, M.L.; Baer, M.R.; Gross, R.J.

    1994-08-01

    A Thermally Reactive, Elastic-plastic eXplosive code, TREX, has been developed to analyze coupled thermal, chemical and mechanical effects associated with cookoff simulation of confined or unconfined energetic materials. In confined systems, pressure buildup precedes thermal runaway, and unconfined energetic material expands to relieve high stress. The model was developed based on nucleation, decomposition chemistry, and elastic/plastic mechanical behavior of a material with a distribution of internal defects represented as clusters of spherical inclusions. A local force balance, with mass continuity constraints, forms the basis of the model requiring input of temperature and reacted gas fraction. This constitutive material model has been incorporated into a quasistatic mechanics code SANTOS as a material module which predicts stress history associated with a given strain history. The thermal-chemical solver XCHEM has been coupled to SANTOS to provide temperature and reacted gas fraction. Predicted spatial history variables include temperature, chemical species, solid/gas pressure, solid/gas density, local yield stress, and gas volume fraction. One-Dimensional Time to explosion (ODTX) experiments for TATB and PBX 9404 (HMX and NC) are simulated using global multistep kinetic mechanisms and the reactive elastic-plastic constitutive model. Pressure explosions, rather than thermal runaway, result in modeling slow cookoff experiments of confined conventional energetic materials such as TATB. For PBX 9404, pressure explosions also occur at fast cookoff conditions because of low temperature reactions of nitrocellulose resulting in substantial pressurization. A demonstrative calculation is also presented for reactive heat flow in a hollow, propellant-filled, stainless steel cylinder, representing a rocket motor. This example simulation show

  20. Chemical reaction equilibrium in nanoporous materials: NO dimerization reaction in carbon slit nanopores

    E-print Network

    Lisal, Martin

    Chemical reaction equilibrium in nanoporous materials: NO dimerization reaction in carbon slit of confinement on chemical reaction equilibrium in nanoporous materials. We use the reaction ensemble Monte Carlo of confinement on chemical properties, particularly on chemical reaction equilibria. A chemical reaction

  1. Controlling chemical reactions of a single particle

    E-print Network

    Ratschbacher, Lothar; Sias, Carlo; Köhl, Michael

    2012-01-01

    The control of chemical reactions is a recurring theme in physics and chemistry. Traditionally, chemical reactions have been investigated by tuning thermodynamic parameters, such as temperature or pressure. More recently, physical methods such as laser or magnetic field control have emerged to provide completely new experimental possibilities, in particular in the realm of cold collisions. The control of reaction pathways is also a critical component to implement molecular quantum information processing. For these undertakings, single particles provide a clean and well-controlled experimental system. Here, we report on the experimental tuning of the exchange reaction rates of a single trapped ion with ultracold neutral atoms by exerting control over both their quantum states. We observe the influence of the hyperfine interaction on chemical reaction rates and branching ratios, and monitor the kinematics of the reaction products. These investigations advance chemistry with single trapped particles towards achi...

  2. Thermal Plasma Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Lu, Zhipeng

    Diamond has many unrivaled properties and has great application potentials in modern industry. Among various metastable chemical vapor deposition methods for producing diamond, thermal plasma chemical vapor deposition has shown advantages of offering high growth rates and high quality. However, systematic parametric studies are needed for optimization of the process. This study investigates the effects of substrate materials, substrate temperatures, substrate pre-treatment methods, precursor concentrations, and process pressures on the initial nucleation, growth rate, morphology, and quality of the diamond films under thermal plasma conditions. X-ray diffraction, optical microscopy, scanning electron microscopy, and Raman spectroscopy have been used for the diamond film characterization. Thermal plasmas have been also used to deposit homoepitaxial diamond films at high growth rates. High quality macro-sized diamond crystals have been grown on {100} and {110} oriented natural type IIa diamond seeds. Raman spectra reveal that the diamond deposit is of high quality. Laue X-ray diffraction patterns show that the diamond grown on the seed is single crystal and oriented epitaxially with the underlying seed crystal. The gas phase chemistry has been calculated using computer code SOLGASMIX to determine the equilibrium gaseous composition in thermal plasmas. Key species concentrations have been obtained under various pressure conditions. Although kinetic factors have not been taken into account, equilibrium conditions offer an estimation of the process justified by the "frozen chemistry" associated with the fast quenching in the boundary layer. Due to the strong emission of the highly luminous plasma plumes, it has been difficult to measure the in -situ substrate temperature distribution with conventional infrared optical pyrometers. A new technique has been developed to obtain the surface temperature distribution of the substrate by combining the experimental temperature measurements of an array of thermocouples imbedded in the substrate and analytical solutions of the two-dimensional heat conduction equation. This method enables an indirect determination of the substrate temperature distribution.

  3. Solar thermal aerosol flow reaction process

    DOEpatents

    Weimer, Alan W.; Dahl, Jaimee K.; Pitts, J. Roland; Lewandowski, Allan A.; Bingham, Carl; Tamburini, Joseph R.

    2005-03-29

    The present invention provides an environmentally beneficial process using concentrated sunlight to heat radiation absorbing particles to carry out highly endothermic gas phase chemical reactions ultimately resulting in the production of hydrogen or hydrogen synthesis gases.

  4. Reaction driven convection around a stably stratified chemical front.

    PubMed

    D'Hernoncourt, J; Zebib, A; De Wit, A

    2006-04-21

    A vertical stratification of a light and hot fluid over a heavy and cold one is expected to be stable with regard to buoyancy-driven convection. Here we show that chemical reactions can trigger convection around chemical fronts even in cases where concentration and heat both contribute to a stable density stratification. The balance between intrinsic thermal and solutal density gradients initiated by a spatially localized reaction zone and double diffusive mechanisms are at the origin of a new convective instability, the mechanism of which is explained by a displaced particle argument. Linear stability analysis of a reaction-diffusion-convection model confirmed by nonlinear simulations delimits the instability region in the parameter space spanned by the thermal and solutal Rayleigh numbers. Experimental systems in which to test our theoretical predictions are proposed. PMID:16712159

  5. Thermo-chemical dynamics and chemical quasi-equilibrium of plasmas in thermal non-equilibrium

    SciTech Connect

    Massot, Marc [Laboratoire EM2C, UPR 288 CNRS - Ecole Centrale Paris (France); Graille, Benjamin [Laboratoire de Mathematiques d'Orsay, UMR 8628 CNRS - Universite Paris-Sud (France); Magin, Thierry E. [Aeronautics and Aerospace Department, von Karman Institute for Fluid Dynamics (Belgium)

    2011-05-20

    We examine both processes of ionization by electron and heavy-particle impact in spatially uniform plasmas at rest in the absence of external forces. A singular perturbation analysis is used to study the following physical scenario, in which thermal relaxation becomes much slower than chemical reactions. First, electron-impact ionization is investigated. The dynamics of the system rapidly becomes close to a slow dynamics manifold that allows for defining a unique chemical quasi-equilibrium for two-temperature plasmas and proving that the second law of thermodynamics is satisfied. Then, all ionization reactions are taken into account simultaneously, leading to a surprising conclusion: the inner layer for short time scale (or time boundary layer) directly leads to thermal equilibrium. Global thermo-chemical equilibrium is reached within a short time scale, involving only chemical reactions, even if thermal relaxation through elastic collisions is assumed to be slow.

  6. Tracking thermal fronts with temperature-sensitive, chemically reactive tracers

    SciTech Connect

    Robinson, B.A.; Birdsell, S.A.

    1987-01-01

    Los Alamos is developing tracer techniques using reactive chemicals to track thermal fronts in fractured geothermal reservoirs. If a nonadsorbing tracer flowing from the injection to production well chemically reacts, its reaction rate will be a strong function of temperature. Thus the extent of chemical reaction will be greatest early in the lifetime of the system, and less as the thermal front progresses from the injection to production well. Early laboratory experiments identified tracers with chemical kinetics suitable for reservoirs in the temperature range of 75 to 100/sup 0/C. Recent kinetics studies have focused on the kinetics of hydrolysis of derivatives of bromobenzene. This class of reactions can be used in reservoirs ranging in temperature from 150 to 275/sup 0/C, which is of greater interest to the geothermal industry. Future studies will include laboratory adsorption experiments to identify possibly unwanted adsorption on granite, development of sensitive analytical techniques, and a field demonstration of the reactive tracer concept.

  7. Theory of chemical reaction dynamics. Volume 3

    SciTech Connect

    Baer, M.

    1985-01-01

    This book examines some of the basic principles behind chemical reaction kinetics. Topics considered include the classical trajectory approach to reactive scattering; periodic orbits and theory of reactive scattering; and semiclassical reactive scattering.

  8. Deterministic Function Computation with Chemical Reaction Networks

    E-print Network

    Doty, David

    systems, "wet robots", smart drugs, etc. #12;4 Chemical Reaction Networks (CRN) syntax: we use only came free with my toilet brush! #12;3 Cells are smart: controlled by signaling and regulatory networks

  9. FAST ELEMENTARY STEPS IN CHEMICAL REACTION MECHANSIMS

    Microsoft Academic Search

    M. Eigen

    1963-01-01

    A review is presented of studies of fast chemical reaction steps which ; were studied using various relaxation techniques. These studies include ligand ; substitution in metal complexes, proton transfer, and enzymatic hydrolysis. ; (D.L.C.);

  10. Chemical Principles Revisited: Annotating Reaction Equations.

    ERIC Educational Resources Information Center

    Tykodi, R. J.

    1987-01-01

    Urges chemistry teachers to have students annotate the chemical reactions in aqueous-solutions that they see in their textbooks and witness in the laboratory. Suggests this will help students recognize the reaction type more readily. Examples are given for gas formation, precipitate formation, redox interaction, acid-base interaction, and…

  11. Controlling chemical reactions of a single particle

    E-print Network

    Lothar Ratschbacher; Christoph Zipkes; Carlo Sias; Michael Köhl

    2012-09-26

    The control of chemical reactions is a recurring theme in physics and chemistry. Traditionally, chemical reactions have been investigated by tuning thermodynamic parameters, such as temperature or pressure. More recently, physical methods such as laser or magnetic field control have emerged to provide completely new experimental possibilities, in particular in the realm of cold collisions. The control of reaction pathways is also a critical component to implement molecular quantum information processing. For these undertakings, single particles provide a clean and well-controlled experimental system. Here, we report on the experimental tuning of the exchange reaction rates of a single trapped ion with ultracold neutral atoms by exerting control over both their quantum states. We observe the influence of the hyperfine interaction on chemical reaction rates and branching ratios, and monitor the kinematics of the reaction products. These investigations advance chemistry with single trapped particles towards achieving quantum-limited control of chemical reactions and indicate limits for buffer gas cooling of single ion clocks.

  12. Modeling of turbulent chemical reaction

    NASA Technical Reports Server (NTRS)

    Chen, J.-Y.

    1995-01-01

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

  13. Chemical Reactions in Supercritical Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Wai, Chien M.; Hunt, Fred; Ji, Min; Chen, Xiaoyuan

    1998-12-01

    Utilizing supercritical fluids as environmentally benign solvents for chemical synthesis is one of the new approaches in the "greening" of chemistry. Carbon dioxide is the most widely used gas for supercritical fluid studies because of its moderate critical constants, nontoxic nature, and availability in pure form. One unique property of supercritical carbon dioxide (sc-CO2) is its high solubility for fluorinated compounds. Thus sc-CO2 can be used to replace Freons that are conventionally used as solvents for synthesis of perfluoro-polymers. Another property of sc-CO2 is its miscibility with gases such as H2. Heterogeneous reactions involving these gases may become homogeneous reactions in sc-CO2. Reactions in sc-CO2 may offer several advantages including controlling phase behavior and products, increasing speed of reactions, and obtaining specific reaction channels. This paper describes the following nine types of chemical reactions reported in the literature utilizing sc-CO2 as a solvent to illustrate the unique properties of the supercritical fluid reaction systems: (i) hydrogenation and hydroformylation, (ii) synthesis of organometallic compounds, (iii) metal chelation and extraction, (iv) preparation of inorganic nanoparticles, (v) stereo-selectivity of lipase-catalyzed reactions, (vi) asymmetric catalytic hydrogenation, (vii) polymerization, (viii) Diels-Alder reaction, and (ix) free radical reactions.

  14. Neutral theory of chemical reaction networks

    E-print Network

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

    2011-01-01

    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 the key to understanding a complex structure. Yet 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 subject to biological evolution (the chemical reaction network of the 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 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 rando...

  15. Entropy generation in a chemical reaction

    E-print Network

    E. N. Miranda

    2012-08-10

    Entropy generation in a chemical reaction is analyzed 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 second approach assumes that the reaction is near equilibrium to prove that the entropy generated is always greater than zero, without any reference to the kinetics of the reaction. Finally, it is shown that entropy generation is related to fluctuations in the number of particles at equilibrium, i.e. it is associated to a microscopic process.

  16. Entropy generation in a chemical reaction

    E-print Network

    Miranda, E N

    2012-01-01

    Entropy generation in a chemical reaction is analyzed 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 second approach assumes that the reaction is near equilibrium to prove that the entropy generated is always greater than zero, without any reference to the kinetics of the reaction. Finally, it is shown that entropy generation is related to fluctuations in the number of particles at equilibrium, i.e. it is associated to a microscopic process.

  17. Chemical Changes in Lipids Produced by Thermal Processing.

    ERIC Educational Resources Information Center

    Nawar, Wassef W.

    1984-01-01

    Describes heat effects on lipids, indicating that the chemical and physical changes that occur depend on the lipid's composition and conditions of treatment. Thermolytic and oxidation reactions, thermal/oxidative interaction of lipids with other food components and the chemistry of frying are considered. (JN)

  18. Thermal-oxidative aging of DGEBA\\/EPN\\/LMPA epoxy system: Chemical structure and thermal–mechanical properties

    Microsoft Academic Search

    Yan-min Pei; Kai Wang; Mao-sheng Zhan; Wen Xu; Xiao-jun Ding

    2011-01-01

    The evolvement of chemical structure and thermal–mechanical properties of diglycidyl ether of bisphenol-A and novolac epoxy resin blends cured with low molecular polyamide (DGEBA\\/EPN\\/LMPA system) during thermal-oxidative aging were investigated by Attenuated Total Reflectance Fourier Transform Infrared spectrometry (ATR-FTIR) and Dynamic Mechanical Thermal Analysis (DMTA). The results revealed that the chemical reactions during thermal-oxidative aging contained oxidation and chain scission.

  19. A Synthetic Reaction Network: Chemical Amplification Using Nonequilibrium Autocatalytic Reactions Coupled in Time

    E-print Network

    Ismagilov, Rustem F.

    A Synthetic Reaction Network: Chemical Amplification Using Nonequilibrium Autocatalytic Reactions reaction network synthesized in a microfluidic device. This chemical network performs chemical 5000-fold by a reaction autocatalytic in Co2+ . The microfluidic network is used to maintain the two chemical reactions

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

    NASA Technical Reports Server (NTRS)

    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.

  1. Stochastic generator of chemical structure. 3. Reaction network generation.

    PubMed

    Faulon, J L; Sault, A G

    2001-01-01

    A new method to generate chemical reaction network is proposed. The particularity of the method is that network generation and mechanism reduction are performed simultaneously using sampling techniques. Our method is tested for hydrocarbon thermal cracking. Results and theoretical arguments demonstrate that our method scales in polynomial time while other deterministic network generators scale in exponential time. This finding offers the possibility of investigating complex reacting systems such as those studied in petroleum refining and combustion. PMID:11500106

  2. Stochastic Generator of Chemical Structure. 3. Reaction Network Generation

    SciTech Connect

    FAULON,JEAN-LOUP; SAULT,ALLEN G.

    2000-07-15

    A new method to generate chemical reaction network is proposed. The particularity of the method is that network generation and mechanism reduction are performed simultaneously using sampling techniques. Our method is tested for hydrocarbon thermal cracking. Results and theoretical arguments demonstrate that our method scales in polynomial time while other deterministic network generator scale in exponential time. This finding offers the possibility to investigate complex reacting systems such as those studied in petroleum refining and combustion.

  3. CONTINUOUS TIME MARKOV CHAIN MODELS FOR CHEMICAL REACTION NETWORKS

    E-print Network

    Anderson, David F.

    Chapter 1 CONTINUOUS TIME MARKOV CHAIN MODELS FOR CHEMICAL REACTION NETWORKS David F. Anderson@math.wisc.edu Abstract A reaction network is a chemical system involving multiple reactions and chemical species-05793 #12;2 the representation of the stochastic equation for chemical reaction net- works and, under what

  4. Stochastic thermodynamics of chemical reaction networks

    E-print Network

    Tim Schmiedl; Udo Seifert

    2006-12-19

    For chemical reaction networks described by a master equation, we define energy and entropy on a stochastic trajectory and develop a consistent nonequilibrium thermodynamic description along a single stochastic trajectory of reaction events. A first-law like energy balance relates internal energy, applied (chemical) work and dissipated heat for every single reaction. Entropy production along a single trajectory involves a sum over changes in the entropy of the network itself and the entropy of the medium. The latter is given by the exchanged heat identified through the first law. Total entropy production is constrained by an integral fluctuation theorem for networks arbitrarily driven by time-dependent rates and a detailed fluctuation theorem for networks in the steady state. Further exact relations like a generalized Jarzynski relation and a generalized Clausius inequality are discussed. We illustrate these results for a three-species cyclic reaction network which exhibits nonequilibrium steady states as well as transitions between different steady states.

  5. Instantaneous Chemical Reactions in Benzene and Toluene

    E-print Network

    Allen, Herman Camp

    1905-06-07

    KU ScholarWorks | The University of Kansas Pre-1923 Dissertations and Theses Collection Instantaneous Chemical Reac- tions in Benzene and Toluene June 7th, 1905 by Herman Camp Allen This work was digitized by the Scholarly Communications program... Chemistry Allen, H.C. 1905 "Instantaneous reactions (chemical) in benzene and toluene". I ! B f O H B M I O A L REACTIONS IN Bt«2F;»F! AND TQLUBMB, Presented to the faculty of the University of Kansas in partial fulfillment of the requirements...

  6. Decrease of Entropy and Chemical Reactions

    E-print Network

    Yi-Fang Chang

    2008-07-01

    The chemical reactions are very complex, and include oscillation, condensation, catalyst and self-organization, etc. In these case changes of entropy may increase or decrease. The second law of thermodynamics is based on an isolated system and statistical independence. If fluctuations magnified due to internal interactions exist in the system, entropy will decrease possibly. In chemical reactions there are various internal interactions, so that some ordering processes with decrease of entropy are possible on an isolated system. For example, a simplifying Fokker-Planck equation is solved, and the hysteresis as limit cycle is discussed.

  7. Acceleration of chemical reaction by chaotic mixing

    E-print Network

    M. Chertkov; V. Lebedev

    2003-01-27

    Theory of fast binary chemical reaction, ${\\cal A}+{\\cal B}\\to{\\cal C}$, in a statistically stationary chaotic flow at large Schmidt number ${Sc}$ and large Damk\\"ohler number ${Da}$ is developed. For stoichiometric condition we identify subsequent stages of the chemical reaction. The first stage corresponds to the exponential decay, $\\propto\\exp(-\\lambda t)$ (where $\\lambda$ is the Lyapunov exponent of the flow), of the chemicals in the bulk part of the flow. The second and the third stages are related to the chemicals remaining in the boundary region. During the second stage the amounts of ${\\cal A}$ and ${\\cal B}$ decay $\\propto 1/\\sqrt{t}$, whereas the decay law during the third stage is exponential, $\\propto\\exp(-\\gamma t)$, where $\\gamma\\sim\\lambda/\\sqrt{Sc}$.

  8. Continuous Time Markov Chain Models for Chemical Reaction

    E-print Network

    Anderson, David F.

    Chapter 7 Continuous Time Markov Chain Models for Chemical Reaction Networks 7.1 Chemical reaction chemical reactions involving N chemical species, S1, . . . , SN , N i=1 ikSi N i=1 ikSi, k = 1, in Sec- tion 7.1.1 by developing the basic stochastic equations for chemical systems. Next, in Section 7

  9. Concordant Chemical Reaction Networks and the Species-Reaction Graph

    E-print Network

    Shinar, Guy

    2012-01-01

    In a recent paper it was shown that, for chemical reaction networks possessing a subtle structural property called concordance, dynamical behavior of a very circumscribed (and largely stable) kind is enforced, so long as the kinetics lies within the very broad and natural class of weakly monotonic kinetics. In particular, multiple equilibria are precluded, as are degenerate positive equilibria. Moreover, under certain circumstances, also related to concordance, all real eigenvalues associated with a positive equilibrium are negative. Although concordance of a reaction network can be decided by readily available computational means, we show here that, when a nondegenerate network's Species Reaction Graph satisfies certain mild conditions, concordance and its dynamical consequences are ensured. These conditions are weaker than earlier ones invoked to establish kinetic system injectivity, which, in turn, is just one ramication of network concordance. Because the Species Reaction Graph resembles pathway depiction...

  10. Tailoring oxidation degrees of graphene oxide by simple chemical reactions

    SciTech Connect

    Wang Gongkai [Key Laboratory for Anisotropy and Texture of Materials of Ministry of Education, Northeastern University, Shenyang, Liaoning 110004 (China); Department of Mechanical, Aerospace and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, New York 12180 (United States); Sun Xiang; Lian Jie [Department of Mechanical, Aerospace and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, New York 12180 (United States); Liu Changsheng [Key Laboratory for Anisotropy and Texture of Materials of Ministry of Education, Northeastern University, Shenyang, Liaoning 110004 (China)

    2011-08-01

    High quality graphene oxide (GO) with controllable degrees of oxidation was synthesized by simple chemical reactions inspired by approaches to unzip single wall carbon nanotubes using strong oxidizing agents. As compared to the conventional Hummers method, these reactions are less exo-therm involved without emission of toxic gases. The structural characteristics of the synthesized GO with various oxidation degrees were evaluated by x-ray diffraction, x-ray photoelectron spectroscopy, Raman spectroscopy, thermal gravimetric analysis, and UV-vis-IR spectroscopy. GO with tailored degrees of oxidation displays tunable optoelectronic properties and may have a significant impact on developing graphene- or GO-based platforms for various technological applications.

  11. Capture of spatially homogeneous chemical reactions in tissue by freezing.

    PubMed Central

    Clark, A; Clark, P A

    1983-01-01

    A useful technique in studying the saturation of hemoglobin in erythrocytes or myoglobin in tissue is cryophotometry, in which tissue is frozen for later spectrophotometric analysis. A general question associated with this technique is whether the freezing process alters the chemical state. This paper presents a theoretical analysis of the simplest model relevant to that question. We study the effect of rapid cooling on a spatially homogeneous chemical reaction. The analysis shows that changes during freezing are negligible near the boundary to which the heat sink is applied, but can be significant deeper in the sample. The distance from the boundary at which the changes during freezing become appreciable can be expressed simply in terms of the chemical reaction rates and the thermal diffusivity of the tissue. Detailed results are given for the case of oxygen and myoglobin in skeletal muscle. PMID:6838980

  12. An Alternative to Gillespie's Algorithm for Simulating Chemical Reactions

    E-print Network

    Torino, Università di

    An Alternative to Gillespie's Algorithm for Simulating Chemical Reactions Roberto Barbuti, Andrea introduce a probabilistic algorithm for the simulation of chemical reactions, which can be used evolution of chemical reactive systems described by Gillespie. Moreover, we use our algorithm

  13. LIGAND: chemical database of enzyme reactions

    PubMed Central

    Goto, Susumu; Nishioka, Takaaki; Kanehisa, Minoru

    2000-01-01

    LIGAND is a composite database comprising three sections: ENZYME for the information of enzyme molecules and enzymatic reactions, COMPOUND for the information of metabolites and other chemical compounds, and REACTION for the collection of substrate–product relations. The current release includes 3390 enzymes, 5645 compounds and 5207 reactions. The database is indispensable for the reconstruction of metabolic pathways in the completely sequenced organisms. The LIGAND database can be accessed through the WWW (http://www.genome.ad.jp/dbget/ligand.html ) or may be downloaded by anonymous FTP (ftp://kegg.genome.ad.jp/molecules/ligand/ ). PMID:10592281

  14. Simple thermal decomposition reactions for storage of solar thermal energy

    Microsoft Academic Search

    W. E. Wentworth; E. Chen

    1975-01-01

    The paper considers the uncatalyzed decomposition of such classes of salts as ammonium salts and Group IA and IIA hydroxides, carbonates, sulfates, and oxides, for the storage of solar energy. Ten specific criteria are given which can be used to select the most appropriate chemical reaction for storing solar energy, capable of producing high temperature heat sufficient to generate electrical

  15. Classification of Chemical Reactions: Stages of Expertise

    ERIC Educational Resources Information Center

    Stains, Marilyne; Talanquer, Vicente

    2008-01-01

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

  16. Regenerative fuel cell with chemical reactions

    Microsoft Academic Search

    P. B. L. Chaurasia; Yuji Ando; Tadayoshi Tanaka

    2003-01-01

    The function of fuel cells largely depends upon catalytic electrodes which accomplish a chemical reaction to convert fuel into electric energy. For this purpose, a study has been conducted on different catalysts prepared from various precursors and tested in the fuel cells for power generation under identical conditions. A new precursor has been identified to prepare the catalysts, giving encouraging

  17. Computer Animation of a Chemical Reaction.

    ERIC Educational Resources Information Center

    Eaker, Charles W.; Jacobs, Edwin L.

    1982-01-01

    Taking a prototype chemical reaction (molecular hydrogen plus hydrogen atom), constructs an accurate semiempirical, generalized diatomics-in-molecules potential energy surface, calculates motions of these atoms on this surface using REACTS trajectory program, and presents results as moving picture on a microcomputer graphics system. Provides…

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

    PubMed Central

    SUZUKI, Toshinori

    2013-01-01

    Polyatomic molecules have several electronic states that have similar energies. Consequently, their chemical dynamics often involve nonadiabatic transitions between multiple potential energy surfaces. Elucidating the complex reactions of polyatomic molecules is one of the most important tasks of theoretical and experimental studies of chemical dynamics. This paper describes our recent experimental studies of the multidimensional multisurface dynamics of polyatomic molecules based on two-dimensional ion/electron imaging. It also discusses ultrafast photoelectron spectroscopy of liquids for elucidating nonadiabatic electronic dynamics in aqueous solutions. PMID:23318678

  19. Reaction, transformation and delamination of samarium zirconate thermal barrier coatings

    E-print Network

    Wadley, Haydn

    Reaction, transformation and delamination of samarium zirconate thermal barrier coatings Hengbei online 24 March 2011 Keywords: Samarium zirconate Interface reaction Bilayers Delamination The rare earth zirconates have attracted interest for thermal barrier coatings (TBCs) because they have very low intrinsic

  20. Continuous time Markov chain models for chemical reaction networks

    E-print Network

    Kurtz, Tom

    Continuous time Markov chain models for chemical reaction networks David F. Anderson Departments classifications: 60J27, 60J28, 60J80, 60F17, 80A30, 92C40 Keywords: Reaction network, Markov chain, law of mass Abstract A reaction network is a chemical system involving multiple reactions and chemical species

  1. Monotonicity and convergence in chemical reaction networks Patrick De Leenheer

    E-print Network

    Sontag, Eduardo

    Monotonicity and convergence in chemical reaction networks Patrick De Leenheer Dep. of Mathematics- of chemical reaction networks. The results do not assume any particular form for the kinetics of the reactions of the qualitative behavior of chemical reaction networks is an area of growing interest, especially in light

  2. Inferring Chemical Reaction Patterns Using Rule Composition in Graph Grammars

    E-print Network

    Flamm, Christoph

    Inferring Chemical Reaction Patterns Using Rule Composition in Graph Grammars Jakob Lykke Andersen1:studla@bioinf.uni-leipzig.de; Corresponding author Abstract Background: Modeling molecules as undirected graphs and chemical reactions, to summarize several subsequent reactions into a single composite chemical reaction. Results: We introduce

  3. Steady detonation problem for slow and fast chemical reactions

    E-print Network

    Ceragioli, Francesca

    Steady detonation problem for slow and fast chemical reactions F. Conforto1 , M. Groppi2 , R chemical reaction are discussed. The former consists in a system of balance laws for the case of a chemical is a system of conser- vation laws for the case of short chemical relaxation time (fast reaction). After

  4. Chemical computing with reaction-diffusion processes.

    PubMed

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

    2015-07-28

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

  5. Chemical reactions in reverse micelle systems

    DOEpatents

    Matson, Dean W. (Kennewick, WA); Fulton, John L. (Richland, WA); Smith, Richard D. (Richland, WA); Consani, Keith A. (Richland, WA)

    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.

  6. Polymer Reaction Engineering Laboratory Chemical and Biomolecular Engineering

    E-print Network

    Choi, Kyu Yong

    Transporting chemicals Fume hoods and ventilation Refrigerators Incompatible chemicals The followingPolymer Reaction Engineering Laboratory Chemical and Biomolecular Engineering University of the chemicals involved. Know the safety precautions and emergency procedures that protect you from those hazards

  7. Minimum Energy Pathways for Chemical Reactions

    NASA Technical Reports Server (NTRS)

    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.

  8. Quantum Theory of Fast Chemical Reactions

    Microsoft Academic Search

    John C. Light

    2007-01-01

    The aims of the research under this grant were to develop a;\\u000atheoretical understanding and;\\u000apredictive abiility for a variety of processes occurring in the;\\u000agas phase.;\\u000aThese included bimolecular chemical exchange reactions,;\\u000aphotodissociation,;\\u000apredissociation resonances, unimolecular reactions and recombination;\\u000areactions. In general we assumed a knowledge, from quantum chemistry,;\\u000aof the interactions of the atoms and molecular fragments involved.;

  9. Quantum Theory of Chemical Reaction Dynamics.

    NASA Astrophysics Data System (ADS)

    Zhao, Meishan

    The generalized Newton variational principle is extended to treat chemical reactions with nonzero total angular momentum J, and it is applied to various chemical reactions with J = 0 to 20. Chapter 1 reviews the basic theory and discusses the evaluation of nonzero-J matrix elements. Chapters 2-5 report extensive quantum mechanical calculations on the reaction H + p-H_2 to o-H_2 + H. Chapter 2 reports vibrational branching ratios. Chapter 3 reports probabilities and partial cross sections, which are compared to corresponding quantities calculated by the quasiclassical trajectory method. Chapter 4 presents converged quantum mechanical state-to-state cross sections. The converged vibrational branching ratio is in good agreement with recent experiments but the rotational distribution is not. Chapter 5 reports converged quantum mechanical calculations of resonances and time delays for total angular momentum 0, 1, and 4. Chapter 4 compares the results of classical simulations to accurate quantum studies for the reaction D + H _2 to HD + H. Chapter 7 presents accurate state-to-state transition probabilities and delay times for this reaction. Chapter 8 reports fully converged quantum mechanical transition probabilities for the F + H_2 to HF + H reaction. Chapter 9 presents calculations of state-to-state partial reaction cross sections in H + D_2 to HD + D collisions. The results are compared to quasiclassical trajectory calculations to test the classical simulation method. In chapter 10 a new method for constructing efficient basis functions for {cal L}^2 variational calculations of quantum mechanical rearrangements is presented and tested.

  10. Quantum Theory of Fast Chemical Reactions

    SciTech Connect

    Light, John C

    2007-07-30

    The aims of the research under this grant were to develop a theoretical understanding and predictive abiility for a variety of processes occurring in the gas phase. These included bimolecular chemical exchange reactions, photodissociation, predissociation resonances, unimolecular reactions and recombination reactions. In general we assumed a knowledge, from quantum chemistry, of the interactions of the atoms and molecular fragments involved. Our focus was primarily on the accurate (quantum) dynamics of small molecular systems. This has been important for many reactions related to combustion and atmospheric chemistry involving light atom transfer reactions and, for example, resonances in dissociation and recombination reactions. The rates of such reactions, as functions of temperature, internal states, and radiation (light), are fundamental for generating models of overall combustion processes. A number of new approaches to these problems were developed inclluding the use of discrete variable representations (DVR's) for evaluating rate constants with the flux-flux correlation approach, finite range approaches to exact quantum scattering calculations, energy selected basis representations, transition state wave packet approaches and improved semiclassical approaches. These (and others) were applied to a number of reactive systems and molecular systems of interest including (many years ago) the isotopic H + H2 exchange reactions, the H2 + OH (and H + H2O) systems, Ozone resonances, van der Waals molecule reactions, etc. A total of 7 graduate students, and 5 post-doctoral Research Associates were supported, at least in part, under this grant and seven papers were published with a total of 10 external collaborators. The majority of the 36 publications under this grant were supported entirely by DOE.

  11. Chemical Reactions Directed Peptide Self-Assembly

    PubMed Central

    Rasale, Dnyaneshwar B.; Das, Apurba K.

    2015-01-01

    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. PMID:25984603

  12. Semiclassical approaches to controlling chemical reaction dynamics

    E-print Network

    Hiroshi Fujisaki; Yoshiaki Teranishi; Alexey Kondorskiy; Hiroki Nakamura

    2003-02-04

    We propose to use semiclassical methods to treat laser control problems of chemical reaction dynamics. Our basic strategy is as follows: Laser-driven chemical reactions are considered to consist of two processes. One is the wavepacket propagation on an adiabatic potential energy surface (PES), and the other is the electronic transition between PES's. Because the latter process is mathematically equivalent to nonadiabatic transitions between Floquet (dressed) states, we can control such a process using the semiclassical Zhu-Nakamura theory for nonadiabatic transitions. For the former process, we incorporate semiclassical propagation methods such as the Herman-Kluk propagator into optimization procedures like optimal control theory. We show some numerical examples for our strategies. We also develop a semiclassical direct algorithm to treat the adiabatic propagation and nonadiabatic transitions as a whole.

  13. Chemical reactions directed Peptide self-assembly.

    PubMed

    Rasale, Dnyaneshwar B; Das, Apurba K

    2015-01-01

    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. PMID:25984603

  14. Chemical reaction systems with toric steady states

    E-print Network

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

    2011-01-01

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

  15. Internal Active Thermal Control System (IATCS) Sodium Bicarbonate/Carbonate Buffer in an Open Aqueous Carbon Dioxide System and Corollary Electrochemical/Chemical Reactions Relative to System pH Changes

    NASA Technical Reports Server (NTRS)

    Stegman, Thomas W.; Wilson, Mark E.; Glasscock, Brad; Holt, Mike

    2014-01-01

    The International Space Station (ISS) Internal Active Thermal Control System (IATCS) experienced a number of chemical changes driven by system absorption of CO2 which altered the coolant’s pH. The natural effects of the decrease in pH from approximately 9.2 to less than 8.4 had immediate consequences on system corrosion rates and corrosion product interactions with specified coolant constituents. The alkalinity of the system was increased through the development and implementation of a carbonate/bicarbonate buffer that would increase coolant pH to 9.0 – 10.0 and maintain pH above 9.0 in the presence of ISS cabin concentrations of CO2 up to twenty times higher than ground concentrations. This paper defines how a carbonate/bicarbonate buffer works in an open carbon dioxide system and summarizes the analyses performed on the buffer for safe and effective application in the on-orbit system. The importance of the relationship between the cabin environment and the IATCS is demonstrated as the dominant factor in understanding the system chemistry and pH trends before and after addition of the carbonate/bicarbonate buffer. The paper also documents the corollary electrochemical and chemical reactions the system has experienced and the rationale for remediation of these effects with the addition of the carbonate/bicarbonate buffer.

  16. Photochemical reactions of anthropogenic chemicals in seawater

    SciTech Connect

    Toole, A.P.; Crosby, D.G. (Univ. of California, Davis (USA))

    1988-09-01

    Sunlight-driven, photochemical reactions can be a major degradative force for anthropogenic organic compounds in the aquatic environment. Chlorinated phenols, various classes of pesticides, and polycyclic aromatic hydrocarbons are among some examples of the compounds shown to be degraded by sunlight. Most environmental photochemistry has been studied in fresh water, despite the fact that the oceans cover more than 70% of the earths surface and receive large inputs of anthropogenic chemicals via atmospheric transport, runoff, and coastal outfalls. This fact, along with increasing pressure for ocean waste disposal as land options dwindle, present a need for information on the photochemical reactions of anthropogenic organic chemicals in seawater. Several probable seawater pollutants were selected as probes for studying photochemical reactions including, 2-nitrotoluene, 4-nitrotoluene, styrene, 4,5-dichloroguaiacol, 4,5,6-trichloroguaiacol and tetrachloroguaiacol. Dilute solutions of each probe were prepared in buffered (pH 8), distilled water (DW), synthetic seawater (SSW) and natural seawater (NSW), then irradiated in a temperature-controlled photoreactor fitted with a General Electric F40BL fluorescent lamp to simulate sunlight. Samples were taken at regular intervals, concentrated using solid phase extraction techniques and analyzed by gas chromatography. Photolysis rates were determined assuming first, or pseudo-first, order kinetics. Photoproducts were identified by gas chromatography;mass spectrometry and confirmed by comparison to standards when available. By determining rates in DW containing selected components of SSW, at SSW concentrations, the inorganic compounds mediating the photochemical reactions in seawater could be determined.

  17. Density functional study of chemical reaction equilibrium for dimerization reactions in slit and cylindrical nanopores

    E-print Network

    Lisal, Martin

    Density functional study of chemical reaction equilibrium for dimerization reactions in slit a theoretical study of the effects of confinement on chemical reaction equilibrium in slit and cylindrical equilibrium, for which much less is known. The behavior of chemical reactions in confinement spans a wide

  18. CHAPTER 9. CHEMICAL KINETICS In the following chapters we will present various chemical reaction

    E-print Network

    Jacob, Daniel J.

    AND CHEMICAL EQUILIBRIA Reactions are re155 CHAPTER 9. CHEMICAL KINETICS In the following chapters we will present various chemical reaction mechanisms controlling the abundance of stratospheric ozone, the oxidizing power of the atmosphere

  19. Exact Stochastic Simulation of Coupled Chemical Reactions Daniel T. Gillesple

    E-print Network

    Saidak, Filip

    2340 Exact Stochastic Simulation of Coupled Chemical Reactions Daniel T. Gillesple Danlel T chemical reaction channels, then given the numbers of molecules of each species present at some initial importance and usefulness of the differential reaction-rate equations approach to chemical kinetics cannot

  20. Model Reduction of Chemical Reaction Systems using Elimination

    E-print Network

    Paris-Sud XI, Université de

    Model Reduction of Chemical Reaction Systems using Elimination Fran¸cois Boulier, Marc Lefranc for parametric ordinary differential systems arising from chemical reaction systems. In this paper, we focus is different from those of Henri-Micha¨elis-Menten and Briggs-Haldane. 1. Introduction Chemical reaction

  1. GRAPH THEORETIC APPROACHES TO INJECTIVITY IN CHEMICAL REACTION SYSTEMS

    E-print Network

    Craciun, Gheorghe

    GRAPH THEORETIC APPROACHES TO INJECTIVITY IN CHEMICAL REACTION SYSTEMS MURAD BANAJI AND GHEORGHE algebraic and graph theoretic conditions for injectivity of chemical reaction systems. After developing the possibility of multiple equilibria in the systems in question. Key words. Chemical reactions; Injectivity; SR

  2. Chemical Reaction Dynamics accompanying Electron-Transfer Osamu SUGINO

    E-print Network

    Katsumoto, Shingo

    Chemical Reaction Dynamics accompanying Electron-Transfer Osamu SUGINO Institute for Solid State Physics, the University of Tokyo 5-1-5 Kashiwanoha, Chiba 277-8581 1. Introduction Many chemical reactions and the dynamics goes nonadiabatically. The former appears typically in chemical reactions that accompany electron

  3. Gamma and the chemical reaction model: fteen years after?

    E-print Network

    Fradet, Pascal

    Gamma and the chemical reaction model: fteen years after? Jean-Pierre Ban^atre1, Pascal Fradet2 the formalism is to describe computation as a form of chemical reaction on a collection of individual pieces on unexpected applications of the chemical reaction model, showing that this paradigm has been a source

  4. Asymptotic behaviour of reversible chemical reaction-diffusion equations

    E-print Network

    Paris-Sud XI, Université de

    Asymptotic behaviour of reversible chemical reaction-diffusion equations Ivan Gentil and Boguslaw chemical reaction-diffusion equations with the same diffusion. In particular we prove the optimal rate40, 35A05, 35F25 1 Introduction The self-ionization of water is the chemical reaction in which two

  5. P MATRIX PROPERTIES, INJECTIVITY AND STABILITY IN CHEMICAL REACTION SYSTEMS

    E-print Network

    Banaji,. Murad

    P MATRIX PROPERTIES, INJECTIVITY AND STABILITY IN CHEMICAL REACTION SYSTEMS MURAD BANAJI§, PETE. Chemical reactions; P matrices; Injectivity; Stability; Mass action AMS subject classifications. 80A30; 15A48; 34D30 1. Introduction. In this paper we will study chemical reaction systems, and systems derived

  6. Reasoning and Representation: the Sketching of Organic Chemical Reaction Mechanisms

    E-print Network

    Marchese, Francis

    Reasoning and Representation: the Sketching of Organic Chemical Reaction Mechanisms Position paper of sketching chemical reaction mechanisms in order to reason-out the structural transformations that convert. The general chemical reaction patterns of oxidation-reduction, functional group transfer, hydrolysis

  7. CANARDS, BLACK SWANS AND CONTROL OF CHEMICAL REACTIONS Vladimir Sobolev

    E-print Network

    CANARDS, BLACK SWANS AND CONTROL OF CHEMICAL REACTIONS By Vladimir Sobolev and Elena Shchepakina: 612-626-7370 URL: http://www.ima.umn.edu #12;Canards, Black Swans and Control of Chemical Reactions V. The sense of criticality here is as follows. The critical regime corresponds to chemical reaction separating

  8. Chemical Reaction Systems, Computer Algebra and Systems Biology

    E-print Network

    Boyer, Edmond

    Chemical Reaction Systems, Computer Algebra and Systems Biology Fran¸cois Boulier1 , Fran dynam- ics of chemical reaction systems. This cooperation led us to efficient algorithms for building the corre- sponding MAPLE packages. Chemical reaction systems provide a general setting for modeling

  9. Molecular dynamics study of fracture accompanied by chemical reaction

    E-print Network

    Krivtsov, Anton M.

    Molecular dynamics study of fracture accompanied by chemical reaction Anton M. Krivtsov akrivtsov of the chemical reaction (oxidation) on the fracture scenario is investigated. Fracture process for the specimens applications the fracture is closely connected with chemical reactions. In particular, for MEMS made from

  10. Programmability of Chemical Reaction Matthew Cook, David Soloveichik, Erik Winfree,

    E-print Network

    Winfree, Erik

    Programmability of Chemical Reaction Networks Matthew Cook, David Soloveichik, Erik Winfree cells we study Stochastic Chemical Reaction Networks (SCRNs), a for- mal model that considers a set of chemical reactions acting on a finite num- ber of molecules in a well-stirred solution according

  11. Reconstructing Chemical Reaction Networks: Data Mining meets System Identification

    E-print Network

    Ramakrishnan, Naren

    Reconstructing Chemical Reaction Networks: Data Mining meets System Identification Yong Ju Cho typically begins with a chemical reaction network (CRN), which is then converted to a set of simul- taneous in any domain where chemical reaction systems form the origins of the underlying numerical model (ODE

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

  13. Sensitivity of chemical reaction networks: a structural approach.

    E-print Network

    Fiedler, Bernold

    Sensitivity of chemical reaction networks: a structural approach. 2. Regular monomolecular systems to perturbations of reaction rates in chemical reaction networks. Strong motivation for our study comes from recent For the deceptively innocent case of monomolecular reactions, only, we embark on a systematic mathematical analysis

  14. A kinetic mechanism inducing oscillations in simple chemical reactions networks

    E-print Network

    Altafini, Claudio

    A kinetic mechanism inducing oscillations in simple chemical reactions networks J. Coatl´even and C of oscillations in sufficiently simple reaction networks. Keywords: chemical reaction networks, oscillations, Hopf. Altafini September 10, 2009 Abstract It is known that a kinetic reaction network in which one or more

  15. Computed Potential Energy Surfaces for Chemical Reactions

    NASA Technical Reports Server (NTRS)

    Heinemann, K.; Walch, Stephen P.; Levin, Eugene

    1993-01-01

    A manuscript describing the calculations on the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels in the CH3 + OH reaction, which were described in the last progress report, has been accepted for publication in J. Chem. Phys., and a copy of the manuscript is included in the appendix. The production of (1)CH2 in this reaction is important in hydrocarbon combustion since (1)CH2 is highly reactive and would be expected to insert into N2, possibly leading to a new source for prompt NO(x) (vide infra). During the last six months new calculations have been carried out for the NH2 + NO system, which is important in the thermal de-NO(x) process.

  16. Study of the Interaction of ZDDP and Dispersants Using X-ray Absorption Near Edge Structure Spectroscopy—Part 1: Thermal Chemical Reactions

    Microsoft Academic Search

    Z. Zhang; M. Kasrai; G. M. Bancroft; E. S. Yamaguchi

    2003-01-01

    The interactions of ZDDP and different dispersants have been investigated both in oil solutions and on steel substrates at 150–185?°C. X-ray absorption near edge structure (XANES) spectroscopy at P and S L-edge and K-edge has been used to identify the chemical species both in solution and on the surface of the steel. It was found that noticeable ZDDP decomposition in

  17. Chemical Reaction due to Stronger Ramachandran Interaction

    E-print Network

    Andrew Das Arulsamy

    2013-12-26

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

  18. Chemical Reaction of Silicon Clusters with nitrogen monoxide Chemical reaction of small silicon cluster ions (Si n

    E-print Network

    Maruyama, Shigeo

    Si NO Chemical Reaction of Silicon Clusters with nitrogen monoxide * ** * ** *, ** ABSTRACT Chemical reaction of small silicon cluster ions (Si n + :20 n 30) with ethylene and nitrogen monoxideN + Si28N + Cluster ion mass (amu) Fig.2 Chemical reaction of Si cluster with NO 8 12 16 20 24

  19. On the geometrical thermodynamics of chemical reactions

    E-print Network

    Manuel Santoro; Albert S. Benight

    2005-07-08

    The formal structure of geometrical thermodynamics is reviewed with particular emphasis on the geometry of equilibria submanifolds. On these submanifolds thermodynamic metrics are defined as the Hessian of thermodynamic potentials. Links between geometry and thermodynamics are explored for single and multiple component, closed and open systems. For multi-component closed and open systems the Gibbs free energy is employed as the thermodynamic potential to investigate the connection between geometry and thermodynamics. The Gibbs free energy is chosen for the analysis of multicomponent systems and, in particular, chemical reactions.

  20. Stochastic Chemical Reactions in Micro-domains

    E-print Network

    D. Holcman; Z. Schuss

    2004-12-25

    Traditional chemical kinetics may be inappropriate to describe chemical reactions in micro-domains involving only a small number of substrate and reactant molecules. Starting with the stochastic dynamics of the molecules, we derive a master-diffusion equation for the joint probability density of a mobile reactant and the number of bound substrate in a confined domain. We use the equation to calculate the fluctuations in the number of bound substrate molecules as a function of initial reactant distribution. A second model is presented based on a Markov description of the binding and unbinding and on the mean first passage time of a molecule to a small portion of the boundary. These models can be used for the description of noise due to gating of ionic channels by random binding and unbinding of ligands in biological sensor cells, such as olfactory cilia, photo-receptors, hair cells in the cochlea.

  1. THE JOURNAL OF CHEMICAL PHYSICS 138, 144502 (2013) Speeding chemical reactions by focusing

    E-print Network

    Lindenberg, Katja

    2013-01-01

    THE JOURNAL OF CHEMICAL PHYSICS 138, 144502 (2013) Speeding chemical reactions by focusing A. M for a chemical reaction of colloidal particles which are transported by a laminar fluid and are focused their chemical reaction. Our main result is that reactants that arise from non- homogeneous distributions can

  2. Thermal plasma chemical synthesis of powders

    SciTech Connect

    Vogt, G.J.; Newkirk, L.R.

    1985-01-01

    Thermal plasma processing has been increasingly used to synthesize submicron powders of high-purity ceramics and metals. The high temperatures generated with the plasma provide a vapor phase reaction zone for elements with high boiling points and refractory materials. An overview is presented on the general plasma technology used in synthesis and on the properties of plasma powders.

  3. Organic chemical reactions in supercritical water

    SciTech Connect

    Savage, P.E. [Univ. of Michigan, Ann Arbor, MI (United States). Chemical Engineering Dept.] [Univ. of Michigan, Ann Arbor, MI (United States). Chemical Engineering Dept.

    1999-02-01

    Water near or above its critical point (374 C, 218 atm) is attracting increased attention as a medium for organic chemistry. Most of this new attention is driven by the search for more green or environmentally benign chemical processes. Using near-critical or supercritical water (SCW) instead of organic solvents in chemical processes offers environmental advantages and may lead to pollution prevention. Interest in doing chemistry in SCW is not entirely new, however. There has been much previous research in this area with applications in synthetic fuels production, biomass processing, waste treatment, materials synthesis, and geochemistry. Water near its critical point possesses properties very different from those of ambient liquid water. The dielectric constant is much lower, and the number and persistence of hydrogen bonds are both diminished. As a result, high-temperature water behaves like many organic solvents in that organic compounds enjoy high solubilities in near-critical water and complete miscibility with SCW. Moreover, gases are also miscible in SCW so employing a SCW reaction environment provides an opportunity to conduct chemistry in a single fluid phase that would otherwise occur in a multiphase system under more conventional conditions. The paper discusses the use of supercritical water in the following reactions: hydrogenation/dehydrogenation; C-C bond formation; rearrangements; hydration/dehydration; elimination; hydrolysis; partial oxidation; H-D exchange; decomposition; and oxidation.

  4. Chemical analysis of thermal battery components

    Microsoft Academic Search

    V. L. Hammersley; S. G. Stuart

    1998-01-01

    A number of methods using analytical chemistry were used to identify and quantify components in a thermal battery. The purpose of the task was to prepare a Material Safety Data Sheet (MSDS) so that the battery could be shipped. Wet chemical analysis, X-ray diffraction, inductively coupled plasma spectroscopy (ICP) and emission spectroscopy were among the methods used to determine the

  5. REGULAR ARTICLE Coordinate reduction for exploring chemical reaction paths

    E-print Network

    Schlegel, H. Bernhard

    REGULAR ARTICLE Coordinate reduction for exploring chemical reaction paths Adam B. Birkholz · H of coordinates can reproduce the changes in geometry along the reaction path with chemical accuracy and may help The potential energy surface for the reaction of a typical molecular system composed of N atoms is defined

  6. Uncertain dynamics in nonlinear chemical reactions Jichang Wang,a

    E-print Network

    Showalter, Kenneth

    Uncertain dynamics in nonlinear chemical reactions Jichang Wang,a Hongyan Sun,b Stephen K. Scottc a dissociation reaction of the autocatalytic species, B ! X + Y, followed by a recombination reaction, X + Y ! C evolution of the system. 1. Introduction The study of nonlinear chemical kinetics has flourished in the past

  7. Thermophoretic transport in impinging flows including chemical reactions

    NASA Astrophysics Data System (ADS)

    Hsu, Frank Kuan-Chao

    The research constitutes a fundamental study of transport phenomena that has applications to the fabrication of optical fibers. The flow, heat and mass transfer with chemical reactions, and thermophoretic transport of silica particles are studied. The governing equations have been formulated and solved to determine the velocity, temperature and species concentrations, and the effects of buoyancy, variable properties, chemical reactions, and thermophoretic transport on deposition uniformity and efficiency. A path-line/stream-line approach for determining variable particle concentration stagnation deposition with thermophoretic transport is introduced. The research is of fundamental interest and has applications to optical fiber fabrication. A review of the thermophoresis phenomena is provided including a recommended treatment for the thermophoretic coefficient, K. A discussion of the related chemical reactions is given. A study of a H2-N 2 non-premixed jet flame is performed to appraise the proposed H2 oxidation reaction rate and heat release rate. The present results of the velocity and temperature distributions are in very good agreement with the published experimental data. A study of silica (SiO2) particle transport in a free jet system is carried out. The gas entrainment and the thermophoretic transport are two important parameters that determine the particle transport. Both non-reacting and reacting jet flows are studied. The effects of inclination of jet flows on particle transport are also studied. A path-line/stream-line approach for determining deposition with thermophoretic transport in stagnation flow is introduced. This approach allows a variable particle concentration inlet boundary condition to be used. A closed form solution is achieved using this approach. Numerical studies of deposition on a cylindrical preform for both non-reacting and reacting jets are also investigated. A study of a small scale fiber fabrication is made with a cylindrical preform and two burners. Of special interest are the effects of preform temperature and preform thermal conductivity on the deposition efficiency.

  8. Thermal reaction of nickel and Si0.75Ge0.25 alloy K. L. Peya)

    E-print Network

    Thermal reaction of nickel and Si0.75Ge0.25 alloy K. L. Peya) Department of Electrical and Computer; accepted 22 July 2002 The interfacial reactions and chemical phase formation between nickel and ultrahigh vacuum chemical vapor deposited Si0.75Ge0.25 alloy have been studied within the temperature range of 300

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

    PubMed Central

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

    2014-01-01

    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. PMID:24958029

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

    PubMed

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

    2014-01-01

    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. PMID:24958029

  11. Robust Stochastic Chemical Reaction Networks and Bounded Tau-Leaping

    Microsoft Academic Search

    David Soloveichik

    2008-01-01

    The behavior of some stochastic chemical reaction networks is largely unaffected by slight inaccuracies in reaction rates. We formalize the robustness of state probabilities to reaction rate deviations, and describe a formal connection between robustness and efficiency of simulation. Without robustness guarantees, stochastic simulation seems to require computational time proportional to the total number of reaction events. Even if the

  12. Quantum dynamics of chemical reactions by converged algebraic variational calculations

    Microsoft Academic Search

    Donald G. Truhlar; David W. Schwenke; Donald J. Kouri

    1990-01-01

    This paper describes recent progress in using algebraic variational methods and L² basis sets for converged quantum mechanical calculations of chemical reaction dynamics of the H + Hâ, O + Hâ, H + HBr, and F + Hâ reactions and the isotopically substituted reactions D + Hâ and O + HD and some of the reverse reactions. The paper emphasizes

  13. Regimes of chemical reaction waves initiated by nonuniform initial conditions for detailed chemical reaction models.

    PubMed

    Liberman, M A; Kiverin, A D; Ivanov, M F

    2012-05-01

    Regimes of chemical reaction wave propagation initiated by initial temperature nonuniformity in gaseous mixtures, whose chemistry is governed by chain-branching kinetics, are studied using a multispecies transport model and a detailed chemical model. Possible regimes of reaction wave propagation are identified for stoichiometric hydrogen-oxygen and hydrogen-air mixtures in a wide range of initial pressures and temperature levels, depending on the initial non-uniformity steepness. The limits of the regimes of reaction wave propagation depend upon the values of the spontaneous wave speed and the characteristic velocities of the problem. It is shown that one-step kinetics cannot reproduce either quantitative neither qualitative features of the ignition process in real gaseous mixtures because the difference between the induction time and the time when the exothermic reaction begins significantly affects the ignition, evolution, and coupling of the spontaneous reaction wave and the pressure wave, especially at lower temperatures. We show that all the regimes initiated by the temperature gradient occur for much shallower temperature gradients than predicted by a one-step model. The difference is very large for lower initial pressures and for slowly reacting mixtures. In this way the paper provides an answer to questions, important in practice, about the ignition energy, its distribution, and the scale of the initial nonuniformity required for ignition in one or another regime of combustion wave propagation. PMID:23004867

  14. Regimes of chemical reaction waves initiated by nonuniform initial conditions for detailed chemical reaction models

    NASA Astrophysics Data System (ADS)

    Liberman, M. A.; Kiverin, A. D.; Ivanov, M. F.

    2012-05-01

    Regimes of chemical reaction wave propagation initiated by initial temperature nonuniformity in gaseous mixtures, whose chemistry is governed by chain-branching kinetics, are studied using a multispecies transport model and a detailed chemical model. Possible regimes of reaction wave propagation are identified for stoichiometric hydrogen-oxygen and hydrogen-air mixtures in a wide range of initial pressures and temperature levels, depending on the initial non-uniformity steepness. The limits of the regimes of reaction wave propagation depend upon the values of the spontaneous wave speed and the characteristic velocities of the problem. It is shown that one-step kinetics cannot reproduce either quantitative neither qualitative features of the ignition process in real gaseous mixtures because the difference between the induction time and the time when the exothermic reaction begins significantly affects the ignition, evolution, and coupling of the spontaneous reaction wave and the pressure wave, especially at lower temperatures. We show that all the regimes initiated by the temperature gradient occur for much shallower temperature gradients than predicted by a one-step model. The difference is very large for lower initial pressures and for slowly reacting mixtures. In this way the paper provides an answer to questions, important in practice, about the ignition energy, its distribution, and the scale of the initial nonuniformity required for ignition in one or another regime of combustion wave propagation.

  15. Spectroscopy and reactions of molecules important in chemical evolution

    NASA Technical Reports Server (NTRS)

    Becker, R. S.

    1974-01-01

    The research includes: (1) hot hydrogen atom reactions in terms of the nature of products produced, mechanism of the reactions and the implication and application of such reactions for molecules existing in interstellar clouds, in planetary atmospheres, and in chemical evolution; (2) photochemical reactions that can lead to molecules important in chemical evolution, interstellar clouds and as constituents in planetary atmospheres; and (3) spectroscopic and theoretical properties of biomolecules and their precursors and where possible, use these to understand their photochemical behavior.

  16. GREEN CHEMICAL SYNTHESIS THROUGH CATALYSIS AND ALTERNATE REACTION CONDITIONS

    EPA Science Inventory

    Green chemical synthesis through catalysis and alternate reaction conditions Encompassing green chemistry techniques and methodologies, we have initiated several projects at the National Risk Management Research laboratory that focus on the design and development of chemic...

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

    ERIC Educational Resources Information Center

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

    2001-01-01

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

  18. Formation of thermally stable chemical composition gratings in optical fibers

    NASA Astrophysics Data System (ADS)

    Fokine, Michael

    2002-08-01

    Experimental results and a discussion of possible chemical pathways in the formation of thermally stable chemical composition gratings in optical fibers are presented. Gratings are formed through high-temperature treatment of UV-exposed hydrogen-loaded fibers. The final refractive-index modulation is ascribed to variations in fluorine concentration attained by periodically increased diffusion of fluorine. The mechanism behind this increase is the formation of mobile hydrogen fluoride from chemical reactions of fluorine and UV-induced hydroxyl, which occur with the spatial periodicity of the UV pattern. A hydroxyl-assisted increase in fluorine diffusion has been verified by time-of-flight secondary-ion mass spectroscopy. Formation of ultrastable grating by periodic variation of oxygen concentration through diffusion of molecular water is also discussed.

  19. THE JOURNAL OF CHEMICAL PHYSICS 139, 165104 (2013) Exploring chemical reaction mechanisms through harmonic Fourier beads

    E-print Network

    2013-01-01

    THE JOURNAL OF CHEMICAL PHYSICS 139, 165104 (2013) Exploring chemical reaction mechanisms through understanding of complex chemical transformations relies on the identification of elementary reactions involved the harmonic Fourier beads (HFB) path optimization method to study chemical re- actions involving covalent bond

  20. Direct Monte Carlo simulation of chemical reaction systems: Simple bimolecular reactions

    E-print Network

    Anderson, James B.

    Direct Monte Carlo simulation of chemical reaction systems: Simple bimolecular reactions Shannon D and understanding the behavior of gas phase chemical reaction systems. This Monte Carlo method, originated by Bird useful, and the gas dynamics of many systems is more easily predicted and understood by using Monte Carlo

  1. Thermal energy harvesting plasmonic based chemical sensors.

    PubMed

    Karker, Nicholas; Dharmalingam, Gnanaprakash; Carpenter, Michael A

    2014-10-28

    Detection of gases such as H2, CO, and NO2 at 500 °C or greater requires materials with thermal stability and reliability. One of the major barriers toward integration of plasmonic-based chemical sensors is the requirement of multiple components such as light sources and spectrometers. In this work, plasmonic sensing results are presented where thermal energy is harvested using lithographically patterned Au nanorods, replacing the need for an external incident light source. Gas sensing results using the harvested thermal energy are in good agreement with sensing experiments, which used an external incident light source. Principal Component Analysis (PCA) was used to reduce the wavelength parameter space from 665 variables down to 4 variables with similar levels of demonstrated selectivity. The combination of a plasmonic-based energy harvesting sensing paradigm with PCA analysis offers a novel path toward simplification and integration of plasmonic-based sensing methods. PMID:25280004

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

    NASA Technical Reports Server (NTRS)

    Jaffe, R. L.

    1986-01-01

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

  3. Thermal and chemical stability of titanium-substituted MCM-41

    Microsoft Academic Search

    Chang Houn Rhee; Jae Sung Lee

    1996-01-01

    The thermal and chemical stability of a titanium-substituted MCM-41 (TiMCM-41) with Si\\/Ti mole ratio of 39 and pore diameter of 2.4 nm was studied with the small-angle X-ray diffraction and X-ray absorption near-edge structure techniques. The TiMCM-41 was stable in helium flow below 1273 K and under gas-phase reaction conditions of ethanol dehydrogenation (ethanol\\/ O2 = 1 mol\\/mol, 373–723 K).

  4. CHEMSIMUL --a tool for simulating chemical reaction systems Peter Kirkegaard, Erling Bjergbakke, and Frank Markert

    E-print Network

    CHEMSIMUL -- a tool for simulating chemical reaction systems Peter Kirkegaard, Erling Bjergbakke difficult to study elementary chemical reactions without interference from simul- taneous side reactions simulator of chemical kinetics with the following main compo- nents: - Module for input of reaction

  5. Ambient solid-state mechano-chemical reactions between functionalized carbon nanotubes

    PubMed Central

    Kabbani, Mohamad A.; Tiwary, Chandra Sekhar; Autreto, Pedro A.S.; Brunetto, Gustavo; Som, Anirban; Krishnadas, K.R.; Ozden, Sehmus; Hackenberg, Ken P.; Gong, Yongi; Galvao, Douglas S.; Vajtai, Robert; Kabbani, Ahmad T.; Pradeep, Thalappil; Ajayan, Pulickel M.

    2015-01-01

    Carbon nanotubes can be chemically modified by attaching various functionalities to their surfaces, although harsh chemical treatments can lead to their break-up into graphene nanostructures. On the other hand, direct coupling between functionalities bound on individual nanotubes could lead to, as yet unexplored, spontaneous chemical reactions. Here we report an ambient mechano-chemical reaction between two varieties of nanotubes, carrying predominantly carboxyl and hydroxyl functionalities, respectively, facilitated by simple mechanical grinding of the reactants. The purely solid-state reaction between the chemically differentiated nanotube species produces condensation products and unzipping of nanotubes due to local energy release, as confirmed by spectroscopic measurements, thermal analysis and molecular dynamic simulations. PMID:26073564

  6. Ambient solid-state mechano-chemical reactions between functionalized carbon nanotubes.

    PubMed

    Kabbani, Mohamad A; Tiwary, Chandra Sekhar; Autreto, Pedro A S; Brunetto, Gustavo; Som, Anirban; Krishnadas, K R; Ozden, Sehmus; Hackenberg, Ken P; Gong, Yongi; Galvao, Douglas S; Vajtai, Robert; Kabbani, Ahmad T; Pradeep, Thalappil; Ajayan, Pulickel M

    2015-01-01

    Carbon nanotubes can be chemically modified by attaching various functionalities to their surfaces, although harsh chemical treatments can lead to their break-up into graphene nanostructures. On the other hand, direct coupling between functionalities bound on individual nanotubes could lead to, as yet unexplored, spontaneous chemical reactions. Here we report an ambient mechano-chemical reaction between two varieties of nanotubes, carrying predominantly carboxyl and hydroxyl functionalities, respectively, facilitated by simple mechanical grinding of the reactants. The purely solid-state reaction between the chemically differentiated nanotube species produces condensation products and unzipping of nanotubes due to local energy release, as confirmed by spectroscopic measurements, thermal analysis and molecular dynamic simulations. PMID:26073564

  7. Signatures of chemical reactions in the morphology and fluctuations of giant vesicles

    NASA Astrophysics Data System (ADS)

    Döbereiner, Hans-Günther; Petrov, Peter G.; Riske, Karin A.

    2003-01-01

    The behaviour of an amphiphilic membrane is determined by the physical and chemical properties of the molecules which form the bilayer and their interactions with the surrounding medium. Bulk or interfacial chemical reactions modify interaction parameters and/or affect directly the chemical composition of the membrane. We monitor the morphological response and the thermal fluctuations of giant lipid vesicles to chemical reactions in the external vesicle medium using phase-contrast microscopy. Observation of vesicle conformations as a function of time allows us to characterize the statics and dynamics of membrane response as well as the underlying chemical kinetics. As two examples, we present (a) a photochemical reaction of hexacyanoferrate which induces an increase in pH and (b) the enzymatic cleavage of phosphatidyl choline by the phospholipase C from Bacillus cereus.

  8. Chemical reactions in turbulent mixing flows

    NASA Astrophysics Data System (ADS)

    Dimotakis, Paul E.; Leonard, Anthony

    1993-07-01

    In the course of this research we have conducted investigations of turbulent mixing, chemical reaction, and combustion processes in turbulent, subsonic, and supersonic flows. The program was comprised of several parts: an experimental effort, a theoretical and numerical simulation effort, and a development of instrumentation and diagnostics; an upgrade of flow and combustion facilities; and the development of data-acquisition sub-systems. We have carried out a series of theoretical and experimental studies of turbulent mixing in two well-defined, fundamentally important flow fields: free-shear layers and axisymmetric jets. To elucidate molecular transport effects, experiments and theory have dealt with both reacting and non-reacting flows of liquids and gases in fully-developed turbulent flows. A criterion for fully-developed turbulence was recently developed. The computational studies are, at present, focused at fundamental formulation and implementation issues pertaining to the simulation of both compressible and incompressible flows characterized by strong fronts, such as shock waves and flames. In our diagnostic development efforts we have improved the signal-to-noise ratio of flow images, in both gas- and liquid-phase flows, as well as continued with the development of data-acquisition electronics to meet very high-speed, high-volume data requirements; the acquisition of single, or pairs, of two-dimensional images in rapid succession; and the acquisition of data from arrays of supersonic flow sensors.

  9. Slow chemical reactions in power plant plumes: application to sulfates

    SciTech Connect

    Forney, L.J.; Giz, Z.G.

    1980-01-01

    Slow chemical reactions in which plume travel time is short compared with characteristic chemical reaction times are incorporated into the MIT buoyant plume theory. Conservation equations are written for a buoyant plume in a crosswind. Approximate solutions to the conservation equations are derived and compared with numerical results. Approximate solutions compared favorably with representative field data. (1 diagram, 4 graphs, 29 references, 1 table)

  10. On the rate of relativistic surface chemical reactions.

    PubMed

    Veitsman, E V

    2004-07-15

    On the basis of special relativity and the classical theory of chemical reaction rates it is shown how the surface chemical reaction rates vary as v --> c, where v is the velocity of the object under study and c is the velocity of light. PMID:15178286

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

    PubMed

    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. PMID:25725713

  12. Mesoscale simulations of shockwave energy dissipation via chemical reactions

    NASA Astrophysics Data System (ADS)

    Antillon, Edwin; Strachan, Alejandro

    2015-02-01

    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.

  13. LIGAND: database of chemical compounds and reactions in biological pathways

    Microsoft Academic Search

    Susumu Goto; Yasushi Okuno; Masahiro Hattori; Takaaki Nishioka; Minoru Kanehisa

    2002-01-01

    LIGAND is a composite database comprising three sections: COMPOUND for the information about metabolites and other chemical compounds, REACTION for the collection of substrate-product relations representing metabolic and other reactions, and ENZYME for the information about enzyme molecules. The current release (as of September 7, 2001) includes 7298 compounds, 5166 reactions and 3829 enzymes. In addition to the keyword search

  14. Exact Stochastic Simulation of Chemical Reactions with Cycle Leaping*

    E-print Network

    Bruck, Jehoshua (Shuki)

    Exact Stochastic Simulation of Chemical Reactions with Cycle Leaping* Marc D. Riedel Jehoshua Bruck. It tracks in- teger quantities of the molecular species, executing reactions at random based on propensity the re- sults of repeated trials. Unfortunately, for models with many reaction channels and many species

  15. Advanced Chemical Heat Pumps Using Liquid-Vapor Reactions

    E-print Network

    Kirol, L.

    ADVANCED CHEMICAL HEAT PUMPS USING LIQUID-VAPOR REACTIONS LANCE KIROL Senior Program Specialist Idaho National Engineering Laboratory Idaho Falls, Idaho . ABSTRACT Chemical heat pumps utilizing liquid-vapor reactions can be configured... characteristics. A waste heat driven heat pump (temperature amplifier) using liquid-vapor chem1cal reactions- can oper ate with higher coefficient of performance and smaller heat exchangers than an absorption temp erature amplifying heat pump. Higher tempera...

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

    PubMed

    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. PMID:25362839

  17. Incidents of chemical reactions in cell equipment

    SciTech Connect

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

    1991-12-31

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

  18. Deterministic Function Computation with Chemical Reaction Networks.

    PubMed

    Chen, Ho-Lin; Doty, David; Soloveichik, David

    2012-01-01

    Chemical reaction networks (CRNs) formally model chemistry in a well-mixed solution. CRNs are widely used to describe information processing occurring in natural cellular regulatory networks, and with upcoming advances in synthetic biology, CRNs are a promising language for the design of artificial molecular control circuitry. Nonetheless, despite the widespread use of CRNs in the natural sciences, the range of computational behaviors exhibited by CRNs is not well understood. CRNs have been shown to be efficiently Turing-universal (i.e., able to simulate arbitrary algorithms) when allowing for a small probability of error. CRNs that are guaranteed to converge on a correct answer, on the other hand, have been shown to decide only the semilinear predicates (a multi-dimensional generalization of "eventually periodic" sets). We introduce the notion of function, rather than predicate, computation by representing the output of a function f : ? (k) ? ? (l) by a count of some molecular species, i.e., if the CRN starts with x 1, …, xk molecules of some "input" species X 1, …, Xk , the CRN is guaranteed to converge to having f(x 1, …, xk ) molecules of the "output" species Y 1, …, Yl . We show that a function f : ? (k) ? ? (l) is deterministically computed by a CRN if and only if its graph {(x, y) ? ? (k) × ? (l) ? f(x) = y} is a semilinear set. Finally, we show that each semilinear function f (a function whose graph is a semilinear set) can be computed by a CRN on input x in expected time O(polylog ?x?1). PMID:25383068

  19. Injectivity of chemical reaction networks with mass action kinetics revisited

    E-print Network

    Feliu, Elisenda

    2011-01-01

    In this work we extend the characterization of injectivity via the Jacobian criterion first developed by Craciun and Feinberg for chemical reaction networks with outflow reactions to arbitrary chemical reaction networks taken with mass action kinetics. Injective chemical reaction networks do not have the capacity to admit multiple positive steady states for any rate constants and within each stoichiometric class. It is shown that a network is injective if and only if the determinant of the Jacobian of the system of ordinary differential equations associated to the network never vanishes. The determinant is a polynomial on the species concentrations and the rate constants, and its coefficients are fully determined. Previous works apply to chemical reaction networks whose stoichiometric space has maximal dimension. Here we present a direct route, independent of the dimension of the stoichiometric space which precludes at the same time the existence of degenerate steady states.

  20. CHEMICAL TAILORING OF TEICOPLANIN WITH SITE-SELECTIVE REACTIONS

    PubMed Central

    Pathak, Tejas P.; Miller, Scott J.

    2013-01-01

    Semi-synthesis 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 analogs 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 analogs 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 analogs with attenuated or enhanced antibacterial properties, in particular against vancomycin and teicoplanin resistance strains. PMID:23692563

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

    ERIC Educational Resources Information Center

    Wright, Stephen W.

    2002-01-01

    Describes a dramatic chemical demonstration in which chemicals that are black and white combine to produce a colorless liquid. Reactants include tincture of iodine, bleach, white vinegar, Epsom salt, vitamin C tablets, and liquid laundry starch. (DDR)

  2. Non-equilibrium effects in high temperature chemical reactions

    NASA Technical Reports Server (NTRS)

    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. Morphological changes of amphiphilic molecular assemblies induced by chemical reactions.

    PubMed

    Nakagawa, Koh M; Noguchi, Hiroshi

    2015-02-01

    Shape transformations of amphiphilic molecular assemblies induced by chemical reactions are studied using coarse-grained molecular simulations. A binding reaction between hydrophilic and hydrophobic molecules is considered. It is found that the reaction induces transformation of an oil droplet to a tubular vesicle via bicelles and vesicles with discoidal arms. The discoidal arms close into vesicles, which are subsequently fused into the tubular vesicle. Under the chemical reaction, the bicelle-to-vesicle transition occurs at smaller sizes than in the absence of the hydrophobic molecules. It is revealed that the enhancement of this transition is due to embedded hydrophobic particles that reduce the membrane bending rigidity. PMID:25582908

  4. Morphological changes of amphiphilic molecular assemblies induced by chemical reactions

    NASA Astrophysics Data System (ADS)

    Nakagawa, Koh M.; Noguchi, Hiroshi

    Shape transformations of amphiphilic molecular assemblies induced by chemical reaction are studied using coarse-grained molecular simulations. A binding reaction between hydrophilic and hydrophobic molecules is considered. It is found that the reaction induces transformation of an oil droplet to a tubular vesicle via bicelles and vesicles with discoidal arms. The discoidal arms close into vesicles, which are subsequently fused into the tubular vesicle. Under the chemical reaction, the bicelle-to-vesicle transition occurs at smaller sizes than in the absence of the hydrophobic molecules. It is revealed that the enhancement of this transition is due to embedded hydrophobic particles that reduce the membrane bending rigidity.

  5. Morphological changes of amphiphilic molecular assemblies induced by chemical reaction

    E-print Network

    Koh M. Nakagawa; Hiroshi Noguchi

    2014-11-21

    Shape transformations of amphiphilic molecular assemblies induced by chemical reaction are studied using coarse-grained molecular simulations. A binding reaction between hydrophilic and hydrophobic molecules is considered. It is found that the reaction induces transformation of an oil droplet to a tubular vesicle via bicelles and vesicles with discoidal arms. The discoidal arms close into vesicles, which are subsequently fused into the tubular vesicle. Under the chemical reaction, the bicelle-to-vesicle transition occurs at smaller sizes than in the absence of the hydrophobic molecules. It is revealed that the enhancement of this transition is due to embedded hydrophobic particles that reduce the membrane bending rigidity.

  6. Developing Secondary Students' Conceptions of Chemical Reactions: The Introduction of Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Van Driel, Jan H.; De Vos, Wobbe; Verloop, Nico; Dekkers, Hetty

    1998-01-01

    Describes an empirical study concerning the introduction of the concept of chemical equilibrium in chemistry classrooms in a way which challenges students' initial conceptions of chemical reactions. Contains 23 references. (DDR)

  7. The Activated Complex in Chemical Reactions

    Microsoft Academic Search

    Henry Eyring

    1935-01-01

    The calculation of absolute reaction rates is formulated in terms of quantities which are available from the potential surfaces which can be constructed at the present time. The probability of the activated state is calculated using ordinary statistical mechanics. This probability multiplied by the rate of decomposition gives the specific rate of reaction. The occurrence of quantized vibrations in the

  8. The Fluid Mechanics of Chemical Reaction

    NASA Astrophysics Data System (ADS)

    Benson, D. A.; Engdahl, N. B.; Bolster, D.

    2014-12-01

    The ability for reactive constituents to mix is often the key limiting factor for the completion of reactions across a huge range of scales in a variety of media. In flowing systems, deformation and shear enhance mixing by bringing constituents into closer proximity, thus increasing reaction potential. Accurately quantifying this enhanced mixing is key to predicting reactions, and typically is done by observing or simulating scalar transport. To eliminate this computationally expensive step, we use a Lagrangian stochastic framework to derive the enhancement to reaction potential by calculating the collocation probability of particle pairs in a heterogeneous flow field accounting for deformations. We relate the enhanced reaction potential to three well-known flow topology metrics (Okubo-Weiss, finite-time Lyapunov exponent, and right Cauchy-Green tensor) and demonstrate that it is best correlated to the largest eigenvalue of the right Cauchy-Green tensor. The reason is that this eigenvalue reflects compression and shear but ignores rotation, which does not enhance mixing. We demonstrate that regions of high shear and/or compression do indeed have higher rates of reaction in particle-tracking reaction simulations, but this is not necessarily seen in traditional Eulerian simulations due to numerical (artificial) mixing and the amplification of these errors by non-linear reactions.

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

    E-print Network

    Churchill, L R; Chapman, M S

    2010-01-01

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

  10. The How and Why of Chemical Reactions

    ERIC Educational Resources Information Center

    Schubert, Leo

    1970-01-01

    Presents a discussion of some of the fundamental concepts in thermodynamics and quantum mechanics including entropy, enthalpy, free energy, the partition function, chemical kinetics, transition state theory, the making and breaking of chemical bonds, electronegativity, ion sizes, intermolecular energies and of their role in explaining the nature…

  11. Organic chemical reactions in supercritical water

    Microsoft Academic Search

    Phillip E. Savage

    1999-01-01

    Water near or above its critical point (374 C, 218 atm) is attracting increased attention as a medium for organic chemistry. Most of this new attention is driven by the search for more green or environmentally benign chemical processes. Using near-critical or supercritical water (SCW) instead of organic solvents in chemical processes offers environmental advantages and may lead to pollution

  12. Advanced Chemical Heat Pumps Using Liquid-Vapor Reactions 

    E-print Network

    Kirol, L.

    1987-01-01

    Chemical heat pumps utilizing liquid-vapor reactions can be configured in forms analogous to electric drive vapor-compression heat pumps and heat activated absorption heat pumps. Basic thermodynamic considerations eliminate some heat pumps and place...

  13. Log-domain circuit models of chemical reactions

    E-print Network

    Mandal, Soumyajit

    We exploit the detailed similarities between electronics and chemistry to develop efficient, scalable bipolar or subthreshold log-domain circuits that are dynamically equivalent to networks of chemical reactions. Our ...

  14. 29. NORTHWEST VIEW OF BOILER FEEDWATER CHEMICAL REACTION TANKS, WITH ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    29. NORTHWEST VIEW OF BOILER FEEDWATER CHEMICAL REACTION TANKS, WITH FORMER GENERAL OFFICE BUILDING IN BACKGROUND. - U.S. Steel Duquesne Works, Fuel & Utilities Plant, Along Monongahela River, Duquesne, Allegheny County, PA

  15. Determining Interconnections in Chemical Reaction Networks Antonis Papachristodoulou and Ben Recht

    E-print Network

    Nowak, Robert

    Determining Interconnections in Chemical Reaction Networks Antonis Papachristodoulou and Ben Recht Abstract-- We present a methodology for robust determina- tion of chemical reaction network' dynamics. We illustrate our methodology on a hypothetical chemical reaction network under various

  16. APRIORI BOUNDS FOR REACTION-DIFFUSION SYSTEMS ARISING IN CHEMICAL JEFF S. MCGOUGH AND KYLE RILEY

    E-print Network

    McGough, Jeff S.

    APRIORI BOUNDS FOR REACTION-DIFFUSION SYSTEMS ARISING IN CHEMICAL KINETICS JEFF S. MCGOUGH AND KYLE RILEY Abstract. The authors investigate reaction diffusion equations which arise in chemical kinetics diffusion equations, gradient bounds, chemical kinetics, autocatalytic reactions AMS subject classifications

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

    USGS Publications Warehouse

    Grove, David B.; Stollenwerk, Kenneth G.

    1987-01-01

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

  18. Computed potential energy surfaces for chemical reactions

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.; Levin, Eugene

    1993-01-01

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

  19. Kinetics of Heterogeneous Chemical Reactions, II*

    PubMed Central

    Lin, S. H.; Eyring, H.

    1970-01-01

    The first-order and zero-order kinetics of heterogeneous reactions coupled with the diffusion process are studied. The differential equations of these reaction systems are solved for the cases in which the fluid is not stirred and the fluid is well stirred. It is shown that both the rate constants and the diffusion coefficient can be determined in various ways depending on the experimental conditions. PMID:5263761

  20. Development of the reaction time accelerating molecular dynamics method for simulation of chemical reaction

    NASA Astrophysics Data System (ADS)

    Takaba, Hiromitsu; Hayashi, Shigekazu; Zhong, Huifeng; Malani, Hema; Suzuki, Ai; Sahnoun, Riadh; Koyama, Michihisa; Tsuboi, Hideyuki; Hatakeyama, Nozomu; Endou, Akira; Kubo, Momoji; Del Carrpio, Carlos A.; Miyamoto, Akira

    2008-09-01

    We present a novel and efficient method to integrate chemical reactions into molecular dynamics to simulate chemical reaction systems. We have dubbed this method RTAMD, an acronym for reaction time accelerating molecular dynamics. The methodology we propose here requires no more than the knowledge of the empirical intermolecular potentials for the species at play as well as the elementary reaction path among them. Bond formation during the simulation is performed by changing the inter-atomic potentials from those of the non-bonded species to those of the bonded ones, and a reaction is deemed to occur by the distance separating the bond forming atoms. In this way the energy barrier for a reaction is no longer considered; the estimation of the reaction rate, however, is possible by introducing the principles of the transition state theory. The simplicity of the present scheme to simulate chemical reactions enables it to be used in large-scale MD simulations involving a large number of simultaneous chemical reactions and to evaluate kinetic parameters. In this paper, the basic theory of the method is presented and application to simple equiatomic reaction system where the reaction rates were estimated was illustrated.

  1. Shock-induced chemical reactions and synthesis of nickel aluminides

    Microsoft Academic Search

    I. Song; N. N. Thadhani

    1992-01-01

    Chemical reactions in Ni and Al powder mixtures, initiated by the passage of shock waves, are used for the synthesis of nickel\\u000a aluminides. Mechanistic investigations reveal that the extent of these shock-induced chemical reactions and the type (stoichiometry)\\u000a of shock-synthesized compound formed depend on shock-loading conditions and the initial powder particle morphology. More intense\\u000a shock conditions and irregular powder morphology

  2. Chemical reactions of organic compounds on clay surfaces.

    PubMed Central

    Soma, Y; Soma, M

    1989-01-01

    Chemical reactions of organic compounds including pesticides at the interlayer and exterior surfaces of clay minerals and with soil organic matter are reviewed. Representative reactions under moderate conditions possibly occurring in natural soils are described. Attempts have been made to clarify the importance of the chemical nature of molecules, their structures and their functional groups, and the Brönsted or Lewis acidity of clay minerals. PMID:2533556

  3. Chemical pathways in ultracold reactions of SrF molecules

    E-print Network

    Meyer, Edmund R

    2011-01-01

    We present a theoretical investigation of the chemical reaction SrF + SrF $\\rightarrow$ products, focusing on reactions at ultralow temperatures. We find that bond swapping, SrF + SrF $\\rightarrow$ Sr$_2$ + F$_2$, is energetically forbidden at these temperatures. Rather, the only energetically allowed reaction is SrF + SrF $\\rightarrow$ SrF$_2$ + Sr, and even then only singlet states of the SrF$_2$ trimer can form. A calculation along a reduced reaction path demonstrates that this abstraction reaction is barrierless, and proceeds by one SrF molecule "handing off" a fluorine atom to the other molecule.

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  5. Nanochemistry – Chemical Reactions of Iron and Benzene Within Molecular Clusters

    Microsoft Academic Search

    C. S. Feigerle; S. Bililign; John C. Miller

    2000-01-01

    Molecular clusters represent a nanoscale test tube where chemical reactions can be examined in a unique way for the effects of the local environment and the possibility of size-dependent reactions. Previous experiments have shown that the ionization\\/dissociation of iron pentacarbonyl clusters can lead to the formation of iron ions and iron cluster ions and that these species can further react

  6. Plasmonic smart dust for probing local chemical reactions.

    PubMed

    Tittl, Andreas; Yin, Xinghui; Giessen, Harald; Tian, Xiang-Dong; Tian, Zhong-Qun; Kremers, Christian; Chigrin, Dmitry N; Liu, Na

    2013-04-10

    Locally probing chemical reactions or catalytic processes on surfaces under realistic reaction conditions has remained one of the main challenges in materials science and heterogeneous catalysis. Where conventional surface interrogation techniques usually require high-vacuum conditions or ensemble average measurements, plasmonic nanoparticles excel in extreme light focusing and can produce highly confined electromagnetic fields in subwavelength volumes without the need for complex near-field microscopes. Here, we demonstrate an all-optical probing technique based on plasmonic smart dust for monitoring local chemical reactions in real time. The silica shell-isolated gold nanoparticles that form the smart dust can work as strong light concentrators and optically report subtle environmental changes at their pinning sites on the probed surface during reaction processes. As a model system, we investigate the hydrogen dissociation and subsequent uptake trajectory in palladium with both "dust-on-film" and "film-on-dust" platforms. Using time-resolved single particle measurements, we demonstrate that our technique can in situ encode chemical reaction information as optical signals for a variety of surface morphologies. The presented technique offers a unique scheme for real-time, label-free, and high-resolution probing of local reaction kinetics in a plethora of important chemical reactions on surfaces, paving the way toward the development of inexpensive and high-output reaction sensors for real-world applications. PMID:23458121

  7. Cu-free click cycloaddition reactions in chemical biology†

    PubMed Central

    Jewett, John C.

    2010-01-01

    Bioorthogonal chemical reactions are paving the way for new innovations in biology. These reactions possess extreme selectivity and biocompatibility, such that their participating reagents can form covalent bonds within richly functionalized biological systems—in some cases, living organisms. This tutorial review will summarize the history of this emerging field, as well as recent progress in the development and application of bioorthogonal copper-free click cycloaddition reactions. PMID:20349533

  8. Stochastic Chemical Reactions in Micro-domains

    Microsoft Academic Search

    D. Holcman; Z. Schuss

    2004-01-01

    Traditional chemical kinetics may be inappropriate to describe chemical\\u000areactions in micro-domains involving only a small number of substrate and\\u000areactant molecules. Starting with the stochastic dynamics of the molecules, we\\u000aderive a master-diffusion equation for the joint probability density of a\\u000amobile reactant and the number of bound substrate in a confined domain. We use\\u000athe equation to calculate

  9. A Modular Three-Dimensional Transport Model for Simulation of Advection, Dispersion and Chemical Reaction

    E-print Network

    Zheng, Chunmiao

    and Chemical Reaction of Contaminants in Groundwater Systems By C. Zheng S.S. Papadopulos & Associates, Inc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 - 7 2.5 CHEMICAL REACTIONS

  10. Photo, thermal and chemical degradation of riboflavin.

    PubMed

    Sheraz, Muhammad Ali; Kazi, Sadia Hafeez; Ahmed, Sofia; Anwar, Zubair; Ahmad, Iqbal

    2014-01-01

    Riboflavin (RF), also known as vitamin B2, belongs to the class of water-soluble vitamins and is widely present in a variety of food products. It is sensitive to light and high temperature, and therefore, needs a consideration of these factors for its stability in food products and pharmaceutical preparations. A number of other factors have also been identified that affect the stability of RF. These factors include radiation source, its intensity and wavelength, pH, presence of oxygen, buffer concentration and ionic strength, solvent polarity and viscosity, and use of stabilizers and complexing agents. A detailed review of the literature in this field has been made and all those factors that affect the photo, thermal and chemical degradation of RF have been discussed. RF undergoes degradation through several mechanisms and an understanding of the mode of photo- and thermal degradation of RF may help in the stabilization of the vitamin. A general scheme for the photodegradation of RF is presented. PMID:25246959

  11. Computed potential energy surfaces for chemical reactions

    NASA Technical Reports Server (NTRS)

    Heinemann, K.; Walch, Stephen P.

    1992-01-01

    The work on the NH + NO system which was described in the last progress report was written up and a draft of the manuscript is included in the appendix. The appendix also contains a draft of a manuscript on an Ar + H + H surface. New work which was completed in the last six months includes the following: (1) calculations on the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels in the CH3 + OH reaction; (2) calculations for the NH2 + O reaction; (3) calculations for the CH3 + O2 reaction; and (4) calculations for CH3O and the two decomposition channels--CH2OH and H + H2CO. Detailed descriptions of this work will be given in manuscripts; however, brief descriptions of the CH3 + OH and CH3 + O2 projects are given.

  12. Conservation-dissipation structure of chemical reaction systems.

    PubMed

    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. PMID:23368081

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

    ERIC Educational Resources Information Center

    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…

  14. Influence of trace impurities on chemical reaction hazards

    Microsoft Academic Search

    J. L. Gustin

    2002-01-01

    The influence of trace impurities is frequently mentioned as a possible or probable cause of accidents in the chemical industry. In process conditions where there is a potential for a fast exothermic decomposition or polymerisation reaction, the contamination of pure chemicals by trace impurities may cause problems. Typical examples of this situation are described concerning the processing of organic nitrocompounds

  15. Effect of Finite-rate Chemical Reactions on Turbulence in Hypersonic Turbulent Boundary Layers

    E-print Network

    Martín, Pino

    Effect of Finite-rate Chemical Reactions on Turbulence in Hypersonic Turbulent Boundary Layers Lian reaction. The influence of chemical reactions on temperature fluctuation variance, Reynolds stresses that the recombination reaction enhances turbulence, while the dissociation reaction damps turbulence. Chemical reactions

  16. Basics of Chemical Kinetics -1 Rate of reaction = rate of disappearance of A =

    E-print Network

    Albert, Réka

    Basics of Chemical Kinetics - 1 Rate of reaction = rate of disappearance of A = # of moles of Chemical Kinetics - 3 Elementary Reaction: Reaction order of each species is identical reactions: Forward Reaction Backward Reaction CBA + 2 CBA + 2 CBA + 2 CBA + 2 #12;Basics of Chemical

  17. Analysis of the Reaction Rate Coefficients for Slow Bimolecular Chemical Reactions

    E-print Network

    Kremer, Gilberto M

    2012-01-01

    Simple bimolecular reactions $A_1+A_2\\rightleftharpoons A_3+A_4$ are analyzed within the framework of the Boltzmann equation in the initial stage of a chemical reaction with the system far from chemical equilibrium. The Chapman-Enskog methodology is applied to determine the coefficients of the expansion of the distribution functions in terms of Sonine polynomials for peculiar molecular velocities. The results are applied to the reaction $H_2+Cl\\rightleftharpoons HCl+H$, and the influence of the non-Maxwellian distribution and of the activation-energy dependent reactive cross sections upon the forward and reverse reaction rate coefficients are discussed.

  18. Concerted reactions of polynuclear metalloenzymes and their functional chemical models

    NASA Astrophysics Data System (ADS)

    Dzhabiev, T. S.; Shilov, A. E.

    2011-03-01

    The mechanisms of the many-electron oxidation of water by a chemical model of the manganese oxidase cofactor in photosynthesis photosystem II (manganese(IV) clusters) and nitrogen reduction in chemical models of nitrogenase cofactor (vanadium(II) and molybdenum(III) clusters) were considered. The hypothesis was suggested according to which polynuclear enzyme cofactors and their functional chemical models performed two important functions, catalyzed noncomplementary processes and effected many-substrate concerted reactions with decreased activation energies.

  19. Photochemical reactions of anthropogenic chemicals in seawater

    Microsoft Academic Search

    A. P. Toole; D. G. Crosby

    1988-01-01

    Sunlight-driven, photochemical reactions can be a major degradative force for anthropogenic organic compounds in the aquatic environment. Chlorinated phenols, various classes of pesticides, and polycyclic aromatic hydrocarbons are among some examples of the compounds shown to be degraded by sunlight. Most environmental photochemistry has been studied in fresh water, despite the fact that the oceans cover more than 70% of

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

    PubMed

    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 . PMID:24160861

  1. Chemical Memory Reactions Induced Bursting Dynamics in Gene Expression

    PubMed Central

    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. PMID:23349679

  2. LIGAND: Database of Chemical Compounds and Reactions in Biological Pathways

    NSDL National Science Digital Library

    The Institute for Chemical Research at Kyoto University provides this frequently updated and well-documented database of enzyme reactions. With more than 9,300 entries, the LIGAND Chemical Database includes over 3,700 entries for enzymes (the Enzyme Reaction Database) and 5,600 entries for compounds (Chemical Compound Database). The database is searchable by keyword using DBGET (which supports numerous other databases and gene catalogs as well) and is accompanied by clear instructions. The LIGAND database, updated weekly, may be downloaded via anonymous FTP.

  3. Chemical kinetic reaction mechanism for the combustion of propane

    NASA Technical Reports Server (NTRS)

    Jachimowski, C. J.

    1984-01-01

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

  4. Thermal oxidative degradation reactions of perfluoroalklethers

    NASA Technical Reports Server (NTRS)

    Paciorek, K. L.; Harris, D. H.; Smythe, M. E.; Kratzer, R. H.

    1983-01-01

    The objective of this contract was to investigate the mechanisms operative in thermal and thermal oxidative degradation of Fomblin Z and hexafluoropropene oxide derived fluids and the effect of alloys and additives upon these processes. The nature of arrangements responsible for the inherent thermal oxidative instability of the Fomblin Z fluids has not been established. It was determined that this behavior was not associated with hydrogen end-groups or peroxy linkages. The degradation rate of these fluids at elevated temperatures in oxidizing atmospheres was found to be dependent on the surface/volume ratio. Once a limiting ratio was reached, a steady rate appeared to be attained. Based on elemental analysis and oxygen consumption data, -CF2OCF2CF2O-, not -CF2CF2O-, is one of the major arrangements present. The action of the M-50 and Ti(4 Al, 4 Mn) alloys was found to be much more drastic in the case of Fomblin Z fluids than that observed for the hexalfuoropropane oxide derived materials. The effectiveness of antioxidation/anticorrosion additives, P-3 and phospha-s-triazine, in the presence of metal alloys was very limited at 316 C; at 288 C the additives arrested almost completely the fluid degradation. The phospha-s-triazine appeared to be at least twice as effective as the P-3 compound; it also protected the coupon better. The Ti(4 Al, 4 Mn) alloy degraded the fluid mainly by chain scission processes; this took place to a much lesser degree with M-50.

  5. High thermal and chemical stability in pyrazolate-bridged metalorganic frameworks with exposed metal sites

    E-print Network

    High thermal and chemical stability in pyrazolate-bridged metal­organic frameworks with exposed April 2011 DOI: 10.1039/c1sc00136a Reactions between the tritopic pyrazole-based ligand 1,3,5-tris(1H-pyrazol-4-yl)benzene (H3BTP) and transition metal acetate salts in DMF afford microporous pyrazolate

  6. A chemical heat pump using carbon fibers as additive. Part I: enhancement of thermal conduction

    Microsoft Academic Search

    T Dellero; D Sarmeo; Ph Touzain

    1999-01-01

    To use carbon fibers as additive in a chemical heat pump, based on a solid–gas reaction, three mixtures of carbon fibers with the reagent compounds are proposed: simple mixture, impregnation of the carbon fibers with reagent compounds and intercalation of the reagent compounds into graphite fibers. By adding carbon fibers, the thermal conductivity of the reagent bed is enhanced. While

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

    PubMed Central

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

    2014-01-01

    The combination of chemoinformatics approaches with NMR techniques and the increasing availability of data allow the resolution of problems far beyond the original application of NMR in structure elucidation/verification. The diversity of applications can range from process monitoring, metabolic profiling, authentication of products, to quality control. An application related to the automatic analysis of complex mixtures concerns mixtures of chemical reactions. We encoded mixtures of chemical reactions with the difference between the 1H NMR spectra of the products and the reactants. All the signals arising from all the reactants of the co-occurring reactions were taken together (a simulated spectrum of the mixture of reactants) and the same was done for products. The difference spectrum is taken as the representation of the mixture of chemical reactions. A data set of 181 chemical reactions was used, each reaction manually assigned to one of 6 types. From this dataset, we simulated mixtures where two reactions of different types would occur simultaneously. Automatic learning methods were trained to classify the reactions occurring in a mixture from the 1H NMR-based descriptor of the mixture. Unsupervised learning methods (self-organizing maps) produced a reasonable clustering of the mixtures by reaction type, and allowed the correct classification of 80% and 63% of the mixtures in two independent test sets of different similarity to the training set. With random forests (RF), the percentage of correct classifications was increased to 99% and 80% for the same test sets. The RF probability associated to the predictions yielded a robust indication of their reliability. This study demonstrates the possibility of applying machine learning methods to automatically identify types of co-occurring chemical reactions from NMR data. Using no explicit structural information about the reactions participants, reaction elucidation is performed without structure elucidation of the molecules in the mixtures. PMID:24551112

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

    PubMed

    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 the molecules in the mixtures. PMID:24551112

  9. Sequential Voronoi diagram calculations using simple chemical reactions

    E-print Network

    Costello, Ben de Lacy; Adamatzky, Andy

    2012-01-01

    In our recent paper [de Lacy Costello et al. 2010] we described the formation of complex tessellations of the plane arising from the various reactions of metal salts with potassium ferricyanide and ferrocyanide loaded gels. In addition to producing colourful tessellations these reactions are naturally computing generalised Voronoi diagrams of the plane. The reactions reported previously were capable of the calculation of three distinct Voronoi diagrams of the plane. As diffusion coupled with a chemical reaction is responsible for the calculation then this is achieved in parallel. Thus an increase in the complexity of the data input does not utilise additional computational resource. Additional benefits of these chemical reactions is that a permanent record of the Voronoi diagram calculation (in the form of precipitate free bisectors) is achieved, so there is no requirement for further processing to extract the calculation results. Previously it was assumed that the permanence of the results was also a potenti...

  10. Thermal oxidative degradation reactions of perfluoroalkylethers

    NASA Technical Reports Server (NTRS)

    Paciorek, K. L.; Ito, T. I.; Kratzer, R. H.

    1981-01-01

    The mechanisms operative in thermal oxidative degradation of Fomblin Z and hexafluoropropene oxide derived fluids and the effect of alloys and additives upon these processes are investigated. The nature of arrangements responsible for the inherent thermal oxidative instability of the Fomblin Z fluids is not established. It was determined that this behavior is not associated with hydrogen end groups or peroxy linkages. The degradation rate of these fluids at elevated temperatures in oxidizing atmospheres is dependent on the surface/volume ratio. Once a limiting ratio is reached, a steady rate appears to be attained. Based on elemental analysis and oxygen consumption data, CF2OCF2CF2O2, no. CF2CF2O, is one of the major arrangements present. The action of the M-50 and Ti(4 Al, 4 Mn) alloys is much more drastic in the case of Fomblin Z fluids than that observed for the hexafluoropropene derived materials. The effectiveness of antioxidation anticorrosion additives, P-3 and phospha-s-triazine, in the presence of metal alloys is very limited at 316 C; at 288 C the additives arrested almost completely the fluid degradation. The phospha-s-triazine appears to be at least twice as effective as the P-3 compound; it also protected the coupon better. The Ti(4 Al, 4 Mn) alloy degraded the fluid mainly by chain scission processes this takes place to a much lesser degree with M-50.

  11. Symmetry numbers and chemical reaction rates

    Microsoft Academic Search

    Antonio Fernández-Ramos; Benjamin A. Ellingson; Rubén Meana-Pañeda; Jorge M. C. Marques; Donald G. Truhlar

    2007-01-01

    This article shows how to evaluate rotational symmetry numbers for different molecular configurations and how to apply them\\u000a to transition state theory. In general, the symmetry number is given by the ratio of the reactant and transition state rotational\\u000a symmetry numbers. However, special care is advised in the evaluation of symmetry numbers in the following situations: (i)\\u000a if the reaction

  12. Understanding chemical reactions within a generalized Hamilton-Jacobi framework

    E-print Network

    A. S. Sanz; X. Gimenez; J. M. Bofill; S. Miret-Artes

    2009-08-13

    Reaction paths and classical and quantum trajectories are studied within a generalized Hamilton-Jacobi framework, which allows to put on equal footing topology and dynamics in chemical reactivity problems. In doing so, we show how high-dimensional problems could be dealt with by means of Caratheodory plots or how trajectory-based quantum-classical analyses reveal unexpected discrepancies. As a working model, we consider the reaction dynamics associated with a Mueller-Brown potential energy surface, where we focus on the relationship between reaction paths and trajectories as well as on reaction probability calculations from classical and quantum trajectories.

  13. LIGAND: database of chemical compounds and reactions in biological pathways

    PubMed Central

    Goto, Susumu; Okuno, Yasushi; Hattori, Masahiro; Nishioka, Takaaki; Kanehisa, Minoru

    2002-01-01

    LIGAND is a composite database comprising three sections: COMPOUND for the information about metabolites and other chemical compounds, REACTION for the collection of substrate–product relations representing metabolic and other reactions, and ENZYME for the information about enzyme molecules. The current release (as of September 7, 2001) includes 7298 compounds, 5166 reactions and 3829 enzymes. In addition to the keyword search provided by the DBGET/LinkDB system, a substructure search to the COMPOUND and REACTION sections is now available through the World Wide Web (http://www.genome.ad.jp/ligand/). LIGAND may be also downloaded by anonymous FTP (ftp://ftp.genome.ad.jp/pub/kegg/ligand/). PMID:11752349

  14. Advanced deposition model for thermal activated chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Cai, Dang

    Thermal Activated Chemical Vapor Deposition (TACVD) is defined as the formation of a stable solid product on a heated substrate surface from chemical reactions and/or dissociation of gaseous reactants in an activated environment. It has become an essential process for producing solid film, bulk material, coating, fibers, powders and monolithic components. Global market of CVD products has reached multi billions dollars for each year. In the recent years CVD process has been extensively used to manufacture semiconductors and other electronic components such as polysilicon, AlN and GaN. Extensive research effort has been directed to improve deposition quality and throughput. To obtain fast and high quality deposition, operational conditions such as temperature, pressure, fluid velocity and species concentration and geometry conditions such as source-substrate distance need to be well controlled in a CVD system. This thesis will focus on design of CVD processes through understanding the transport and reaction phenomena in the growth reactor. Since the in situ monitor is almost impossible for CVD reactor, many industrial resources have been expended to determine the optimum design by semi-empirical methods and trial-and-error procedures. This approach has allowed the achievement of improvements in the deposition sequence, but begins to show its limitations, as this method cannot always fulfill the more and more stringent specifications of the industry. To resolve this problem, numerical simulation is widely used in studying the growth techniques. The difficulty of numerical simulation of TACVD crystal growth process lies in the simulation of gas phase and surface reactions, especially the latter one, due to the fact that very limited kinetic information is available in the open literature. In this thesis, an advanced deposition model was developed to study the multi-component fluid flow, homogeneous gas phase reactions inside the reactor chamber, heterogeneous surface reactions on the substrate surface, conductive, convective, inductive and radiative heat transfer, species transport and thereto-elastic stress distributions. Gas phase and surface reactions are studied thermodynamically and kinetically. Based on experimental results, detailed reaction mechanisms are proposed and the deposition rates are predicted. The deposition model proposed could be used for other experiments with similar operating conditions. Four different growth systems are presented in this thesis to discuss comprehensive transport phenomena in crystal growth from vapor. The first is the polysilicon bulk growth by modified Siemens technique in which a silicon tube is used as the starting material. The research effort has been focused on system design, geometric and operating parameters optimization, and heterogeneous and homogeneous silane pyrolysis analysis. The second is the GaN thin film growth by iodine vapor phase epitaxy technique. Heat and mass transport is studied analytically and numerically. Gas phase and surface reactions are analyzed thermodynamically and kinetically. Quasi-equilibrium and kinetic deposition models are developed to predict the growth rate. The third one is the AlN thin film growth by halide vapor phase epitaxy technique. The effects of gas phase and surface reactions on the crystal growth rate and deposition uniformity are studied. The last one is the AlN sublimation growth system. The research effort has been focused on the effect of thermal environment evolution on the crystal growth process. The thermoelastic stress formed in the as-grown AlN crystal is also calculated.

  15. [Research on chemical reactions during ginseng processing].

    PubMed

    Zhang, Miao; Qin, Kun-Ming; Li, Wei-Dong; Yin, Fang-Zhou; Cai, Hao; Cai, Bao-Chang

    2014-10-01

    As a kind of commonly used traditional Chinese medicine, ginseng has a high reputation at home and abroad. The research of ginseng has been expanded to medicine, pharmacy, biology, food science and other fields, with great achievements in recent years. Ginseng contains ginsenosides, volatile oil, carbohydrates, amino acids, polypeptides, inorganic elements and othser chemical constituents. Each component has extensive physiological activity, and is the base of ginseng's effect. After processing, the complicated changes are taken place in the constituents of ginseng, and some new substances produced. This paper aims to review the studies on chemical constituents and their mechanisms during ginseng processing, and the ideas, methods and the direction of the development of traditional Chinese medicine processing in the future. PMID:25612424

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

    NASA Technical Reports Server (NTRS)

    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.

  17. Quantifying chemical reactions by using mixing analysis.

    PubMed

    Jurado, Anna; Vázquez-Suñé, Enric; Carrera, Jesús; Tubau, Isabel; Pujades, Estanislao

    2015-01-01

    This work is motivated by a sound understanding of the chemical processes that affect the organic pollutants in an urban aquifer. We propose an approach to quantify such processes using mixing calculations. The methodology consists of the following steps: (1) identification of the recharge sources (end-members) and selection of the species (conservative and non-conservative) to be used, (2) identification of the chemical processes and (3) evaluation of mixing ratios including the chemical processes. This methodology has been applied in the Besòs River Delta (NE Barcelona, Spain), where the River Besòs is the main aquifer recharge source. A total number of 51 groundwater samples were collected from July 2007 to May 2010 during four field campaigns. Three river end-members were necessary to explain the temporal variability of the River Besòs: one river end-member is from the wet periods (W1) and two are from dry periods (D1 and D2). This methodology has proved to be useful not only to compute the mixing ratios but also to quantify processes such as calcite and magnesite dissolution, aerobic respiration and denitrification undergone at each observation point. PMID:25280248

  18. THERMAL AND CHEMICAL EVOLUTION OF COLLAPSING FILAMENTS

    SciTech Connect

    Gray, William J. [Lawrence Livermore National Laboratory, P.O. Box 808, L-038, Livermore, CA 94550 (United States); Scannapieco, Evan [School of Earth and Space Exploration, Arizona State University, P.O. Box 871404, Tempe, AZ 85287-1494 (United States)

    2013-05-10

    Intergalactic filaments form the foundation of the cosmic web that connect galaxies together, and provide an important reservoir of gas for galaxy growth and accretion. Here we present very high resolution two-dimensional simulations of the thermal and chemical evolution of such filaments, making use of a 32 species chemistry network that tracks the evolution of key molecules formed from hydrogen, oxygen, and carbon. We study the evolution of filaments over a wide range of parameters including the initial density, initial temperature, strength of the dissociating UV background, and metallicity. In low-redshift, Z Almost-Equal-To 0.1 Z{sub Sun} filaments, the evolution is determined completely by the initial cooling time. If this is sufficiently short, the center of the filament always collapses to form a dense, cold core containing a substantial fraction of molecules. In high-redshift, Z = 10{sup -3} Z{sub Sun} filaments, the collapse proceeds much more slowly. This is mostly due to the lower initial temperatures, which lead to a much more modest increase in density before the atomic cooling limit is reached, making subsequent molecular cooling much less efficient. Finally, we study how the gravitational potential from a nearby dwarf galaxy affects the collapse of the filament and compare this to NGC 5253, a nearby starbursting dwarf galaxy thought to be fueled by the accretion of filament gas. In contrast to our fiducial case, a substantial density peak forms at the center of the potential. This peak evolves faster than the rest of the filament due to the increased rate at which chemical species form and cooling occurs. We find that we achieve similar accretion rates as NGC 5253 but our two-dimensional simulations do not recover the formation of the giant molecular clouds that are seen in radio observations.

  19. Shock-Induced Chemical Reactions in Structural Energetic Materials

    NASA Astrophysics Data System (ADS)

    Narayanan, V.; Lu, X.; Hanagud, S.

    2006-07-01

    Various powder mixtures like intermetallic mixtures and mixtures of metals and metal oxides have potential applications as structural energetic materials (SEMs). Technologies of varying the compositions and the powder sizes and their synthesis are being investigated to provide multiple desirable characteristics, like high strength and high energy content. In this paper, we formulate a model for SEMs for their application in shock conditions, in the framework of nonequilibrium thermodynamics and continuum mechanics. A mixture of Al and KClO4 is selected as the example for SEMs. A mixture, pore collapse and chemical reaction model are included. By adapting energy barriers for reaction as a function of temperature, particle size and pressure and introducing a relaxation mechanism in the reaction model, a shock-induced chemical reaction model is developed. The variation of the relaxation mechanism is also modeled. The initiation and propagation of chemical reactions are studied. The time and spatial dependency of chemical reaction on the shock wave conditions are investigated.

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

    PubMed

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

    2014-10-30

    Recently, a new metaheuristic called chemical reaction optimization was proposed. This search algorithm, inspired by chemical reactions launched during collisions, inherits several features from other metaheuristics such as simulated annealing and particle swarm optimization. This fact has made it, nowadays, one of the most powerful search algorithms in solving mono-objective optimization problems. In this paper, we propose a multiobjective variant of chemical reaction optimization, called nondominated sorting chemical reaction optimization, in an attempt to exploit chemical reaction optimization features in tackling problems involving multiple conflicting criteria. Since our approach is based on nondominated sorting, one of the main contributions of this paper is the proposal of a new quasi-linear average time complexity quick nondominated sorting algorithm; therebymaking our multiobjective algorithm efficient from a computational cost viewpoint. The experimental comparisons against several other multiobjective algorithms on a variety of benchmark problems involving various difficulties show the effectiveness and the efficiency of this multiobjective version in providing a wellconverged and well-diversified approximation of the Pareto front. PMID:25373137

  1. METHODOLOGICAL NOTES: Brusselator — an abstract chemical reaction?

    NASA Astrophysics Data System (ADS)

    Lavrova, Anastasiya I.; Postnikov, E. B.; Romanovsky, Yurii M.

    2009-12-01

    In this paper we consider the Brusselator and the Sel'kov model, which describes the irreversible reaction of glycolysis in the regime of self-sustained oscillations. We show that these two differently constructed models can be reduced to a single equation — a generalized Rayleigh equation. The physical basis for this generality is investigated. The advantages of this equation as a tool for qualitative and quantitative analyses, as well as the similarities and differences of the solutions realized for each of the two concrete models in the cases of almost harmonic and relaxation self-sustained oscillations, are discussed.

  2. Laser cutting with chemical reaction assist

    DOEpatents

    Gettemy, Donald J. (Los Alamos, NM)

    1992-01-01

    A method for cutting with a laser beam where an oxygen-hydrocarbon reaction is used to provide auxiliary energy to a metal workpiece to supplement the energy supplied by the laser. Oxygen is supplied to the laser focus point on the workpiece by a nozzle through which the laser beam also passes. A liquid hydrocarbon is supplied by coating the workpiece along the cutting path with the hydrocarbon prior to laser irradiation or by spraying a stream of hydrocarbon through a nozzle aimed at a point on the cutting path which is just ahead of the focus point during irradiation.

  3. Laser cutting with chemical reaction assist

    DOEpatents

    Gettemy, D.J.

    1992-11-17

    A method is described for cutting with a laser beam where an oxygen-hydrocarbon reaction is used to provide auxiliary energy to a metal workpiece to supplement the energy supplied by the laser. Oxygen is supplied to the laser focus point on the workpiece by a nozzle through which the laser beam also passes. A liquid hydrocarbon is supplied by coating the workpiece along the cutting path with the hydrocarbon prior to laser irradiation or by spraying a stream of hydrocarbon through a nozzle aimed at a point on the cutting path which is just ahead of the focus point during irradiation. 1 figure.

  4. Simulation of chemical reaction equilibria by the reaction ensemble Monte Carlo method: a review†

    Microsoft Academic Search

    C. Heath Turner; John K. Brennan; Martin Lísal; William R. Smith; J. Karl Johnson; Keith E. Gubbins

    2008-01-01

    Understanding and predicting the equilibrium behaviour of chemically reacting systems in highly non-ideal environments is critical to many fields of science and technology, including solvation, nanoporous materials, catalyst design, combustion and propulsion science, shock physics and many more. A method with recent success in predicting the equilibrium behaviour of reactions under non-ideal conditions is the reaction ensemble Monte Carlo method

  5. VoIume57, ncmber 3 -CAL PHYSICSLEITERS 1 Augst 1978 INFEWRED LASER INDUCED CHEMIC_AL REACTIONS

    E-print Network

    Miller, William H.

    VoIume57, ncmber 3 -CAL PHYSICSLEITERS 1 Augst 1978 INFEWRED LASER INDUCED CHEMIC_AL REACTIONS X)even if the reactants are infrared izctive. It is well-known that an infrared laser can accei- erate chemical reactions state. This letter points out that infrared Iaserscan en- hance chemical reactions even if they are far

  6. 5.0 Application of Chemical Reaction Codes 5.1. Background

    E-print Network

    5.1 5.0 Application of Chemical Reaction Codes 5.1. Background Determination of species analyses of water compositions and a competent chemical reaction model. Computerized chemical reaction that may leach from waste, an understanding of the capabilities and application of chemical reaction models

  7. Using hyperheuristics to improve the determination of the kinetic constants of a chemical reaction in

    E-print Network

    Giménez, Domingo

    Using hyperheuristics to improve the determination of the kinetic constants of a chemical reaction constants of a chemical reaction Kinetic parameters of a chemical reaction are determined with metaheuristic of a chemical reaction that occurs in heterogeneous phase involves the simulation of the processes occurring

  8. Chemical reaction network theory for in-silico biologists Jeremy Gunawardena

    E-print Network

    Gunawardena, Jeremy

    Chemical reaction network theory for in-silico biologists Jeremy Gunawardena Bauer Center@cgr.harvard.edu June 20, 2003 Contents 1 Introduction 1 2 Chemical reaction networks 2 3 Linearity in chemical reaction of a system of nonlinear ODEs. The second is Chemical Reaction Network Theory (CRNT), which establishes

  9. Chemical vapor detection with a multispectral thermal imager

    E-print Network

    Chang, Chein-I

    Chemical vapor detection with a multispectral thermal imager Mark 1. G. Aithouse, MEMBER SPIE U.S. Army Chemical Research Development and Engineering Center SMCCR-DDT Aberdeen Proving Ground, Maryland algorithm 7. Conclusions 8. Acknowledgments 9. References 1. INTRODUCTION Detection of chemical vapor clouds

  10. Enargy taken up by co-seismic chemical reactions during a large earthquake : An example from the 1999 Taiwan Chi-Chi earth quake

    Microsoft Academic Search

    Y. Hamada; T. Hirono; W. Tanikawa; S. Song

    2009-01-01

    Frictional heat in a fault zone during earthquake slip transiently induces chemical reactions that may use energy released during the earthquake. We estimated the energy used by such reactions (EC) by a numerical analysis incorporating frictional heat, thermal diffusion, chemical kinetics, and energy conservation, and found that EC has an auto-feedback effect that inhibits temperature rise in fault zone. During

  11. Preparation and thermal conductivity of CuO nanofluid via a wet chemical method

    PubMed Central

    2011-01-01

    In this article, a wet chemical method was developed to prepare stable CuO nanofluids. The influences of synthesis parameters, such as kinds and amounts of copper salts, reaction time, were studied. The thermal conductivities of CuO nanofluids were also investigated. The results showed that different copper salts resulted in different particle morphology. The concentration of copper acetate and reaction time affected the size and shape of clusters of primary nanoparticles. Nanofluids with different microstructures could be obtained by changing the synthesis parameters. The thermal conductivities of CuO nanofluids increased with the increase of particle loading. PMID:21711693

  12. Chemical reactions on solid surfaces of astrophysical interest

    NASA Astrophysics Data System (ADS)

    Biham, Ofer; Pirronello, Valerio; Vidali, Gianfranco

    Observed abundances of chemical species in interstellar clouds can be explained in most cases by reaction schemes involving only species in the gas phase. There is however clear evidence that reactions occurring on the surface of dust grains, helping the formation of key molecules, play a fundamental role into shaping the universe as we see it today. In this chapter we focus our attention on surface reactions on solids and in conditions close to those encountered in interstellar clouds. We will describe how experimental techniques of surface science have been used to study the recombination reaction of hydrogen on interstellar dust grain analogues and the oxidation of carbon monoxide in the interaction of oxygen atoms in water ice layers. Using theoretical methods and computer simulations, we show that it is possible to relate experimental results obtained in the laboratory to actual physical and chemical processes occurring in the interstellar space.

  13. International chemical identifier for reactions (RInChI)

    PubMed Central

    2013-01-01

    The IUPAC International Chemical Identifier (InChI) provides a method to generate a unique text descriptor of molecular structures. Building on this work, we report a process to generate a unique text descriptor for reactions, RInChI. By carefully selecting the information that is included and by ordering the data carefully, different scientists studying the same reaction should produce the same RInChI. If differences arise, these are most likely the minor layers of the InChI, and so may be readily handled. RInChI provides a concise description of the key data in a chemical reaction, and will help enable the rapid searching and analysis of reaction databases. PMID:24152584

  14. Reaction Kinetics and Catalysis Letters, Vol. 1, No. 1, 113-117/1974/ STOCHASTIC SIMULATION OF CHEMICAL REACTION BY

    E-print Network

    Tóth, János

    OF CHEMICAL REACTION BY DIGITAL COMPUTER, I. THE MODEL T. Sipos, 1 j. T6th, 2 and P. l~rdi 1 1. Danube Oil Received November 9, 1972 A stochastic model of complex chemical reactions is outlined. A discrete Markovprocess corresponds to the complex chemical reaction in the model i.e. the concentrations

  15. Molecular-level simulations of chemical reaction equilibrium and diffusion in slit and cylindrical nanopores: model dimerisation reactions

    E-print Network

    Lisal, Martin

    Molecular-level simulations of chemical reaction equilibrium and diffusion in slit and cylindrical study of the effects of confinement on chemical reaction equilibrium and diffusion in both slit nanopores 1. Introduction The behaviour of chemical reactions confined in nanopores is of extensive

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

    PubMed

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

    2015-05-18

    Chemical glycosylation is central to carbohydrate chemistry and is generally recognised as a challenging reaction. This review describes the most reoccurring side reactions of glycosyl donors in glycosylation and how scientists have attempted to explain their observations and in some cases succeeded in solving a particular encountered problem. The topics covered are donor hydrolysis, elimination to form glycals, intermolecular aglycon transfer of thioglycosides and glycosyl imidate rearrangement. PMID:25862946

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

    NASA Technical Reports Server (NTRS)

    Gokoglu, Suleyman A.

    1988-01-01

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

  18. Waste dissolution with chemical reaction, diffusion and advection

    SciTech Connect

    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.

  19. Toward a Thermodynamic Characterization of Chemical Reaction Networks

    NASA Astrophysics Data System (ADS)

    Cantú, Anselmo García; Nicolis, Gregoire

    2006-01-01

    The relation between the topology of a chemical reaction network and its thermodynamic properties, particularly the energy dissipation patterns, is analyzed. Both regular and complex structures are considered. For networks consisting of linear reactions, this task is analytically accomplished by formulating the network dynamics in terms of the network's connectivity matrix. The thermodynamic effect of nonlinear feedback dynamics on chemical networks is considered in the limits of close to and far away from equilibrium and discussed in connection with the robustness of the response to external disturbances.

  20. Freezing of Spinodal Decompostion by Irreversible Chemical Growth Reaction

    E-print Network

    Michael Schulz; Benjamin Paul

    1998-08-10

    We present a description of the freezing of spinodal decomposition in systems, which contain simultaneous irreversible chemical reactions, in the hydrodynamic limit approximation. From own results we conclude, that the chemical reaction leads to an onset of spinodal decomposition also in the case of an initial system which is completely miscible and can lead to an extreme retardation of the dynamics of the spinodal decomposition, with the probability of a general freezing of this process, which can be experimetally observed in simultaneous IPN formation.

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

    E-print Network

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

    2011-01-01

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

  2. Reaction Kinetics and Catalysis Letters, Vol. 1, No. 2/1974/209-213 STOCHASTIC SIMULATION OF CHEMICAL REACTIONS BY

    E-print Network

    Tóth, János

    OF CHEMICAL REACTIONS BY DIGITAL COMPUTER, H. APPLICATIONS T. Sipos1, J.TSth 2 and P. ~.rdi1 1. Danube Oil chemical reactions (especially those of biological interest, e.g. reactions exhibiting oscillationReaction Kinetics and Catalysis Letters, Vol. 1, No. 2/1974/209-213 STOCHASTIC SIMULATION

  3. KINETICS: A computer program to analyze chemical reaction data. Revision 2

    SciTech Connect

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

    1994-09-01

    KINETICS (Version 3.2) is a copyrighted, user-friendly kinetics analysis computer program designed for reactions such-as kerogen or polymer decomposition. It can fit rate parameters to chemical reaction data (rate or cumulative reacted) measured at a series of constant temperatures, constant heating rates, or arbitrary thermal histories. The program uses two models with conversion-dependent Azrhenius parameters and two models with activation energy distributions. The discrete distribution model fits an average frequency factor and relative fractions and activation energies for up to 25 parallel, fast-order reactions. The Gaussian distribution model fits a frequency factor, activation energy, Gaussian distribution parameter, and reaction order for up to 3 parallel reactions. For both distribution models, if the experiments are at a series of constant heating rates, the program uses a very fast approximate fitting procedure to determine possible initial parameter-estimates for the subsequent nonlinear regression analysis. This increases the probability that the regression analysis will properly. converge with a minimum of computer time. Once convergence is reached by the discrete model, the parameter space is further systematically searched to achieve global convergence. With the Gaussian model, the calculated rates or integrals can be convoluted with an experimental tracer signal during the nonlinear regression to account for dispersion effects often found in real chemical reaction data. KINETICS can also be used in an application mode to calculate reaction rates and integrals for previously determined Gaussian or discrete, parameters, using an arbitrary thermal history. Four additional models have been incorporated for the kinetics analysis of polymers and other materials, including some kerogens, which have a reaction-rate profile that is narrower than that for a single first-order reaction.

  4. Computed potential energy surfaces for chemical reactions

    NASA Technical Reports Server (NTRS)

    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.

  5. CHARACTERIZATION OF CHEMICALLY MODIFIED HYPERTHERMOPHILIC ENZYMES FOR CHEMICAL SYNTHESES AND BIOREMEDIATION REACTIONS

    EPA Science Inventory

    Research developments in the area of biocatalysis in organic solvents are expected to greatly expand the role of bioprocessing in chemical synthesis, fuel processing, and bioremediation technologies. Many biological transformation reactions of interest to DOE site remediation inv...

  6. Chemical Looping Combustion Reactions and Systems

    SciTech Connect

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

    2011-07-01

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

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

    NASA Technical Reports Server (NTRS)

    Muehlner, E.

    1943-01-01

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

  8. Amplitude Equations and Chemical Reaction-Diffusion Systems

    E-print Network

    M. Ipsen; F. Hynne; P. G. Soerensen

    1997-11-03

    The paper discusses the use of amplitude equations to describe the spatio-temporal dynamics of a chemical reaction-diffusion system based on an Oregonator model of the Belousov-Zhabotinsky reaction. Sufficiently close to a supercritical Hopf bifurcation the reaction-diffusion equation can be approximated by a complex Ginzburg-Landau equation with parameters determined by the original equation at the point of operation considered. We illustrate the validity of this reduction by comparing numerical spiral wave solutions to the Oregonator reaction-diffusion equation with the corresponding solutions to the complex Ginzburg-Landau equation at finite distances from the bifurcation point. We also compare the solutions at a bifurcation point where the systems develop spatio-temporal chaos. We show that the complex Ginzburg-Landau equation represents the dynamical behavior of the reaction-diffusion equation remarkably well sufficiently far from the bifurcation point for experimental applications to be feasible.

  9. Direct measurement of the reaction front in chemically amplified photoresists.

    PubMed

    Lin, Eric K; Soles, Christopher L; Goldfarb, Dario L; Trinque, Brian C; Burns, Sean D; Jones, Ronald L; Lenhart, Joseph L; Angelopoulos, Marie; Willson, C Grant; Satija, Sushil K; Wu, Wen-Li

    2002-07-19

    The continuing drive by the semiconductor industry to fabricate smaller structures using photolithography will soon require dimensional control at length scales comparable to the size of the polymeric molecules in the materials used to pattern them. The current technology, chemically amplified photoresists, uses a complex reaction-diffusion process to delineate patterned areas with high spatial resolution. However, nanometer-level control of this critical process is limited by the lack of direct measurements of the reaction front. We demonstrate the use of x-ray and neutron reflectometry as a general method to measure the spatial evolution of the reaction-diffusion process with nanometer resolution. Measuring compositional profiles, provided by deuterium-labeled reactant groups for neutron scattering contrast, we show that the reaction front within the material is broad rather than sharply defined and the compositional profile is altered during development. Measuring the density profile, we directly correlate the developed film structure with that of the reaction front. PMID:12130778

  10. Reduction of chemical reaction networks through delay distributions

    NASA Astrophysics Data System (ADS)

    Barrio, Manuel; Leier, André; Marquez-Lago, Tatiana T.

    2013-03-01

    Accurate modelling and simulation of dynamic cellular events require two main ingredients: an adequate description of key chemical reactions and simulation of such chemical events in reasonable time spans. Quite logically, posing the right model is a crucial step for any endeavour in Computational Biology. However, more often than not, it is the associated computational costs which actually limit our capabilities of representing complex cellular behaviour. In this paper, we propose a methodology aimed at representing chains of chemical reactions by much simpler, reduced models. The abridgement is achieved by generation of model-specific delay distribution functions, consecutively fed to a delay stochastic simulation algorithm. We show how such delay distributions can be analytically described whenever the system is solely composed of consecutive first-order reactions, with or without additional "backward" bypass reactions, yielding an exact reduction. For models including other types of monomolecular reactions (constitutive synthesis, degradation, or "forward" bypass reactions), we discuss why one must adopt a numerical approach for its accurate stochastic representation, and propose two alternatives for this. In these cases, the accuracy depends on the respective numerical sample size. Our model reduction methodology yields significantly lower computational costs while retaining accuracy. Quite naturally, computational costs increase alongside network size and separation of time scales. Thus, we expect our model reduction methodologies to significantly decrease computational costs in these instances. We anticipate the use of delays in model reduction will greatly alleviate some of the current restrictions in simulating large sets of chemical reactions, largely applicable in pharmaceutical and biological research.

  11. Program Helps To Determine Chemical-Reaction Mechanisms

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.; Radhakrishnan, K.

    1995-01-01

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

  12. Network Theory II: Stochastic Petri Nets, Chemical Reaction Networks

    E-print Network

    Baez, John

    inverses! So, we only evolve forwards in time in stochastic physics. #12;Suppose we have a Petri netNetwork Theory II: Stochastic Petri Nets, Chemical Reaction Networks and Feynman Diagrams John Baez, Jacob Biamonte, Brendan Fong #12;A Petri net is a way of drawing a finite set S of species, a finite set

  13. A chemical reaction-based boundary condition for flow electrification

    Microsoft Academic Search

    A. P. Washabaugh; M. Zahn

    1997-01-01

    A physical model is developed for the charge transfer boundary condition in semi-insulating liquids. The boundary condition is based upon interfacial chemical reactions and extends established relations for the interface by including the effects of interfacial surface charge and charge desorption at the interface. A steady state model for flow electrification in a rotating cylindrical electrode apparatus incorporated this boundary

  14. Chemical etching of manganese oxides for electrocatalytic oxygen reduction reaction.

    PubMed

    Lei, Kaixiang; Han, Xiaopeng; Hu, Yuxiang; Liu, Xue; Cong, Liang; Cheng, Fangyi; Chen, Jun

    2015-07-25

    Mixed-valent MnOx (1 < x < 2) was selectively synthesized by chemically etching MnO and Mn2O3 with ceric ammonium nitrate. The obtained MnOx exhibited greatly enhanced electrocatalytic activity toward the oxygen reduction reaction (ORR) as compared to the corresponding pristine oxides. PMID:26097914

  15. Chemical reaction models for non-equilibrium phase transitions

    Microsoft Academic Search

    F. Schlögl

    1972-01-01

    Chemical model reactions are discussed the steady states of which show the phenomenon of non equilibrium phase transitions. One example shows a phase transition of second order, another one shows a phase transition of first order. If diffusion occurs in the case of first order transition, coexistence of two phases in different domains is possible. For plane boundary layers between

  16. Interaction between chemical reactions and mixing on various scales

    Microsoft Academic Search

    S. J. Hearn

    1997-01-01

    The way in which reagents are mixed can have a large influence on the product distribution of a chemical reaction. This has been analysed earlier when micromixing is the limiting mixing step. Additional segregation at a larger scale has only been treated in detail when the local turbulent dispersion of a feed stream was relevant. Here additional segregation due to

  17. Supersonic molecular beam experiments on surface chemical reactions.

    PubMed

    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. PMID:25044656

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

    PubMed Central

    Rubin, C M; Schmid, C W

    1980-01-01

    Potassium permanganate reacts selectively with thymidine residues in DNA (1) while hydroxylamine hydrochloride at pH 6 specifically attacks cytosine (2). We have adopted these reactions for use with the chemical sequencing method developed by Maxam and Gilbert (3). Images PMID:7443522

  19. Fabrication of superhydrophobic copper by wet chemical reaction

    Microsoft Academic Search

    Zhiguang Guo; Jian Fang; Libo Wang; Weimin Liu

    2007-01-01

    A wet chemical reaction was employed herein to fabricate a stable superhydrophobic surface on a polished copper substrate at ambient temperature. The resulting surface showed superhydrophobic properties as evidenced by a water contact angle (CA) of about 154° and a water sliding angle (SA) of about 4°, which may be attributed to the combination of the roughened surface morphology by

  20. Dissipation Scale Fluctuations and Chemical Reaction Rates in Turbulent Flows

    E-print Network

    Victor Yakhot

    2007-06-29

    Small separation between reactants, not exceeding $10^{-8}-10^{-7}cm$, is the necessary condition for various chemical reactions. It is shown that random advection and stretching by turbulence leads to formation of scalar-enriched sheets of {\\it strongly fluctuating thickness} $\\eta_{c}$. The molecular-level mixing is achieved by diffusion across these sheets (interfaces) separating the reactants. Since diffusion time scale is $\\tau_{d}\\propto \\eta_{c}^{2}$, the knowledge of probability density $Q(\\eta_{c},Re)$ is crucial for evaluation of chemical reaction rates. In this paper we derive the probability density $Q(\\eta_{c},Re,Sc)$ and predict a transition in the reaction rate behavior from ${\\cal R}\\propto \\sqrt{Re}$ ($Re\\leq 10^{4}$) to the high-Re asymptotics ${\\cal R}\\propto Re^{0}$. The theory leads to an approximate universality of transitional Reynolds number $Re_{tr}\\approx 10^{4}$. It is also shown that if chemical reaction involves short-lived reactants, very strong anomalous fluctuations of the length-scale $\\eta_{c}$ may lead to non-negligibly small reaction rates.

  1. Levels of 186Re populated in thermal neutron capture reaction

    NASA Astrophysics Data System (ADS)

    B?rzinš, J.; Krasta, T.; Simonova, L.; Jentschel, M.; Urban, W.

    2015-05-01

    Levels of 186Re have been studied in the thermal neutron capture reaction with an enriched 185Re target. Evaluation of spectrum measured with GAMS5 allowed to obtain energies and intensities of more than 500 ?-lines assigned to 186Re. Most of the obtained transitions have been placed in the model-independent level scheme of the doubly odd 186Re nucleus, taking into account the available data of earlier experiments as well as the results of recent 187Re(p, d)186Re reaction measurements. Structure of the 186Re low-lying levels has been analysed in terms of the particle-plus-rotor coupling model.

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

    ERIC Educational Resources Information Center

    Boo, Hong Kwen

    1998-01-01

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

  3. Identification of responsible volatile chemicals that induce hypersensitive reactions to multiple chemical sensitivity patients

    Microsoft Academic Search

    Naohide Shinohara; Atsushi Mizukoshi; Yukio Yanagisawa

    2004-01-01

    Multiple chemical sensitivity (MCS) has become a serious problem as a result of airtight techniques in modern construction. The mechanism of the MCS, however, has not been clarified. Responsible chemicals and their exposure levels for patient's hypersensitive reactions need to be identified. We measured the exposure of 15 MCS patients to both carbonyl compounds and volatile organic compounds (VOCs) that

  4. Development of a chemical oxygen - iodine laser with production of atomic iodine in a chemical reaction

    SciTech Connect

    Censky, M; Spalek, O; Jirasek, V; Kodymova, J [Institute of Physics, Czech Academy of Sciences, Prague (Czech Republic); Jakubec, I [Institute of Inorganic Chemistry, Czech Academy of Sciences, Rez (Czech Republic)

    2009-11-30

    The alternative method of atomic iodine generation for a chemical oxygen - iodine laser (COIL) in chemical reactions with gaseous reactants is investigated experimentally. The influence of the configuration of iodine atom injection into the laser cavity on the efficiency of the atomic iodine generation and small-signal gain is studied. (lasers)

  5. Theoretical Chemical Dynamics Studies of Elementary Combustion Reactions

    SciTech Connect

    Donald L. Thompson

    2006-04-27

    The purpose of this research was the development and application of theoretical/computational methods for accurate predictions of the rates of reactions in many-atom systems. The specific aim was to improve computational methods for studying the chemical dynamics of large, complex systems and to obtain a better understanding of the chemical reactions involving large polyatomic molecules and radicals. The focus was on the development an automatic potential energy surface generation algorithm that takes advantage of high-performance computing environments; e.g., software for rate calculations that direct quantum chemistry codes to produce ab initio predictions of reaction rates and related dynamics quantities. Specifically, we developed interpolative moving least-squares (IMLS) methods for accurately fitting ab initio energies to provide global PESs and for use in direct dynamics simulations.

  6. Multiscale stochastic simulations of chemical reactions with regulated scale separation

    SciTech Connect

    Koumoutsakos, Petros, E-mail: petros@ethz.ch [Chair of Computational Science, Clausiusstrasse 33, ETH Zurich, CH-8092 (Switzerland)] [Chair of Computational Science, Clausiusstrasse 33, ETH Zurich, CH-8092 (Switzerland); Feigelman, Justin [Chair of Computational Science, Clausiusstrasse 33, ETH Zurich, CH-8092 (Switzerland)] [Chair of Computational Science, Clausiusstrasse 33, ETH Zurich, CH-8092 (Switzerland)

    2013-07-01

    We present a coupling of multiscale frameworks with accelerated stochastic simulation algorithms for systems of chemical reactions with disparate propensities. The algorithms regulate the propensities of the fast and slow reactions of the system, using alternating micro and macro sub-steps simulated with accelerated algorithms such as ? and R-leaping. The proposed algorithms are shown to provide significant speedups in simulations of stiff systems of chemical reactions with a trade-off in accuracy as controlled by a regulating parameter. More importantly, the error of the methods exhibits a cutoff phenomenon that allows for optimal parameter choices. Numerical experiments demonstrate that hybrid algorithms involving accelerated stochastic simulations can be, in certain cases, more accurate while faster, than their corresponding stochastic simulation algorithm counterparts.

  7. The role of chemical reactions in the Chernobyl accident

    NASA Astrophysics Data System (ADS)

    Grishanin, E. I.

    2010-12-01

    It is shown that chemical reactions played an essential role in the Chernobyl accident at all of its stages. It is important that the reactor before the explosion was at maximal xenon poisoning, and its reactivity, apparently, was not destroyed by the explosion. The reactivity release due to decay of Xe-235 on the second day after the explosion led to a reactor power of 80-110 MW. Owing to this power, the chemical reactions of reduction of uranium, plutonium, and other metals at a temperature of about 2000°C occurred in the core. The yield of fission products thus sharply increased. Uranium and other metals flew down in the bottom water communications and rooms. After reduction of the uranium and its separation from the graphite, the chain reaction stopped, the temperature of the core decreased, and the activity yield stopped.

  8. Department of Chemical Engineering Thermal and Flow Engineering Laboratory

    E-print Network

    Zevenhoven, Ron

    Department of Chemical Engineering Thermal and Flow Engineering Laboratory Ron Zevenhoven Course 424101 Processteknikens grunder ("PTG") Introduction to Process Engineering Aug. 2013 0 > V (m3/s University 424101 Processteknikens Grunder Introduction to Process Engineering by / av: Ron Zevenhoven 0

  9. Moment equations for chemical reactions on interstellar dust grains

    E-print Network

    Azi Lipshtat; Ofer Biham

    2002-12-09

    While most chemical reactions in the interstellar medium take place in the gas phase, those occurring on the surfaces of dust grains play an essential role. Chemical models based on rate equations including both gas phase and grain surface reactions have been used in order to simulate the formation of chemical complexity in interstellar clouds. For reactions in the gas phase and on large grains, rate equations, which are highly efficient to simulate, are an ideal tool. However, for small grains under low flux, the typical number of atoms or molecules of certain reactive species on a grain may go down to order one or less. In this case the discrete nature of the opulations of reactive species as well as the fluctuations become dominant, thus the mean-field approximation on which the rate equations are based does not apply. Recently, a master equation approach, that provides a good description of chemical reactions on interstellar dust grains, was proposed. Here we present a related approach based on moment equations that can be obtained from the master equation. These equations describe the time evolution of the moments of the distribution of the population of the various chemical species on the grain. An advantage of this approach is the fact that the production rates of molecular species are expressed directly in terms of these moments. Here we use the moment equations to calculate the rate of molecular hydrogen formation on small grains. It is shown that the moment equation approach is efficient in this case in which only a single reactive specie is involved. The set of equations for the case of two species is presented and the difficulties in implementing this approach for complex reaction networks involving multiple species are discussed.

  10. Mass Spectroscopy of Chemical Reaction of 3d Metal Clusters Involved in Chemical Vapor Deposition Synthesis of Carbon Nanotubes

    E-print Network

    Maruyama, Shigeo

    Mass Spectroscopy of Chemical Reaction of 3d Metal Clusters Involved in Chemical Vapor Deposition, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan The chemical reactions of transition metal importance. For example, these reactions are involved in the synthesis of single-walled carbon nanotubes

  11. Modelling of gas-solid reaction—Coupling of heat and mass transfer with chemical reaction

    Microsoft Academic Search

    Hui-Bo Lu; Nathalie Mazet; Bernard Spinner

    1996-01-01

    A general gas-solid reaction model is formulated. This work is the further development of the previous modelling work of Mazet (1988, Ph.D. Thesis, University of Perpignan) and Goetz (1991, Ph.D. Thesis, University of Perpignan) to simulate reversible gas-solid reactions that have been extensively applied to the new chemical heat pump technology developed at CNRS-IMP. In the present paper, a general

  12. Jet Quenching and Holographic Thermalization with a Chemical Potential

    E-print Network

    Elena Caceres; Arnab Kundu; Di-Lun Yang

    2014-01-07

    We investigate jet quenching of virtual gluons and thermalization of a strongly-coupled plasma with a non-zero chemical potential via the gauge/gravity duality. By tracking a charged shell falling in an asymptotic AdS$_{d+1}$ background for $d=3$ and $d=4$, which is characterized by the AdS-Reissner-Nordstr\\"om-Vaidya (AdS-RN-Vaidya) geometry, we extract a thermalization time of the medium with a non-zero chemical potential. In addition, we study the falling string as the holographic dual of a virtual gluon in the AdS-RN-Vaidya spacetime. The stopping distance of the massless particle representing the tip of the falling string in such a spacetime could reveal the jet quenching of an energetic light probe traversing the medium in the presence of a chemical potential. We find that the stopping distance decreases when the chemical potential is increased in both AdS-RN and AdS-RN-Vaidya spacetimes, which correspond to the thermalized and thermalizing media respectively. Moreover, we find that the soft gluon with an energy comparable to the thermalization temperature and chemical potential in the medium travels further in the non-equilibrium plasma. The thermalization time obtained here by tracking a falling charged shell does not exhibit, generically, the same qualitative features as the one obtained studying non-local observables. This indicates that --holographically-- the definition of thermalization time is observer dependent and there is no unambiguos definition.

  13. Jet quenching and holographic thermalization with a chemical potential

    NASA Astrophysics Data System (ADS)

    Caceres, Elena; Kundu, Arnab; Yang, Di-Lun

    2014-03-01

    We investigate jet quenching of virtual gluons and thermalization of a strongly-coupled plasma with a non-zero chemical potential via the gauge/gravity duality. By tracking a charged shell falling in an asymptotic AdS d+1 background for d = 3 and d = 4, which is characterized by the AdS-Reissner-Nordström-Vaidya (AdS-RN-Vaidya) geometry, we extract a thermalization time of the medium with a non-zero chemical potential. In addition, we study the falling string as the holographic dual of a virtual gluon in the AdS-RN-Vaidya spacetime. The stopping distance of the massless particle representing the tip of the falling string in such a spacetime could reveal the jet quenching of an energetic light probe traversing the medium in the presence of a chemical potential. We find that the stopping distance decreases when the chemical potential is increased in both AdS-RN and AdS-RN-Vaidya spacetimes, which correspond to the thermalized and thermalizing media respectively. Moreover, we find that the soft gluon with an energy comparable to the thermalization temperature and chemical potential in the medium travels further in the non-equilibrium plasma. The thermalization time obtained here by tracking a falling charged shell does not exhibit, generically, the same qualitative features as the one obtained studying non-local observables. This indicates that — holographically — the definition of thermalization time is observer dependent and there is no unambiguos definition.

  14. Accurate hybrid stochastic simulation of a system of coupled chemical or biochemical reactions

    E-print Network

    Minnesota, University of

    Accurate hybrid stochastic simulation of a system of coupled chemical or biochemical reactions reactions, approximates the fast reactions as a continuous Markov process, using a chemical Langevin multiple slow reactions may occur within a time step of the numerical integration of the chemical Langevin

  15. "Kinetics of Chemical Reactions in Environmental Systems: Research Needs and Challenges"

    E-print Network

    Sparks, Donald L.

    "Kinetics of Chemical Reactions in Environmental Systems: Research Needs and Challenges" Donald(oid)s, nutrients, radionuclides, and organic chemicals have shown that reaction rates are initially rapid followed by a slow approach to a steady state. The rapid reaction has been ascribed to chemical reactions and film

  16. Journal of Mathematical Chemistry 0 1999 ? ? 1 Chemical Clock Reactions: The E ect of Precursor

    E-print Network

    Billingham, John

    Journal of Mathematical Chemistry 0 1999 ? ? 1 Chemical Clock Reactions: The E ect of Precursor reaction is a chemical reaction which gives rise to a signi cant in- duction period during which one increases, for example cubic autocatal- #12;2 S. J. Preece et al Chemical Clock Reactions ysis: A + 2B ,! 3B

  17. Extinction and Spread of Isothemal Flame Balls in An Autocatalytic Chemical Reaction

    E-print Network

    Shi, Jun-Ping

    Extinction and Spread of Isothemal Flame Balls in An Autocatalytic Chemical Reaction Junping Shi: reaction rate Reaction-diffusion system of chemical reaction: a t = DAa - kabp, b t = DBb + kabp, t > 0, x(?). Remember that there are more than 4000 universities in USA! #12;An isothermal autocatalytic chemical

  18. 227-0684-00L Control Methods in Systems Biology May 12, 2011 Lecture 10: Chemical Reaction Network Theory (CRNT)

    E-print Network

    Lygeros, John

    227-0684-00L Control Methods in Systems Biology May 12, 2011 Lecture 10: Chemical Reaction Network's lecture · Stochastic simulation ­ Mass (moiety) conservation · Chemical reaction network theory ­ Chemical kinetics ­ Definitions central to chemical reaction network theory ­ Nonnegativity ­ Deficiency Zero

  19. Chemical reaction of metal-fullerene in gas phase (2) >Masamichi Konoa

    E-print Network

    Maruyama, Shigeo

    f18-068 Chemical reaction of metal-fullerene in gas phase (2) ·>Masamichi Konoa , Syuhei Inoueb structure, formation mechanism, chemical reactivity, and so on. To examine these question, chemical reaction clusters. In order to observe the chemical reaction product on a clean baseline, all clusters except for C

  20. Spatial patterns and double diffusion in chemical reactions

    PubMed Central

    Dewel, G.; Borckmans, P.; Walgraef, D.

    1983-01-01

    Spatial ordering has been observed recently during various photochemical reactions. Convoluted concentration bands first appear near the surface of shallow irradiated solutions. They thereafter extend into the bulk, and finger-like structures spontaneously develop. We discuss here the possible role of double-diffusion effects in the onset of this phenomenon. Indeed, chemical reactions occurring near the surface or evaporation of the solvent, or both, induce in the bulk adverse gradients of a pair of properties (concentrations of solute or concentration and temperature) having different diffusivities. This difference can then destabilize the homogeneous solution and trigger the observed patterns. PMID:16593384

  1. Towards chemically accurate simulation of molecule-surface reactions.

    PubMed

    Kroes, Geert-Jan

    2012-11-21

    This perspective addresses four challenges facing theorists whose aim is to make quantitatively accurate predictions for reactions of molecules on metal surfaces, and suggests ways of meeting these challenges, focusing on dissociative chemisorption reactions of H(2), N(2), and CH(4). Addressing these challenges is ultimately of practical importance to a more accurate description of overall heterogeneously catalysed reactions, which play a role in the production of more than 90% of man-made chemicals. One challenge is to describe the interaction of a molecule with a metal surface with chemical accuracy, i.e., with errors in reaction barrier heights less than 1 kcal mol(-1). In this framework, the potential of a new implementation of specific reaction parameter density functional theory (SRP-DFT) will be discussed, with emphasis on applications to reaction of H(2) with metal surfaces. Two additional challenges are to come up with improved descriptions of the effects of phonons and electron-hole pairs on reaction of molecules like N(2) on metal surfaces. Phonons can be tackled using sudden approximations in quantum dynamics, and through Ab Initio Molecular Dynamics (AIMD) calculations using classical dynamics. To additionally achieve an accurate description of the effect of electron-hole pair excitation on dissociative chemisorption within a classical dynamics framework, it may be possible to combine AIMD with electronic friction. The fourth challenge we will consider is how to achieve an accurate quantum mechanical description of the dissociative chemisorption of a polyatomic molecule, like methane, on a metal surface. A method of potential interest is the Multi-Configuration Time-Dependent Hartree (MCTDH) method. PMID:23037951

  2. Potential for exothermic chemical reactions in waste tanks

    SciTech Connect

    Van Tuyl, H.H.

    1983-02-03

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

  3. Controlling ultracold chemical reactions via Rydberg-dressed interactions

    E-print Network

    Jia Wang; Jason N. Byrd; Ion Simbotin; R. Côté

    2014-03-24

    We show that ultracold chemical reactions can be manipulated and controlled by using Rydberg-dressed interactions. Scattering in the ultracold regime is sensitive to long-range interactions, especially when weakly bound (or quasi-bound) states exist near the collision threshold. We investigate how, by Rydberg-dressing a reactant, one enhances its polarizability and modifies the long-range van der Waals collision complex, which can alter chemical reaction rates by shifting the position of near threshold bound states. We carry out a full quantum mechanical scattering calculation for the benchmark system H$_2$+D, and show that resonances can be moved substantially and that rate coefficients at cold and ultracold temperatures can be increased by several orders of magnitude.

  4. Tuning ultracold chemical reactions via Rydberg-dressed interactions.

    PubMed

    Wang, Jia; Byrd, Jason N; Simbotin, Ion; Côté, R

    2014-07-11

    We show that ultracold chemical reactions with an activation barrier can be tuned using Rydberg-dressed interactions. Scattering in the ultracold regime is sensitive to long-range interactions, especially when weakly bound (or quasibound) states exist near the collision threshold. We investigate how, by Rydberg dressing a reactant, one enhances its polarizability and modifies the long-range van der Waals collision complex, which can alter chemical reaction rates by shifting the position of near-threshold bound states. We carry out a full quantum mechanical scattering calculation for the benchmark system H(2)+D, and show that resonances can be moved substantially and that rate coefficients at cold and ultracold temperatures can be increased by several orders of magnitude. PMID:25062202

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

    NASA Technical Reports Server (NTRS)

    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.

  6. Quantum chemical analysis of the deferiprone–iron binding reaction

    PubMed Central

    Wiwanitkit, Viroj

    2006-01-01

    To prevent side effects of excessive accumulation of iron in the body, chelation therapy is recommended in transfusion-dependent patients. The reaction between deferiprone and iron to form a complex red substance can be described as 3 molecules of the chelator, deferiprone, reacting with a molecule of iron. However, the actual mechanism of the deferiprone – iron binding reaction is not well understood. A quantum chemical analysis of the deferiprone – iron binding reaction was performed, focusing on the reaction between 1 molecule of deferiprone and 1 molecule of iron. The two main alternative pathways for the deferiprone – iron binding reaction were shown to be C-C cleavage and C-O cleavage. The required energy for complex formation in C-C cleavage was less than for C-O cleavage. The total energy requirement for C-C cleavage was negative, implying that this reaction can occur without any external energy source. The resulting complex fits the reported tertiary structure model for the deferiprone – iron complex PMID:17722270

  7. Modeling of Thermal-Hydrological-Chemical Laboratory Experiments

    SciTech Connect

    P. F. Dobson; T. J. Kneafsey; E. L. Sonnenthal; Nicolas Spycher

    2001-05-31

    The emplacement of heat-generating nuclear waste in the potential geologic repository at Yucca Mountain, Nevada, will result in enhanced water-rock interaction around the emplacement drifts. Water present in the matrix and fractures of the rock around the drift may vaporize and migrate via fractures to cooler regions where condensation would occur. The condensate would react with the surrounding rock, resulting in mineral dissolution. Mineralized water flowing under gravity back towards the heat zone would boil, depositing the dissolved minerals. Such mineral deposition would reduce porosity and permeability above the repository, thus altering the flow paths of percolating water. The objective of this research is to use coupled thermal-hydrological-chemical (THC) models to simulate previously conducted laboratory experiments involving tuff dissolution and mineral precipitation in a boiling, unsaturated fracture. Numerical simulations of tuff dissolution and fracture plugging were performed using a modified version of the TOUGHREACT code developed at LBNL by T. Xu and K. Pruess. The models consider the transport of heat, water, gas and dissolved constituents, reactions between gas, mineral and aqueous phases, and the coupling of porosity and permeability to mineral dissolution and precipitation. The model dimensions and initial fluid chemistry, rock mineralogy, permeability, and porosity were defined using the experimental conditions. A 1-D plug-flow model was used to simulate dissolution resulting from reaction between deionized water and crushed ash flow tuff. A 2-D model was developed to simulate the flow of mineralized water through a planar fracture within a block of ash flow tuff where boiling conditions led to mineral precipitation. Matrix blocks were assigned zero permeability to confine fluid flow to the fracture, and permeability changes in the fracture were specified using the porosity cubic law relationship.

  8. Modeling Chemical Reactions with First-Principle Molecular Dynamics

    Microsoft Academic Search

    Artur Michalak; Tom Ziegler

    Density functional theory (DFT)-based molecular dynamics (MD) has established itself as a valuable and powerful tool in studies\\u000a of chemical reactions. Thanks to the rapid increase in power of modern computers, ab initio MD has nowadays become practical. Within the Car-Parinello approach, first-principle MD is already quite popular methodology\\u000a in molecular modeling. MD reveals the dynamical effects at finite temperatures

  9. Electric and Magnetic Detection of Avalanche Behavior in Chemical Reactions

    Microsoft Academic Search

    James Claycomb; M. Nersesyan; Martin Miller; John Miller; Dan Luss

    2001-01-01

    Intermittent bursts of chemical activity, displaying avalanche like behavior, have been observed in liquid-solid replacement reactions between metals and liquid electrolytes by measuring the time-dependent electric and magnetic fields. Magnetic measurements are conducted using a high-Tc SQUID inside a magnetically shielded enclosure. Electric potential difference measurements exhibit temporal behavior that is qualitatively similar to the recorded magnetic signals. The observed

  10. Beating polymer gels coupled with a nonlinear chemical reaction

    Microsoft Academic Search

    Ryo Yoshida; Etsuo Kokufuta; Tomohiko Yamaguchi

    1999-01-01

    We report on a beating polymer gel that exhibits periodical volume changes (swelling and deswelling) in a closed solution without external stimuli, like autonomous heartbeat. The mechanical oscillation is driven by the chemical energy of the oscillatory Belousov-Zhabotinsky (BZ) reaction. The gel is a copolymer gel of N-isopropylacrylamide (NIPAAm) in which ruthenium tris(2,2'-bipyridine) [Ru(bpy)3], known as a catalyst of the

  11. Gamma and the Chemical Reaction Model: Fifteen Years After

    Microsoft Academic Search

    Jean-Pierre Ban?tre; Pascal Fradet; Daniel Le Métayer

    Gamma was originally proposed in 1986 as a formalism for the definition of programs without artificial sequentiality. The\\u000a basic idea underlying the formalism is to describe computation as a form of chemical reaction on a collection of individual pieces of data. Due to the very minimal nature of the language, and its absence of sequential\\u000a bias, it has been possible

  12. A microvascular system for chemical reactions using surface waste heat.

    PubMed

    Nguyen, Du Thai; Esser-Kahn, Aaron P

    2013-12-16

    Coffee-powered chemistry: Low-grade waste heat on surfaces can be used to drive chemical reactions, including the regeneration of a CO2 capture solution. Flowing two-phase heat transfer has been implemented within microvascular systems. This stripping system can be adapted to pre-fabricated surfaces, as demonstrated by a coffee mug containing a 1.2?m long microchannel. MEA=monoethanolamine. PMID:24307247

  13. Chemical reactions in viscous liquids under space conditions

    Microsoft Academic Search

    A. Kondyurin; B. Lauke; E. Richter

    2004-01-01

    A long-term human flight needs a large-size space ships with artificial self-regulating ecological life-support system. The best way for creation of large-size space ship is a synthesis of light construction on Earth orbit, that does not need a high energy transportation carriers from Earth surface. The construction can be created by the way of chemical polymerisation reaction under space environment.

  14. STM control of chemical reaction: single-molecule synthesis.

    PubMed

    Hla, Saw-Wai; Rieder, Karl-Heinz

    2003-01-01

    The fascinating advances in single atom/molecule manipulation with a scanning tunneling microscope (STM) tip allow scientists to fabricate atomic-scale structures or to probe chemical and physical properties of matters at an atomic level. Owing to these advances, it has become possible for the basic chemical reaction steps, such as dissociation, diffusion, adsorption, readsorption, and bond-formation processes, to be performed by using the STM tip. Complete sequences of chemical reactions are able to induce at a single-molecule level. New molecules can be constructed from the basic molecular building blocks on a one-molecule-at-a-time basis by using a variety of STM manipulation schemes in a systematic step-by-step manner. These achievements open up entirely new opportunities in nanochemistry and nanochemical technology. In this review, various STM manipulation techniques useful in the single-molecule reaction process are reviewed, and their impact on the future of nanoscience and technology are discussed. PMID:12626735

  15. Exploring complex chemical reactions by ab-initio simulation

    NASA Astrophysics Data System (ADS)

    Parrinello, Michele

    1998-03-01

    Recent progress in the ab-initio molecular dynamics method and the power of parallel computing, allow the detailed study of complex chemical reaction of great industrial relevance. We illustrate this unprecedented capability by investigating the second generation Ziegler-Natta catalytic process. In this inhomogeneous catalyst, a polymerization reaction is induced by TiCl4 molecules deposited on an MgCl2 solid support. A density functional based ab-initio molecular dynamics calculation conducted with a minimum of initial assumption allows to understand the nature of the catalytic center and to determine the reaction path with the associated free energy barrier. Furthermore our calculation can explain in a nontrivial way the stereo-selectivity of the process.

  16. How is entropy production rate related to chemical reaction rate?

    E-print Network

    Banerjee, Kinshuk

    2013-01-01

    The entropy production rate is a key quantity in irreversible thermodynamics. In this work, we concentrate on the realization of entropy production rate in chemical reaction systems in terms of the experimentally measurable reaction rate. Both triangular and linear networks have been studied. They attain either thermodynamic equilibrium or a non-equilibrium steady state, under suitable external constraints. We have shown that the entropy production rate is proportional to the square of the reaction velocity only around equilibrium and not any arbitrary non-equilibrium steady state. This feature can act as a guide in revealing the nature of a steady state, very much like the minimum entropy production principle. A discussion on this point has also been presented.

  17. Printing chemical libraries on microarrays for fluid phase nanoliter reactions

    PubMed Central

    Gosalia, Dhaval N.; Diamond, Scott L.

    2003-01-01

    Chemical compounds within individual nanoliter droplets of glycerol were microarrayed onto glass slides at 400 spots/cm2. Using aerosol deposition, subsequent reagents and water were metered into each reaction center to rapidly assemble diverse multicomponent reactions without crosscontamination or the need for surface linkage. This proteomics technique allowed the kinetic profiling of protease mixtures, protease–substrate interactions, and high-throughput screening reactions. An inhibitor of caspases 2, 4, and 6 was identified by using a 352-compound combinatorial library microarrayed in quadruplicates on 100 slides and screened against caspases 2, 4, and 6, as well as thrombin and chymotrypsin. From one printing run that consumes <1 nanomole of each compound, large combinatorial libraries can be subjected to numerous separation-free homogeneous assays at volumes 103–104 smaller than current high-throughput methods. PMID:12851459

  18. Spatiotemporal regulation of chemical reactions by active cytoskeletal remodeling

    PubMed Central

    Chaudhuri, Abhishek; Bhattacharya, Bhaswati; Gowrishankar, Kripa; Mayor, Satyajit; Rao, Madan

    2011-01-01

    Efficient and reproducible construction of signaling and sorting complexes, both on the surface and within the living cell, is contingent on local regulation of biochemical reactions by the cellular milieu. We propose that in many cases this spatiotemporal regulation can be mediated by interaction with components of the dynamic cytoskeleton. We show how the interplay between active contractility and remodeling of the cytoskeleton can result in transient focusing of passive molecules to form clusters, leading to a dramatic increase in the reaction efficiency and output levels. The dynamic cytoskeletal elements that drive focusing behave as quasienzymes catalyzing the chemical reaction. These ideas are directly applicable to the cortical actin-dependent clustering of cell surface proteins such as lipid-tethered GPI-anchored proteins, Ras proteins, as well as many proteins that have domains that confer the ability to interact with the actin cytoskeleton. In general such cytoskeletal driven clustering of proteins could be a cellular mechanism to spatiotemporally regulate and amplify local chemical reaction rates in a variety of contexts such as signaling, transcription, sorting, and endocytosis. PMID:21873247

  19. Influence of Chemical Reactions on the Nonlinear Dynamics of Dissipative Flows

    E-print Network

    Karimov, A R; Beklemishev, V V

    2015-01-01

    The nonlinear dynamics of resistive flow with a chemical reaction is studied. Proceeding from the Lagrangian description, the influence of a chemical reaction on the development of fluid singularities is considered.

  20. Influence of Chemical Reactions on the Nonlinear Dynamics of Dissipative Flows

    E-print Network

    A. R. Karimov; A. M. Korshunov; V. V. Beklemishev

    2015-04-16

    The nonlinear dynamics of resistive flow with a chemical reaction is studied. Proceeding from the Lagrangian description, the influence of a chemical reaction on the development of fluid singularities is considered.

  1. Physio-chemical reactions in recycle aggregate concrete.

    PubMed

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

    2009-04-30

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

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

    PubMed

    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. PMID:25872277

  3. Chemical reaction dynamics using the Advanced Light Source

    SciTech Connect

    Yang, X.; Blank, D.A.; Heimann, P.A.; Lee, Y.T.; Suits, A.G. [Univ. of California, Berkeley, CA (US). Dept. of Chemistry]|[Lawrence Berkeley Lab., CA (US); Lin, J. [Univ. of California, Berkeley, CA (US). Dept. of Chemistry; Wodtke, A.M. [Univ. of California, Santa Barbara, CA (US). Dept. of Chemistry

    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{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.

  4. Reversible chemical reactions for single-color multiplexing microscopy.

    PubMed

    Brox, Dominik; Schwering, Michael; Engelhardt, Johann; Herten, Dirk-Peter

    2014-08-01

    Recent developments in biology demand an increasing number of simultaneously imaged structures with standard fluorescence microscopy. However, the number of multiplexed channels is limited for most multiplexing modalities, such as spectral multiplexing or fluorescence-lifetime imaging. We propose extending the number of imaging channels by using chemical reactions, controlling the emissive state of fluorescent dyes. As proof of concept, we reversibly switch a fluorescent copper sensor to enable successive imaging of two different structures in the same spectral channel. We also show that this chemical multiplexing is orthogonal to existing methods. By using two different dyes, we combine chemical with spectral multiplexing for the simultaneous imaging of four different structures with only two spectrally different channels. We characterize and discuss the approach and provide perspectives for extending imaging modalities in stimulated emission depletion microscopy, for which spectral multiplexing is technically demanding. PMID:24753024

  5. Steam reduction of CO2 on Pd/TiO2 catalysts: a comparison between thermal and photocatalytic reactions.

    PubMed

    Vaiano, V; Sannino, D; Ciambelli, P

    2015-03-01

    The aim of this work was to compare traditional catalysis, which drives chemical reactions by thermal energy, with a photocatalytic process that can induce chemical reactions by light activation. Taking apart the obvious economic advantage to operate under mild conditions, a closer view of the characteristic behaviours of the thermal and light activation can give new insights for the selection of the more appropriate process. The performances of Pd/TiO2 catalysts in the steam reduction of CO2 were analyzed in a photocatalytic and in a thermo-catalytic system. The comparison in the range 140 °C-600 °C showed, for this reaction, the superiority of the photocatalytic route, since at any temperature level, no relevant products or higher selectivities towards the formation of methane and CO were observed. The CH4 photo-formation rate achieved a value of about 64 ?mol g(-1) h(-1) at Pd loading equal to 1 wt%. PMID:25358545

  6. Compare and contrast the reaction coordinate diagrams for chemical reactions and cytoskeletal force generators

    PubMed Central

    Scholey, Jonathan M.

    2013-01-01

    Reaction coordinate diagrams are used to relate the free energy changes that occur during the progress of chemical processes to the rate and equilibrium constants of the process. Here I briefly review the application of these diagrams to the thermodynamics and kinetics of the generation of force and motion by cytoskeletal motors and polymer ratchets as they mediate intracellular transport, organelle dynamics, cell locomotion, and cell division. To provide a familiar biochemical context for discussing these subcellular force generators, I first review the application of reaction coordinate diagrams to the mechanisms of simple chemical and enzyme-catalyzed reactions. My description of reaction coordinate diagrams of motors and polymer ratchets is simplified relative to the rigorous biophysical treatment found in many of the references that I use and cite, but I hope that the essay provides a valuable qualitative representation of the physical chemical parameters that underlie the generation of force and motility at molecular scales. In any case, I have found that this approach represents a useful interdisciplinary framework for understanding, researching, and teaching the basic molecular mechanisms by which motors contribute to fundamental cell biological processes. PMID:23408787

  7. Propagation of Reactions in Thermally-damaged PBX-9501

    SciTech Connect

    Tringe, J W; Glascoe, E A; Kercher, J R; Willey, T M; Springer, H K; Greenwood, D W; Molitoris, J D; Smilowitz, L; Henson, B F; Maienschein, J L

    2010-03-05

    A thermally-initiated explosion in PBX-9501 (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) is observed in situ by flash x-ray imaging, and modeled with the LLNL multi-physics arbitrary-Lagrangian-Eulerian code ALE3D. The containment vessel deformation provides a useful estimate of the reaction pressure at the time of the explosion, which we calculate to be in the range 0.8-1.4 GPa. Closely-coupled ALE3D simulations of these experiments, utilizing the multi-phase convective burn model, provide detailed predictions of the reacted mass fraction and deflagration front acceleration. During the preinitiation heating phase of these experiments, the solid HMX portion of the PBX-9501 undergoes a {beta}-phase to {delta}-phase transition which damages the explosive and induces porosity. The multi-phase convective burn model results demonstrate that damaged particle size and pressure are critical for predicting reaction speed and violence. In the model, energetic parameters are taken from LLNL's thermochemical-kinetics code Cheetah and burn rate parameters from Son et al. (2000). Model predictions of an accelerating deflagration front are in qualitative agreement with the experimental images assuming a mode particle diameter in the range 300-400 {micro}m. There is uncertainty in the initial porosity caused by thermal damage of PBX-9501 and, thus, the effective surface area for burning. To better understand these structures, we employ x-ray computed tomography (XRCT) to examine the microstructure of PBX-9501 before and after thermal damage. Although lack of contrast between grains and binder prevents the determination of full grain size distribution in this material, there are many domains visible in thermally damaged PBX-9501 with diameters in the 300-400 {micro}m range.

  8. SHEAR LOCALIZATION AND CHEMICAL REACTION IN HIGH-STRAIN, HIGH-STRAIN-RATE DEFORMATION OF

    E-print Network

    Meyers, Marc A.

    SHEAR LOCALIZATION AND CHEMICAL REACTION IN HIGH-STRAIN, HIGH-STRAIN-RATE DEFORMATION OF Ti regions can initiate chemical reaction inside a reac- tive powder mixture. The shear band spacing was H0-induced chemical reactions in silicide systems have been investigated in recent years. Vreeland and coworkers [7

  9. Log-Domain Circuit Models of Chemical Reactions Soumyajit Mandal and Rahul Sarpeshkar

    E-print Network

    Sarpeshkar, Rahul

    Log-Domain Circuit Models of Chemical Reactions Soumyajit Mandal and Rahul Sarpeshkar Department to networks of chemical reactions. Our circuits can be used for transient and steady-state simulations the energy barrier of a chemical reaction, exponentially changing its speed. In an analogous fashion, gate

  10. A Petri Net Approach to Persistence Analysis in Chemical Reaction Networks

    E-print Network

    Sontag, Eduardo

    A Petri Net Approach to Persistence Analysis in Chemical Reaction Networks David Angeli, Patrick De not approach the boundary of this orthant. For chemical reaction networks and other models in biology as well as sufficient conditions for persistence of chemical species in reaction networks

  11. Computational analysis of an instantaneous chemical reaction in a T-microreactor

    E-print Network

    Bothe, Dieter

    Computational analysis of an instantaneous chemical reaction in a T-microreactor Dieter Bothe 1 in liquid systems with very fast irreversible chemical reaction to the case of unequal diffusivities and energy transport. Hence, they are well suited for fast chemical reactions which are seriously affected

  12. Modeling Chemical Reactions with Single Reactant Specie Abhyudai Singh and Jo~ao Pedro Hespanha

    E-print Network

    Hespanha, João Pedro

    Modeling Chemical Reactions with Single Reactant Specie Abhyudai Singh and Jo~ao Pedro Hespanha Abstract-- A procedure for constructing approximate stochastic models for chemical reactions involving involved in a chemical reaction as the continuous state of a polynomial Stochastic Hybrid System (p

  13. Memory Switches in Chemical Reaction Space Naren Ramakrishnan1,2

    E-print Network

    Ramakrishnan, Naren

    Memory Switches in Chemical Reaction Space Naren Ramakrishnan1,2 , Upinder S. Bhalla3 * 1 and family relationships among such switches. We performed a systematic exploration of chemical reaction of bistable systems. Thus, our systematic exploration of chemical reaction space has produced a valuable

  14. Predicting the Progress of Diffusively Limited Chemical Reactions in the Presence of Chaotic Advection

    E-print Network

    Gollub, Jerry P.

    Predicting the Progress of Diffusively Limited Chemical Reactions in the Presence of Chaotic chemical reactions in two-dimensional fluid flows are investigated using experimentally measured stretchingRevLett.96.024501 PACS numbers: 47.52.+j, 05.45.ÿa, 47.70.Fw, 82.40.Ck Chemical reactions in solution

  15. CHEMICAL REACTIONS AS -LIMIT OF DIFFUSION MARK A. PELETIER, GIUSEPPE SAVARE, AND MARCO VENERONI

    E-print Network

    Veneroni, Marco

    CHEMICAL REACTIONS AS -LIMIT OF DIFFUSION MARK A. PELETIER, GIUSEPPE SAVAR´E, AND MARCO VENERONI a rigorous proof of Kramers's formal derivation, and we show how chemical reactions and diffusion processes can be embedded in a common framework. This allows one to derive a chemical reaction as a singular

  16. STRAIN-INDUCED STRUCTURAL CHANGES AND CHEMICAL REACTIONSII. MODELLING OF REACTIONS

    E-print Network

    Meyers, Marc A.

    STRAIN-INDUCED STRUCTURAL CHANGES AND CHEMICAL REACTIONSÐII. MODELLING OF REACTIONS IN SHEAR BAND V 1997; accepted in revised form 26 April 1998) AbstractÐThe problem on strain-induced chemical reaction is connected with the additional heating due to RIP. A kinetic criterion of chemical reaction is formulated

  17. DNS of a Mach 4 Boundary Layer with Chemical Reactions M. Pino Martin

    E-print Network

    Martín, Pino

    DNS of a Mach 4 Boundary Layer with Chemical Reactions M. Pino Mart´in Graham V. Candler Aerospace understanding of the interaction between turbulent motion and chemical reactions in hypersonic flows is limited to perform a fundamental study of isotropic turbulence interacting with finite-rate chemical reactions

  18. Explicit Collision Simulation of Chemical Reactions in a Graph Based Artifical Chemistry

    E-print Network

    Stadler, Peter F.

    Explicit Collision Simulation of Chemical Reactions in a Graph Based Artifical Chemistry Gil Benk¨uckel Theory method. Here we describe an extension of the model that models chemical reactions as the result, the reactions are simulated in a way that treats the formation and breakage of individual chemical bonds

  19. Boundary Effects on Chaotic Advection-Diffusion Chemical Reactions M. Chertkov1

    E-print Network

    Lebedev, Vladimir

    Boundary Effects on Chaotic Advection-Diffusion Chemical Reactions M. Chertkov1 and V. Lebedev1,2 1 chemical reaction, A B ! C, in a statistically stationary bounded chaotic flow at large Peclet number Pe advection should essentially accelerate chemical reactions rate in fluid phase, since it should lead

  20. A Petri Net Approach to Persistence Analysis in Chemical Reaction Networks

    E-print Network

    De Leenheer, Patrick

    A Petri Net Approach to Persistence Analysis in Chemical Reaction Networks David Angeli, Patrick De not approach the boundary of this orthant. For chemical reaction networks and other models in biology as well as sufficient conditions for of chemical species in reaction networks, and the applicability

  1. HOW TO AVOID OVERCOOKING: OPTIMAL YIELD OF B FROM THE CONSECUTIVE CHEMICAL REACTIONS ABC

    E-print Network

    Salamon, Peter

    HOW TO AVOID OVERCOOKING: OPTIMAL YIELD OF B FROM THE CONSECUTIVE CHEMICAL REACTIONS A´B´C Thor A the consecutive chemical reactions A´B´C both numerically and analytically using temperature as the control. Keywords: Optimal control, Chemical reactions, Temperature control, Optimal yield INTRODUCTION Already half

  2. Molecular dynamics simulations of a chemical reaction; conditions for local equilibrium in a temperature gradient

    E-print Network

    Kjelstrup, Signe

    Molecular dynamics simulations of a chemical reaction; conditions for local equilibrium have examined a simple chemical reaction in a temperature gradient; 2F $ F2. A mechanical model molecular dynamics simulations showed that the chemical reaction is in local thermodynamic as well

  3. Models for Multi-Specie Chemical Reactions Using Polynomial Stochastic Hybrid Systems

    E-print Network

    Hespanha, João Pedro

    Models for Multi-Specie Chemical Reactions Using Polynomial Stochastic Hybrid Systems Abhyudai for chemical reactions is presented. This is done by representing the population of various species involved in a chemical reaction as the continuous state of a polynomial Stochastic Hybrid System (pSHS). An important

  4. On persistence of chemical reaction networks with time-dependent kinetics and no global conservation laws

    E-print Network

    Sontag, Eduardo

    On persistence of chemical reaction networks with time-dependent kinetics and no global for persistence of chemical reaction networks are proposed, which extend those obtained by the authors in previous. Interpreted for chemical reactions and population models, this translates into a "non-extinction property

  5. Multiple equilibria in complex chemical reaction networks: extensions to entrapped species models

    E-print Network

    Craciun, Gheorghe

    Multiple equilibria in complex chemical reaction networks: extensions to entrapped species models G of complex chemical reaction networks, taken with mass-action kinetics, to admit multiple equilibria.) In both papers, it was understood that the reactions were taking place in the context of what chemical

  6. Chemical reactions between cold trapped Ba+ ions and neutral molecules in the gas phase

    E-print Network

    Schiller, Stephan

    Chemical reactions between cold trapped Ba+ ions and neutral molecules in the gas phase B. Roth, D-cooled ion trapping apparatus, we have investigated laser-induced chemical reactions between cold trapped Ba is to investigate chemical reactions between cold atomic and molecular ions trapped in radio-frequency traps

  7. Effect of chemical reactions on decaying isotropic turbulence M. Pino Martin and Graham V. Candler

    E-print Network

    Martín, Pino

    Effect of chemical reactions on decaying isotropic turbulence M. Pino Marti´n and Graham V. Candler combustion flows, however the interaction between turbulent motion and the chemical reactions that occur. In hypersonic flows the dominant chemical reactions are the dissociation and recombination of nitrogen

  8. Single-molecule chemical reactions: Reexamination of the Kramers approach G. Margolin1

    E-print Network

    Barkai, Eli

    Single-molecule chemical reactions: Reexamination of the Kramers approach G. Margolin1 and E; published 2 August 2005 Single-molecule chemical reactions yield insight into fluctuation phenomena.1103/PhysRevE.72.025101 PACS number s : 02.50. r, 82.37.Np, 05.40. a Chemical reaction of a single molecule

  9. WATER RESOURCES RESEARCH, VOL. ???, XXXX, DOI:10.1029/, Simulation of chemical reaction via particle tracking

    E-print Network

    WATER RESOURCES RESEARCH, VOL. ???, XXXX, DOI:10.1029/, Simulation of chemical reaction via Abstract. Chemical reactions may be simulated without regard to local concentrations by ap- plying simple. Introduction Chemical reactions are commonly idealized as an interac- tion between fluids with certain

  10. A general method for the computation of probabilities in systems of first order chemical reactions

    E-print Network

    Djuriæ, Petar M.

    A general method for the computation of probabilities in systems of first order chemical reactions for the computation of molecular population distributions in a system of first-order chemical reactions. The method to model the chemical reactions in a stochastic way rather than with the traditional differential equations

  11. in Press, Physical Review Letters Predicting the progress of diffusively limited chemical reactions

    E-print Network

    Gollub, Jerry P.

    in Press, Physical Review Letters Predicting the progress of diffusively limited chemical reactions: December 9, 2005) The effects of chaotic advection and diffusion on fast chemical reactions in two, fast chemical reactions, numeri- cal studies have attempted to relate product concentra- tion growth

  12. Explicit Collision Simulation of Chemical Reactions in a Graph Based Artifical Chemistry

    E-print Network

    Stadler, Peter F.

    Explicit Collision Simulation of Chemical Reactions in a Graph Based Artifical Chemistry Gil BenkË?uckel Theory method. Here we describe an extension of the model that models chemical reactions as the result, the reactions are simulated in a way that treats the formation and breakage of individual chemical bonds

  13. Toward Accurate Potentials for Condensed-Phase Chemical Reactions: Electrostatically Embedded Multi-Configuration Molecular Mechanics

    E-print Network

    Truhlar, Donald G

    Toward Accurate Potentials for Condensed-Phase Chemical Reactions: Electrostatically Embedded Multi and molecular mechanical (QM/MM) methods have provided powerful means for studying chemical reactions be used in QM/MM methods. The result is a key step toward studying chemical reactions in condensed phases

  14. SENSITIVITY OF CHEMICAL REACTION NETWORKS: A STRUCTURALAPPROACH. 1. EXAMPLES AND THE CARBON METABOLIC NETWORK

    E-print Network

    Fiedler, Bernold

    -1- SENSITIVITY OF CHEMICAL REACTION NETWORKS: A STRUCTURALAPPROACH. 1. EXAMPLES AND THE CARBON of Theoretical Biology, June 21, 2014) #12;-2- Abstract In biological cells, chemical reaction pathways lead information on the network alone. We investigate how the sensitivity responses of chemicals in a reaction

  15. Explicit Collision Simulation of Chemical Reactions in a Graph Based Artificial Chemistry

    E-print Network

    Flamm, Christoph

    Explicit Collision Simulation of Chemical Reactions in a Graph Based Artificial Chemistry Gil Benk¨uckel Theory method. Here we describe an extension of the model that models chemical reactions as the result, the reactions are simulated in a way that treats the formation and breakage of individual chemical bonds

  16. Grad's distribution functions in the kinetic equations for a chemical reaction

    E-print Network

    Spiga, Giampiero

    Grad's distribution functions in the kinetic equations for a chemical reaction Marzia Bisi, Maria of four species undergoing a bimolecular reversible chemical reaction, along with all possible elastic] and Prigogine-Xhrouet [2], kinetic approaches to chemical reactions in a gas have gained interest and importance

  17. A bisimulation approach to verification of molecular implementations of formal chemical reaction networks

    E-print Network

    Winfree, Erik

    A bisimulation approach to verification of molecular implementations of formal chemical reaction implementations of formal chemical reaction networks by Qing Dong Master of Science in Computer Science Stony Brook University 2012 In molecular computing, chemical reaction networks have been proposed as a high

  18. Explicit Collision Simulation of Chemical Reactions in a Graph Based Artificial Chemistry

    E-print Network

    Flamm, Christoph

    Explicit Collision Simulation of Chemical Reactions in a Graph Based Artificial Chemistry Gil BenkË?uckel Theory method. Here we describe an extension of the model that models chemical reactions as the result, the reactions are simulated in a way that treats the formation and breakage of individual chemical bonds

  19. Chemical reaction rates using the semiclassical Van Vleck initial value representation

    E-print Network

    Miller, William H.

    Chemical reaction rates using the semiclassical Van Vleck initial value representation Charulatha gas phase H+CH4 reaction to a model for a chemical reaction in a polar solvent.15 However, as any, California 94720; and Chemical Sciences Division, Lawrence Berkeley National Laboratory, University

  20. Kinetics of OCN- formation from the HNCO + NH3 solid-state thermal reaction

    NASA Astrophysics Data System (ADS)

    Mispelaer, F.; Theule, P.; Duvernay, F.; Roubin, P.; Chiavassa, T.

    2012-04-01

    Context. Solid-state features in infrared astronomical spectra can provide useful information on interstellar ices within different astrophysical environments. Solid OCN- has an absorption feature at 4.62 ?m, which is observed in star formation regions only with a large source-to-source abundance variation. Aims: We aim to investigate the thermal formation mechanism of solid OCN- from HNCO on the basis of kinetic arguments. Methods: We experimentally studied the kinetics of the low-temperature OCN- formation from the purely thermal reaction between HNCO and NH3 in interstellar ice analogs using Fourier transform infrared spectroscopy. We used a rate equation approach, a kinetic Monte Carlo approach and a gamma probability distribution approach to derive kinetic parameters from experimental data. Results: The kinetics can de divided into two-processes, a fast process corresponding to the chemical reaction, and a slow process that we interpret as the spatial orientation of the two reactants within the ice. The three approaches give the same results. The HNCO + NH3 ? OCN- + NH4+ reaction rate follows an Arrhenius law with an activation energy of 0.4 ± 0.1 kJ mol-1 (48 ± 12 K) and a pre-exponential factor of 0.0035 ± 0.0015 s-1. Conclusions: The present experiment has the important implication that the HNCO + NH3 reaction can account for the observed abundances of solid OCN- and the HNCO non detection in young stellar objects.

  1. Building robust chemical reaction mechanisms : next generation of automatic model construction software

    E-print Network

    Song, Jing, 1972-

    2004-01-01

    Building proper reaction mechanisms is crucial to model the system dynamic properties for many industrial processes with complex chemical reaction phenomena. Because of the complexity of a reaction mechanism, computer-aided ...

  2. [Anaphylactic reactions to low-molecular weight chemicals].

    PubMed

    Nowak, Daria; Panaszek, Bernard

    2015-01-01

    Low-molecular weight chemicals (haptens) include a large group of chemical compounds occurring in work environment, items of everyday use (cleaning products, clothing, footwear, gloves, furniture), jewelry (earrings, bracelets), drugs, especially in cosmetics. They cause type IV hypersensitive reactions. During the induction phase of delayed-type hypersensitivity, haptens form complexes with skin proteins. After internalization through antigen presenting cells, they are bound to MHC class II molecules. Next, they are exposed against specific T-lymphocytes, what triggers activation of Th1 cells mainly. After repeating exposition to that hapten, during effector phase, Th1 induce production of cytokines affecting non-specific inflammatory cells. Usually, it causes contact dermatitis. However, occasionally incidence of immediate generalized reactions after contact with some kinds of haptens is noticed. A question arises, how the hapten does induce symptoms which are typical for anaphylaxis, and what contributes to amplification of this mechanism. It seems that this phenomenon arises from pathomechanism occurring in contact urticaria syndrome in which an anaphylactic reaction may be caused either by contact of sensitized skin with protein antigens, high-molecular weight allergens, or haptens. One of the hypotheses indicates the leading role of basophiles in this process. Their contact with haptens, may cause to release mediators of immediate allergic reaction (histamine, eicosanoids) and to produce cytokines corresponding to Th2 cells profile. Furthermore, Th17 lymphocytes secreting pro-inflammatory interleukin-17 might be engaged into amplifying hypersensitivity into immediate reactions and regulatory T-cells may play role in the process, due to insufficient control of the activity of effector cells. PMID:25661919

  3. Surface Reaction Kinetics of Ga 1x In x P Growth During Pulsed Chemical Beam Epitaxy

    E-print Network

    Surface Reaction Kinetics of Ga 1­x In x P Growth During Pulsed Chemical Beam Epitaxy N. Dietz 1 growth has been a slow process because little is known about chemical reaction properties and reaction into the surface reaction kinetics during an organometallic deposition process. These insights will allow us

  4. AURORA: A FORTRAN program for modeling well stirred plasma and thermal reactors with gas and surface reactions

    SciTech Connect

    Meeks, E.; Grcar, J.F.; Kee, R.J. [Sandia National Labs., Livermore, CA (United States). Thermal and Plasma Processes Dept.] [Sandia National Labs., Livermore, CA (United States). Thermal and Plasma Processes Dept.; Moffat, H.K. [Sandia National Labs., Albuquerque, NM (United States). Surface Processing Sciences Dept.] [Sandia National Labs., Albuquerque, NM (United States). Surface Processing Sciences Dept.

    1996-02-01

    The AURORA Software is a FORTRAN computer program that predicts the steady-state or time-averaged properties of a well mixed or perfectly stirred reactor for plasma or thermal chemistry systems. The software was based on the previously released software, SURFACE PSR which was written for application to thermal CVD reactor systems. AURORA allows modeling of non-thermal, plasma reactors with the determination of ion and electron concentrations and the electron temperature, in addition to the neutral radical species concentrations. Well stirred reactors are characterized by a reactor volume, residence time or mass flow rate, heat loss or gas temperature, surface area, surface temperature, the incoming temperature and mixture composition, as well as the power deposited into the plasma for non-thermal systems. The model described here accounts for finite-rate elementary chemical reactions both in the gas phase and on the surface. The governing equations are a system of nonlinear algebraic relations. The program solves these equations using a hybrid Newton/time-integration method embodied by the software package TWOPNT. The program runs in conjunction with the new CHEMKIN-III and SURFACE CHEMKIN-III packages, which handle the chemical reaction mechanisms for thermal and non-thermal systems. CHEMKIN-III allows for specification of electron-impact reactions, excitation losses, and elastic-collision losses for electrons.

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

    ERIC Educational Resources Information Center

    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…

  6. Solar-chemical energy conversion via reversible liquid phase Diels-Alder reactions. Final technical report

    SciTech Connect

    Lenz, T.G.; Hegedus, L.S.; Vaughan, J.D.

    1983-05-01

    Thermochemical energy conversion at moderate or low temperature (< about 400/sup 0/C) employing liquid phase components throughout a cycle is suggested as a promising concept for high-efficiency conversion of solar energy to a convenient chemical form. In particular, we propose liquid phase Diels-Alder cycloaddition chemistry as an important class of reversible reactions for such low or moderate temperature thermochemical energy conversion systems. One of the important attributes of thermally driven Diels-Alder reactions is their concerted mechanism, with consequent high yields and efficiencies relative to liquid photochemical systems. Since the systems we propose involve organic species, with thermal stability concerns about 400/sup 0/C, it is important to demonstrate equilibrium shift capability for the highly energetic reactions sought. We have therefore carried out experimental studies with model liquid Diels-Alder systems that clearly demonstrate the degree of control over equilibrium available through substituent entropy effects. These results are of importance as regards subsequent systematic identification of Diels-Alder reactions having ideal thermochemical and physical properties.

  7. EFFECTS OF THERMAL TREATMENTS ON THE CHEMICAL REACTIVITY OF TRICHLOROETHYLENE

    EPA Science Inventory

    A series of experiments was completed to investigate abiotic degradation and reaction product formation of trichloroethylene (TCE) when heated. A quartz-tube apparatus was used to study short residence time and high temperature conditions that are thought to occur during thermal ...

  8. Mechano-chemical coupling in Belousov-Zhabotinskii reactions.

    PubMed

    Klika, Václav; Grmela, Miroslav

    2014-03-28

    Mechano-chemical coupling has been recently recognised as an important effect in various systems as chemical reactivity can be controlled through an applied mechanical loading. Namely, Belousov-Zhabotinskii reactions in polymer gels exhibit self-sustained oscillations and have been identified to be reasonably controllable and definable to the extent that they can be harnessed to perform mechanical work at specific locations. In this paper, we use our theoretical work of nonlinear mechano-chemical coupling and investigate the possibility of providing an explanation of phenomena found in experimental research by means of this theory. We show that mechanotransduction occurs as a response to both static and dynamic mechanical stimulation, e.g., volume change and its rate, as observed experimentally and discuss the difference of their effects on oscillations. Plausible values of the quasi-stoichiometric parameter f of Oregonator model are estimated together with its dependence on mechanical stimulation. An increase in static loading, e.g., pressure, is predicted to have stimulatory effect whereas dynamic loading, e.g., rate of volume change, is predicted to be stimulatory only up to a certain threshold. Further, we offer a physically consistent explanation of the observed phenomena why some Belousov-Zhabotinskii gels require an additional mechanical stimulation to show emergence of oscillation or why "revival" of oscillations in Belousov-Zhabotinskii reactions is possible together with indications for further experimental setups. PMID:24697427

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

    NASA Astrophysics Data System (ADS)

    Matsuzawa, Mitsuhiro; Togashi, Shigenori; Hasebe, Shinji

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

  10. Solving the chemical master equation for monomolecular reaction systems analytically.

    PubMed

    Jahnke, Tobias; Huisinga, Wilhelm

    2007-01-01

    The stochastic dynamics of a well-stirred mixture of molecular species interacting through different biochemical reactions can be accurately modelled by the chemical master equation (CME). Research in the biology and scientific computing community has concentrated mostly on the development of numerical techniques to approximate the solution of the CME via many realizations of the associated Markov jump process. The domain of exact and/or efficient methods for directly solving the CME is still widely open, which is due to its large dimension that grows exponentially with the number of molecular species involved. In this article, we present an exact solution formula of the CME for arbitrary initial conditions in the case where the underlying system is governed by monomolecular reactions. The solution can be expressed in terms of the convolution of multinomial and product Poisson distributions with time-dependent parameters evolving according to the traditional reaction-rate equations. This very structured representation allows to deduce easily many properties of the solution. The model class includes many interesting examples. For more complex reaction systems, our results can be seen as a first step towards the construction of new numerical integrators, because solutions to the monomolecular case provide promising ansatz functions for Galerkin-type methods. PMID:16953443

  11. A quantum informational approach for dissecting chemical reactions

    NASA Astrophysics Data System (ADS)

    Duperrouzel, Corinne; Tecmer, Pawe?; Boguslawski, Katharina; Barcza, Gergely; Legeza, Örs; Ayers, Paul W.

    2015-02-01

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

  12. Structural cluster analysis of chemical reactions in solution

    NASA Astrophysics Data System (ADS)

    Gallet, Grégoire A.; Pietrucci, Fabio

    2013-08-01

    We introduce a simple and general approach to the problem of clustering structures from atomic trajectories of chemical reactions in solution. By considering distance metrics which are invariant under permutation of identical atoms or molecules, we demonstrate that it is possible to automatically resolve as distinct structural clusters the configurations corresponding to reactants, products, and transition states, even in presence of atom-exchanges and of hundreds of solvent molecules. Our approach strongly simplifies the analysis of large trajectories and it opens the way to the construction of kinetic network models of activated processes in solution employing the available efficient schemes developed for proteins conformational ensembles.

  13. Method for detecting pollutants. [through chemical reactions and heat treatment

    NASA Technical Reports Server (NTRS)

    Rogowski, R. S.; Richards, R. R.; Conway, E. J. (inventors)

    1976-01-01

    A method is described for detecting and measuring trace amounts of pollutants of the group consisting of ozone, nitrogen dioxide, and carbon monoxide in a gaseous environment. A sample organic solid material that will undergo a chemical reaction with the test pollutant is exposed to the test environment and thereafter, when heated in the temperature range of 100-200 C., undergoes chemiluminescence that is measured and recorded as a function of concentration of the test pollutant. The chemiluminescence of the solid organic material is specific to the pollutant being tested.

  14. Assessment of reaction-rate predictions of a collision-energy approach for chemical reactions in atmospheric flows.

    SciTech Connect

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

    2010-06-01

    A recently proposed approach for the Direct Simulation Monte Carlo (DSMC) method to calculate chemical-reaction rates is assessed for high-temperature atmospheric species. The new DSMC model reproduces measured equilibrium reaction rates without using any macroscopic reaction-rate information. Since it uses only molecular properties, the new model is inherently able to predict reaction rates for arbitrary non-equilibrium conditions. DSMC non-equilibrium reaction rates are compared to Park's phenomenological nonequilibrium reaction-rate model, the predominant model for hypersonic-flow-field calculations. For near-equilibrium conditions, Park's model is in good agreement with the DSMC-calculated reaction rates. For far-from-equilibrium conditions, corresponding to a typical shock layer, significant differences can be found. The DSMC predictions are also found to be in very good agreement with measured and calculated non-equilibrium reaction rates, offering strong evidence that this is a viable and reliable technique to predict chemical reaction rates.

  15. Materials problems in reversible chemical reaction storage systems for solar energy

    Microsoft Academic Search

    R. W. Mar

    1978-01-01

    Materials problems encountered in the development of thermochemical energy storage systems for solar energy are discussed. Concerns with catalyzed reaction systems include effects of thermal cycling on reactor materials, catalyst availability and lifetime, and undesirable side reactions. Problems have arisen in thermal decomposition systems due to poor or variable kinetics, volume expansion effects, and poor intrinsic heat transfer properties. Reactions

  16. Engineered Barrier Systems Thermal-Hydraulic-Chemical Column Test Report

    SciTech Connect

    W.E. Lowry

    2001-12-13

    The Engineered Barrier System (EBS) Thermal-Hydraulic-Chemical (THC) Column Tests provide data needed for model validation. The EBS Degradation, Flow, and Transport Process Modeling Report (PMR) will be based on supporting models for in-drift THC coupled processes, and the in-drift physical and chemical environment. These models describe the complex chemical interaction of EBS materials, including granular materials, with the thermal and hydrologic conditions that will be present in the repository emplacement drifts. Of particular interest are the coupled processes that result in mineral and salt dissolution/precipitation in the EBS environment. Test data are needed for thermal, hydrologic, and geochemical model validation and to support selection of introduced materials (CRWMS M&O 1999c). These column tests evaluated granular crushed tuff as potential invert ballast or backfill material, under accelerated thermal and hydrologic environments. The objectives of the THC column testing are to: (1) Characterize THC coupled processes that could affect performance of EBS components, particularly the magnitude of permeability reduction (increases or decreases), the nature of minerals produced, and chemical fractionation (i.e., concentrative separation of salts and minerals due to boiling-point elevation). (2) Generate data for validating THC predictive models that will support the EBS Degradation, Flow, and Transport PMR, Rev. 01.

  17. Fuels and chemicals from biomass using solar thermal energy

    NASA Technical Reports Server (NTRS)

    Giori, G.; Leitheiser, R.; Wayman, M.

    1981-01-01

    The significant nearer term opportunities for the application of solar thermal energy to the manufacture of fuels and chemicals from biomass are summarized, with some comments on resource availability, market potential and economics. Consideration is given to the production of furfural from agricultural residues, and the role of furfural and its derivatives as a replacement for petrochemicals in the plastics industry.

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

    PubMed

    Keser?, György M; Soós, Tibor; Kappe, C Oliver

    2014-08-01

    How do skilled synthetic chemists develop good intuitive expertise? Why can we only access such a small amount of the available chemical space-both in terms of the reactions used and the chemical scaffolds we make? We argue here that these seemingly unrelated questions have a common root and are strongly interdependent. We performed a comprehensive analysis of organic reaction parameters dating back to 1771 and discovered that there are several anthropogenic factors that limit reaction parameters and thus the scope of synthetic chemistry. Nevertheless, many of the anthropogenic limitations such as narrow parameter space and the opportunity for rapid and clear feedback on the progress of reactions appear to be crucial for the acquisition of valid and reliable chemical intuition. In parallel, however, all of these same factors represent limitations for the exploration of available chemistry space and we argue that these are thus at least partly responsible for limited access to new chemistries. We advocate, therefore, that the present anthropogenic boundaries can be expanded by a more conscious exploration of "off-road" chemistry that would also extend the intuitive knowledge of trained chemists. PMID:24877159

  19. Systematic exploration of the mechanism of chemical reactions: the global reaction route mapping (GRRM) strategy using the ADDF and AFIR methods.

    PubMed

    Maeda, Satoshi; Ohno, Koichi; Morokuma, Keiji

    2013-03-21

    Global reaction route mapping (GRRM), a fully-automated search for all important reaction pathways relevant to a given purpose, on the basis of quantum chemical calculations enables systematic elucidation of complex chemical reaction mechanisms. However, GRRM had previously been limited to very simple systems. This is mainly because such calculations are highly demanding even in small systems when a brute-force sampling is considered. Hence, we have developed two independent but complementary methods: anharmonic downward distortion following (ADDF) and artificial force induced reaction (AFIR) methods. ADDF can follow reaction pathways starting from local minima on the potential energy surface (PES) toward transition structures (TSs) and dissociation channels. AFIR can find pathways starting from two or more reactants toward TSs for their associative reactions. In other words, ADDF searches for A ? X type isomerization and A ? X + Y type dissociation pathways, whereas AFIR finds A + B ? X (+ Y) type associative pathways. Both follow special paths called the ADDF path and the AFIR path, and these tend to pass through near TSs of corresponding reaction pathways, giving approximate TSs. Such approximate TSs can easily be re-optimized to corresponding true TSs by standard geometry optimizations. On the basis of these two methods, we have proposed practical strategies of GRRM. The GRRM strategies have been applied to a variety of chemical systems ranging from thermal- and photochemical-reactions in small systems to organometallic- and enzyme-catalysis, on the basis of quantum chemical calculations. In this perspective, we present an overview of the GRRM strategies and some results of applications. Their practical usage for systematic prediction is also discussed. PMID:23389653

  20. Fischer-Tropsch reaction on a thermally conductive and reusable silicon carbide support.

    PubMed

    Liu, Yuefeng; Ersen, Ovidiu; Meny, Christian; Luck, Francis; Pham-Huu, Cuong

    2014-05-01

    The Fischer-Tropsch (FT) process, in which synthesis gas (syngas) derived from coal, natural gas, and biomass is converted into synthetic liquid fuels and chemicals, is a strongly exothermic reaction, and thus, a large amount of heat is generated during the reaction that could severely modify the overall selectivity of the process. In this Review, we report the advantages that can be offered by different thermally conductive supports, that is, carbon nanomaterials and silicon carbide, pure or doped with different promoters, for the development of more active and selective FT catalysts. This Review follows a discussion regarding the clear trend in the advantages and drawbacks of these systems in terms of energy efficiency and catalytic performance for this most-demanded catalytic process. It is demonstrated that the use of a support with an appropriate pore size and thermal conductivity is an effective strategy to tune and improve the activity of the catalyst and to improve product selectivity in the FT process. The active phase and the recovery of the support, which also represents a main concern in terms of the large amount of FT catalyst used and the cost of the active cobalt phase, is also discussed within the framework of this Review. It is expected that a thermally conductive support such as ?-SiC will not only improve the development of the FT process, but that it will also be part of a new support for different catalytic processes for which high catalytic performance and selectivity are strongly needed. PMID:24616239

  1. Following a chemical reaction using high-harmonic interferometry.

    PubMed

    Wörner, H J; Bertrand, J B; Kartashov, D V; Corkum, P B; Villeneuve, D M

    2010-07-29

    The study of chemical reactions on the molecular (femtosecond) timescale typically uses pump laser pulses to excite molecules and subsequent probe pulses to interrogate them. The ultrashort pump pulse can excite only a small fraction of molecules, and the probe wavelength must be carefully chosen to discriminate between excited and unexcited molecules. The past decade has seen the emergence of new methods that are also aimed at imaging chemical reactions as they occur, based on X-ray diffraction, electron diffraction or laser-induced recollision--with spectral selection not available for any of these new methods. Here we show that in the case of high-harmonic spectroscopy based on recollision, this apparent limitation becomes a major advantage owing to the coherent nature of the attosecond high-harmonic pulse generation. The coherence allows the unexcited molecules to act as local oscillators against which the dynamics are observed, so a transient grating technique can be used to reconstruct the amplitude and phase of emission from the excited molecules. We then extract structural information from the amplitude, which encodes the internuclear separation, by quantum interference at short times and by scattering of the recollision electron at longer times. The phase records the attosecond dynamics of the electrons, giving access to the evolving ionization potentials and the electronic structure of the transient molecule. In our experiment, we are able to document a temporal shift of the high-harmonic field of less than an attosecond (1 as = 10(-18) s) between the stretched and compressed geometry of weakly vibrationally excited Br(2) in the electronic ground state. The ability to probe structural and electronic features, combined with high time resolution, make high-harmonic spectroscopy ideally suited to measuring coupled electronic and nuclear dynamics occurring in photochemical reactions and to characterizing the electronic structure of transition states. PMID:20671706

  2. Physico-Geometrical Kinetics of Solid-State Reactions in an Undergraduate Thermal Analysis Laboratory

    ERIC Educational Resources Information Center

    Koga, Nobuyoshi; Goshi, Yuri; Yoshikawa, Masahiro; Tatsuoka, Tomoyuki

    2014-01-01

    An undergraduate kinetic experiment of the thermal decomposition of solids by microscopic observation and thermal analysis was developed by investigating a suitable reaction, applicable techniques of thermal analysis and microscopic observation, and a reliable kinetic calculation method. The thermal decomposition of sodium hydrogen carbonate is…

  3. Thermal chemical-mechanical reactive flow model of shock initiation in solid explosives

    SciTech Connect

    Nicholls, A L., III; Tarver, C M

    1998-08-26

    The three dimensional Arbitrary Lagrange Eulerian hydrodynamic computer code ALE3D with fully coupled thermal-chemical-mechanical material models provides the framework for the development of a physically realistic model of shock initiation and detonation of solid explosives. The processes of hot spot formation during shock compression, subsequent ignition of reaction or failure to react, growth of reaction in individual hot spots, and coalescence of reacting hot spots during the transition to detonation can now be modeled using Arrhenius chemical kinetic rate laws and heat transfer to propagate the reactive flow. This paper discusses the growth rates of reacting hot spots in HMX and TATB and their coalescence during shock to detonation transition. Hot spot deflagration rates are found to be fast enough to consume explosive particles less than 10 mm in diameter during typical shock duration times, but larger particles must fragment and create more reactive surface area in order to be rapidly consumed.

  4. Distinguishing solid bitumens formed by thermochemical sulfate reduction and thermal chemical alteration

    USGS Publications Warehouse

    Kelemen, S.R.; Walters, C.C.; Kwiatek, P.J.; Afeworki, M.; Sansone, M.; Freund, H.; Pottorf, R.J.; Machel, H.G.; Zhang, T.; Ellis, G.S.; Tang, Y.; Peters, K.E.

    2008-01-01

    Insoluble solid bitumens are organic residues that can form by the thermal chemical alteration (TCA) or thermochemical sulfate reduction (TSR) of migrated petroleum. TCA may actually encompass several low temperature processes, such as biodegradation and asphaltene precipitation, followed by thermal alteration. TSR is an abiotic redox reaction where petroleum is oxidized by sulfate. It is difficult to distinguish solid bitumens associated with TCA of petroleum from those associated with TSR when both processes occur at relatively high temperature. The focus of the present work was to characterize solid bitumen samples associated with TCA or TSR using X-ray photoelectron spectroscopy (XPS). XPS is a surface analysis conducted on either isolated or in situ (>25 ??m diameter) solid bitumen that can provide the relative abundance and chemical speciation of carbon, organic and inorganic heteroatoms (NSO). In this study, naturally occurring solid bitumens from three locations, Nisku Fm. Brazeau River area (TSR-related), LaBarge Field Madison Fm. (TSR-related), and the Alaskan Brooks range (TCA-related), are compared to organic solids generated during laboratory simulation of the TSR and TCA processes. The abundance and chemical nature of organic nitrogen and sulfur in solid bitumens can be understood in terms of the nature of (1) petroleum precursor molecules, (2) the concentration of nitrogen by way of thermal stress and (3) the mode of sulfur incorporation. TCA solid bitumens originate from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. Organic sulfur in TCA organic solids remains fairly constant with increasing maturation (3.5 to ???17 sulfur per 100 carbons) into aromatic structures and to the low levels of nitrogen in their hydrocarbon precursors. Hence, XPS results provide organic chemical composition information that helps to distinguish whether solid bitumen, either in situ or removed and concentrated from the rock matrix, was formed via the TCA or TRS process. ?? 2008 Elsevier Ltd.

  5. The quantum dynamics of electronically nonadiabatic chemical reactions

    NASA Technical Reports Server (NTRS)

    Truhlar, Donald G.

    1993-01-01

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

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

    SciTech Connect

    Alves, Giselle M. [Escola Tecnica, Universidade Federal do Parana, Curitiba (Brazil); Kremer, Gilberto M. [Departamento de Fisica, Universidade Federal do Parana, Curitiba (Brazil); Soares, Ana Jacinta [Departamento de Matematica, Universidade do Minho, Braga (Portugal)

    2011-05-20

    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.

  7. A chemical reaction heat pump system adopting the reactive distillation process

    Microsoft Academic Search

    Yonsoo Chung; Seungki Hong; Hyung Keun Song

    1996-01-01

    A new configuration of the chemical reaction heat pump system using 2-propanol dehydrogenation and acetone hydrogenation reactions was proposed in this study. To overcome the intrinsic thermodynamic limitation of chemical reaction heat pump systems, the reactive distillation process was adopted. Through the experimental study, the new configuration showed the better performance compared to previous ones. This study revealed a new

  8. Experimental Re-Examination of the Law of Conservation of Mass in Chemical Reactions

    Microsoft Academic Search

    KLAUS VOLKAMER; CHRISTOPH STREICHER; KENNETH G. WALTON; JOHN FAGAN

    At the beginning of the century the law of conservation of mass in chemical reactions was checked experimentally by Landolt and various other experimenters. Even though in 8 of the 10 chemical reactions studied by Landolt the validity of conservation of mass was confirmed within the margin of experimental errors, in 2 reactions the pre vs. post comparison of the

  9. A modified next reaction method for simulating chemical systems with time dependent propensities and delays

    E-print Network

    Anderson, David F.

    A modified next reaction method for simulating chemical systems with time dependent propensities; publisher error corrected 28 January 2008 Chemical reaction systems with a low to moderate number with methods that produce statistically exact sample paths such as the Gillespie algorithm or the next reaction

  10. Progression in High School Students' (Aged 16-18) Conceptualizations about Chemical Reactions in Solution.

    ERIC Educational Resources Information Center

    Boo, Hong-Kwen; Watson, J. R.

    2001-01-01

    Explores the development over time of students' understandings of the concept of chemical reaction in the context of two familiar reactions in solution. Based on interviews (n=48), results show that students made some progress in their understanding of the concept of chemical reaction but some fundamental misconceptions remained. (Author/MM)

  11. Reaction ensemble molecular dynamics: Direct simulation of the dynamic equilibrium properties of chemically reacting mixtures

    E-print Network

    Lisal, Martin

    diffusion) as well as reaction equilibria for chemically reacting mixtures. DOI: 10.1103/PhysRevE.70.) on chemical reaction equilibria is critical in many fields of science including mixture separationReaction ensemble molecular dynamics: Direct simulation of the dynamic equilibrium properties

  12. Low-energy electron-stimulated chemical reactions of CO in water ice

    NASA Astrophysics Data System (ADS)

    Yamamoto, S.; Beniya, A.; Mukai, K.; Yamashita, Y.; Yoshinobu, J.

    2004-04-01

    We investigated low-energy electron-stimulated chemical reactions between CO and water molecules in low-temperature ice using infrared reflection absorption spectroscopy. Carbon dioxide, the formyl radical, formaldehyde, and methanol were produced by electron irradiation of the water/CO/water layered ice. The electron energy threshold and temperature dependence for the chemical reactions were investigated to elucidate the reaction mechanisms.

  13. Analytical Modeling of Shear-Induced Chemical Reactions in Mixed Powders

    NASA Astrophysics Data System (ADS)

    Horie, Yasuyuki

    1999-06-01

    A theoretical model is formulated to describe a complex interplay of mechanical, thermal, chemical processes associated with intense shear in mixed powders. The model is an outgrowth of a recent numerical study of chemical reactions in Nb-Si and Ni-Al mixtures. In the analytical model, mass mixing of constituents is represented effectively by a mixing characteristic time, which is assumed to be a function of strain rate. The overall governing equations resemble a theory of continuously stirred chemical reactors. Using a dimensionless system of equations, we show a variety of flow regimes in terms of the mixing time, whcih is found to be equivalent to residence time in the reactor theory. Solutions include oscillatory as well as discontious behavior. The conditions of spontaneous ignition and extinction are evaluated in terms of dimensionnless groups that are functions of process parameters such as surface heat transfer coefficient, heat of reaction, and the width of shear bands. The ignition conditions are also examined in the context of shock-wave processing.

  14. Lyapunov functions, stationary distributions, and non-equilibrium potential for chemical reaction networks

    E-print Network

    Anderson, David F.

    Lyapunov functions, stationary distributions, and non-equilibrium potential for chemical reaction the well known Lyapunov function of chemical reaction network theory as a scaling limit of the non-equilibrium Abstract We consider the relationship between stationary distributions for stochastic models of chemical

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

    E-print Network

    Lacoste, David

    Non-invasive estimation of dissipation from non-equilibrium fluctuations in chemical reactions S JOURNAL OF CHEMICAL PHYSICS 139, 124109 (2013) Non-invasive estimation of dissipation from non-equilibrium fluctuations in chemical reactions S. Muy,1 A. Kundu,2 and D. Lacoste1 1 Laboratoire de Physico

  16. Molecular Orbital Studies of Zinc Oxide Chemical Vapor Deposition: Gas-Phase Radical Reactions

    E-print Network

    Schlegel, H. Bernhard

    Molecular Orbital Studies of Zinc Oxide Chemical Vapor Deposition: Gas-Phase Radical Reactions-phase reactions involved in the radical mechanism for zinc oxide chemical vapor deposition have been examined in the radical and closed shell mechanisms for zinc oxide chemical vapor deposition shows that the barrier

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

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

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

  18. Waste Heat Recovery from Blast Furnace Slag by Chemical Reactions

    NASA Astrophysics Data System (ADS)

    Qin, Yuelin; Lv, Xuewei; Bai, Chenguang; Qiu, Guibao; Chen, Pan

    2012-08-01

    Blast furnace (BF) slag, which is the main byproduct in the ironmaking process, contains large amounts of sensible heat. To recover the heat, a new waste heat-recovery system—granulating molten BF slag by rotary multinozzles cup atomizer and pyrolyzing printed circuited board with obtained hot BF slag particle—was proposed in this study. The feasibility of the waste heat-recovery system was verified by dry granulation and pyrolyzation experiments. The energy of hot BF slag could be converted to chemical energy through the pyrolysis reaction, and a large amount of combustible gas like CO, H2, C m H n , and CH4 can be generated during the process.

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

    Hot-pressing of MoSi2 powders with carbon at high temperatures reduces the siliceous grain boundary phase in the resultant compact. The chemical reactions in this process were examined using the Knudsen cell technique. A 2.3 wt pct oxygen MoSi2 powder and a 0.59 wt pct oxygen MoSi2 powder, both with additions of 2 wt pct carbon, were examined. The reduction of the siliceous grain boundary phase was examined at 1350 K and the resultant P(SiO)/P(CO) ratios interpreted in terms of the SiO(g) and CO(g) isobars on the Si-C-O predominance diagram. The MoSi2 + carbon mixtures were then heated at the hot-pressing temperature of 2100 K. Large weight losses were observed and could be correlated with the formation of a low-melting eutectic and the formation and vaporization of SiC.

  20. A Thermal Desorption Chemical Ionization Ion Trap Mass Spectrometer for the Chemical Characterization of Ultrafine Aerosol Particles

    Microsoft Academic Search

    Andreas Held; G. Jeffrey Rathbone; James N. Smith

    2009-01-01

    The development of a thermal desorption chemical ionization ion trap mass spectrometer for the chemical characterization of ultrafine aerosol particles is reported and first experimental results are presented. Atmospheric particles are size-classified and collected using a unipolar charger, a radial differential mobility analyzer and an electrostatic precipitator, and analyzed after thermal desorption and chemical ionization using an ion trap mass

  1. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks

    PubMed Central

    Park, Kyo Sung; Ni, Zheng; Côté, Adrien P.; Choi, Jae Yong; Huang, Rudan; Uribe-Romo, Fernando J.; Chae, Hee K.; O’Keeffe, Michael; Yaghi, Omar M.

    2006-01-01

    Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) have been synthesized as crystals by copolymerization of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, respectively. In addition, one example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m2/g), high thermal stability (up to 550°C), and remarkable chemical resistance to boiling alkaline water and organic solvents. PMID:16798880

  2. No electron left behind: a rule-based expert system to predict chemical reactions and reaction mechanisms

    PubMed Central

    Chen, Jonathan H.; Baldi, Pierre

    2009-01-01

    Predicting the course and major products of arbitrary reactions is a fundamental problem in chemistry, one that chemists must address in a variety of tasks ranging from synthesis design to reaction discovery. Described here is an expert system to predict organic chemical reactions based on a knowledge base of over 1,500 manually composed reaction transformation rules. Novel rule extensions are introduced to enable robust predictions and describe detailed reaction mechanisms at the level of electron flows in elementary reaction steps, ensuring that all reactions are properly balanced and atom-mapped. The core reaction prediction functionalities of this expert system are illustrated with applications including: (1) prediction of detailed reaction mechanisms; (2) computer-based learning in organic chemistry; (3) retro synthetic analysis; and (4) combinatorial library design. Select applications available via http://cdb.ics.uci.edu. PMID:19719121

  3. Enzyme catalysis Enzyme catalysis is the catalysis of chemical reactions by

    E-print Network

    Cavanagh, John

    Enzyme catalysis Enzyme catalysis is the catalysis of chemical reactions by specialized proteins known as enzymes. Catalysis of biochemical reactions in the cell is vital due to the very low reaction rates of the uncatalysed reactions. The mechanism of enzyme catalysis is similar in principle to other

  4. Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks

    SciTech Connect

    Ziaul Huque

    2007-08-31

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

  5. Synthesis of aligned carbon nanotubes using thermal chemical vapor deposition

    Microsoft Academic Search

    Cheol Jin Lee; Dae Woon Kim; Tae Jae Lee; Young Chul Choi; Young Soo Park; Young Hee Lee; Won Bong Choi; Nae Sung Lee; Gyeong-Su Park; Jong Min Kim

    1999-01-01

    Aligned carbon nanotubes have been synthesized on transition metal-coated silicon substrates with C2H2 using thermal chemical vapor deposition. It was found that nanotubes can be mostly vertically aligned on a large area of plain Si substrates when the density of metal domains reaches a certain value. Pretreatment of Co–Ni alloy by HF dipping and etching with NH3 gas prior to

  6. Progress in an oxygen-carrier reaction kinetics experiment for rotary-bed chemical looping combustion

    E-print Network

    Jester-Weinstein, Jack (Jack L.)

    2013-01-01

    The design process for an experimental platform measuring reaction kinetics in a chemical looping combustion (CLC) process is documented and justified. To enable an experiment designed to characterize the reaction kinetics ...

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

    SciTech Connect

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

    2010-01-22

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

  8. Thermalization with chemical potentials, and higher spin black holes

    E-print Network

    Gautam Mandal; Ritam Sinha; Nilakash Sorokhaibam

    2015-03-06

    We study the long time behaviour of local observables following a quantum quench in 1+1 dimensional conformal field theories possessing additional conserved charges besides the energy. We show that the expectation value of an arbitrary string of {\\it local} observables supported on a finite interval exponentially approaches an equilibrium value. The equilibrium is characterized by a temperature and chemical potentials defined in terms of the quenched state. For an infinite number of commuting conserved charges, the equilibrium ensemble is a generalized Gibbs ensemble (GGE). We compute the thermalization rate in a systematic perturbation in the chemical potentials, using a new technique to sum over an infinite number of Feynman diagrams. The above technique also allows us to compute relaxation times for thermal Green's functions in the presence of an arbitrary number of chemical potentials. In the context of a higher spin (hs[\\lambda]) holography, the partition function of the final equilibrium GGE is known to agree with that of a higher spin black hole. The thermalization rate from the CFT computed in our paper agrees with the quasinormal frequency of a scalar field in this black hole.

  9. Shock slip-relations for thermal and chemical nonequilibrium flows

    NASA Astrophysics Data System (ADS)

    Jinrong, Tang

    1996-05-01

    This paper appears to be the first where the multi-temperature shock slip-relations for the thermal and chemical nonequilibrium flows are derived. The derivation is based on analysis of the influences of thermal nonequilibrium and viscous effects on the mass, momentum and emergy flux balance relations at the shock wave. When the relaxation times for all internal energy modes tend to zero, the multi-tmperature shock slip-relations are converted into single-temperature ones for thermal equilibrium flows. The present results can be applied to flow over vehicles of different geometries with or without angles of attack. In addition, the present single-temperature shock slip-relations are compared with those in the literature, and some defects and limitations in the latter are clarified.

  10. The Impact of Fluid Deformation on Mixing and Fast Chemical Reaction Along Reaction Fronts in Porous Media

    NASA Astrophysics Data System (ADS)

    Dentz, Marco; Le Borgne, Tanguy; Ginn, Timothy; Nassar, Mohamed; Bennethum, Lynn S.

    2015-04-01

    Fast chemical reactions in heterogeneous flows are controlled by fluid mixing, which perturbs local chemical equilibria and thus triggers chemical reactions. The deformation of material fluid elements in inhomogeneous flow fields leads to solute spreading and increased mixing due to the steepening of concentration gradients on one hand, and the increase of interfacial surface area between chemicals on the other. We present an approach based on a lamellar representation of fluid mixing that links fluid deformation, the distribution of concentration gradiens, and the upscaled reaction rates for fast reversible reactions. The evolution of effective reaction rates are governed by the flow topology, which determines the distribution of local velocity gradients, and the elongation rate of the reaction front. This leads to a significant increase of reaction efficiency, which turns out to be orders of magnitude larger than in homogeneous flow. This lamella based approach allows for the systematic evaluation of the temporal evolution of equilibrium reaction rates in inhomogeneous flows, and establishes a direct link between the reaction efficiency and the spatial characteristics of the underlying flow field as quantified by the deformation of material fluid elements.

  11. Thermal-chemical Mantle Convection Models With Adaptive Mesh Refinement

    NASA Astrophysics Data System (ADS)

    Leng, W.; Zhong, S.

    2008-12-01

    In numerical modeling of mantle convection, resolution is often crucial for resolving small-scale features. New techniques, adaptive mesh refinement (AMR), allow local mesh refinement wherever high resolution is needed, while leaving other regions with relatively low resolution. Both computational efficiency for large- scale simulation and accuracy for small-scale features can thus be achieved with AMR. Based on the octree data structure [Tu et al. 2005], we implement the AMR techniques into the 2-D mantle convection models. For pure thermal convection models, benchmark tests show that our code can achieve high accuracy with relatively small number of elements both for isoviscous cases (i.e. 7492 AMR elements v.s. 65536 uniform elements) and for temperature-dependent viscosity cases (i.e. 14620 AMR elements v.s. 65536 uniform elements). We further implement tracer-method into the models for simulating thermal-chemical convection. By appropriately adding and removing tracers according to the refinement of the meshes, our code successfully reproduces the benchmark results in van Keken et al. [1997] with much fewer elements and tracers compared with uniform-mesh models (i.e. 7552 AMR elements v.s. 16384 uniform elements, and ~83000 tracers v.s. ~410000 tracers). The boundaries of the chemical piles in our AMR code can be easily refined to the scales of a few kilometers for the Earth's mantle and the tracers are concentrated near the chemical boundaries to precisely trace the evolvement of the boundaries. It is thus very suitable for our AMR code to study the thermal-chemical convection problems which need high resolution to resolve the evolvement of chemical boundaries, such as the entrainment problems [Sleep, 1988].

  12. Modeling thermal/chemical/mechanical response of energetic materials

    SciTech Connect

    Baer, M.R.; Hobbs, M.L.; Gross, R.J. [and others

    1995-07-01

    An overview of modeling at Sandia National Laboratories is presented which describes coupled thermal, chemical and mechanical response of energetic materials. This modeling addresses cookoff scenarios for safety assessment studies in systems containing energetic materials. Foundation work is discussed which establishes a method for incorporating chemistry and mechanics into multidimensional analysis. Finite element analysis offers the capabilities to simultaneously resolve reactive heat transfer and structural mechanics in complex geometries. Nonlinear conduction heat transfer, with multiple step finite-rate chemistry, is resolved using a thermal finite element code. Rate equations are solved element-by-element using a modified matrix-free stiff solver This finite element software was developed for the simulation of systems requiring large numbers of finite elements. An iterative implicit scheme, based on the conjugate gradient method, is used and a hemi-cube algorithm is employed for the determination of view factors in surface-to-surface radiation transfer The critical link between the reactive heat transfer and mechanics is the introduction of an appropriate constitutive material model providing a stress-strain relationship for quasi-static mechanics analysis. This model is formally derived from bubble nucleation theory, and parameter variations of critical model parameters indicate that a small degree of decomposition leads to significant mechanical response. Coupled thermal/chemical/mechanical analysis is presented which simulates experiments designed to probe cookoff thermal-mechanical response of energetic materials.

  13. Thermal, chemical, and mechanical response of rigid polyurethane foam

    SciTech Connect

    Hobbs, M.L.

    1997-12-01

    Rigid polyurethane foams are frequently used as encapsulants to isolate and support thermally sensitive components within weapon systems. When exposed to abnormal thermal environments, such as fire, the polyurethane foam decomposes to form products having a wide distribution of molecular weights and can dominate the overall thermal response of the system. Mechanical response of the decomposing foam, such as thermal expansion under various loading conditions created by gas generation, remains a major unsolved problem. A constitutive model of the reactive foam is needed to describe the coupling between mechanical response and chemical decomposition of foam exposed to environments such as fire. Towards this end, a reactive elastic-plastic constitutive model based on bubble mechanics describing nucleation, decomposition chemistry, and elastic/plastic mechanical behavior of rigid polyurethane foam has been developed. A local force balance, with mass continuity constraints, forms the basis of the constitutive model requiring input of temperature and the fraction of the material converted to gas. This constitutive model provides a stress-strain relationship which is applicable for a broad class of reacting materials such as explosives, propellants, pyrotechnics, and decomposing foams. The model is applied to a block of foam exposed to various thermal fluxes. The model is also applied to a sphere of foam confined in brass. The predicted mechanical deformation of the foam block and sphere are shown to qualitatively agree with experimental observations.

  14. Optomechanical manipulation of chemical reactions on the nanoscale with optofluidic nanotweezers

    NASA Astrophysics Data System (ADS)

    O'Dell, Dakota; Serey, Xavier; Erickson, David

    2014-03-01

    Chemical reactions are often described as a progression along a reaction coordinate. Waveguide evanescent fields generate an electromagnetic force that spans tens of nanometers and have been used previously to trap protein molecules. Applying this force along a reaction coordinate could radically alter the chemical reaction by modifying the activation energy or biasing the reaction towards a specific pathway. Here, we show that the adsorption of proteins onto carbon nanotubes can be controlled with opto-mechanical forces. An analytic model for the reaction was developed, the predictions of which were explored by probing the energy barrier under various experimental conditions.

  15. Direct Monte Carlo simulation of chemical reaction systems: Internal energy transfer and an energy-dependent unimolecular reaction

    E-print Network

    Anderson, James B.

    Direct Monte Carlo simulation of chemical reaction systems: Internal energy transfer and an energy a direct Monte Carlo simulation of an energy-dependent t&molecular reaction system of the type A+ B can be treated by Monte Carlo simulations. One of the most useful methods is Bird's direct simulation

  16. Thermal/chemical degradation of ceramic cross-flow filter materials

    SciTech Connect

    Alvin, M.A.; Lane, J.E.; Lippert, T.E.

    1989-11-01

    This report summarizes the 14-month, Phase 1 effort conducted by Westinghouse on the Thermal/Chemical Degradation of Ceramic Cross-Flow Filter Materials program. In Phase 1 expected filter process conditions were identified for a fixed-bed, fluid-bed, and entrained-bed gasification, direct coal fired turbine, and pressurized fluidized-bed combustion system. Ceramic cross-flow filter materials were also selected, procured, and subjected to chemical and physical characterization. The stability of each of the ceramic cross-flow materials was assessed in terms of potential reactions or phase change as a result of process temperature, and effluent gas compositions containing alkali and fines. In addition chemical and physical characterization was conducted on cross-flow filters that were exposed to the METC fluid-bed gasifier and the New York University pressurized fluidized-bed combustor. Long-term high temperature degradation mechanisms were proposed for each ceramic cross-flow material at process operating conditions. An experimental bench-scale test program is recommended to be conducted in Phase 2, generating data that support the proposed cross-flow filter material thermal/chemical degradation mechanisms. Papers on the individual subtasks have been processed separately for inclusion on the data base.

  17. On the relation between reactions and complexes of (bio)chemical reaction networks

    E-print Network

    Neigenfind, Jost; Nikoloski, Zoran

    2012-01-01

    Robustness of biochemical systems has become one of the central questions in systems biology although it is notoriously difficult to formally capture its multifaceted nature. Maintenance of normal system function depends not only on the stoichiometry of the underlying interrelated components, but also on a multitude of kinetic parameters. Invariant flux ratios, obtained within flux coupling analysis, as well as invariant complex ratios, derived within chemical reaction network theory, can characterize robust properties of a system at steady state. However, the existing formalisms for the description of these invariants do not provide full characterization as they either only focus on the flux-centric or the concentration-centric view. Here we develop a novel mathematical framework which combines both views and thereby overcomes the limitations of the classical methodologies. Our unified framework will be helpful in analyzing biologically important system properties.

  18. Free-Electron Lasers, Thermal Diffusion, Chemical Kinetics, and Surgery

    NASA Astrophysics Data System (ADS)

    Edwards, Glenn; Hutson, M. Shane

    2001-11-01

    Experiments demonstrate that the Mark-III FEL is a particularly effective tool for etching soft matter with remarkably little damage surrounding the site when tuned to wavelengths near 6.45 microns. Based on these observatons, human neuorsurgical and ophthalmic procedures were developed and have been performed successfully. A thermodynamic model was proposed to account for the wavelength dependence; however, the dynamics have not been well understood. We have theoretically investigated thermal diffusion and chemical kinetics in a system of alternating layers of protein and water as heated by a Mark-III FEL. The model is representative of cornea and the exposure conditions are comparable to previous experimental FEL investigations. A substantial temperature enhancement develops in the surface layer on the ten-nanosecond time scale. We consider the onset of both the helix-coil transition and chemical bond breaking of collagen in terms of the thermal, chemical, and structural properties of the system as well as laser wavelength and pulse structure.

  19. Chemical Reactions and Atomic Removal Dynamics during Gallium Nitride Chemical Mechanical Polishing Process: Quantum Chemical Molecular Dynamics Simulations

    NASA Astrophysics Data System (ADS)

    Kawaguchi, Kentaro; Higuchi, Yuji; Ozawa, Nobuki; Kubo, Momoji

    2015-03-01

    The chemical mechanical polishing (CMP) is promising for efficient polishing of the GaN substrate, and it is essential for manufacturing of GaN devices. However, the detailed CMP mechanisms are unclear, and then the design of efficient and precise CMP process is difficult. We performed polishing simulations of a GaN substrate by a SiO2 abrasive grain in a solution including OH radicals in order to reveal effects of OH radicals on the polishing process. The OH radicals in the solution are adsorbed on the GaN surface and occupy the hollow sites on the surface. Then, a surface-adsorbed O atom is generated by the chemical reaction between the surface-adsorbed OH species and a OH radical in the solution. In the friction interface between the GaN substrate and the abrasive grain, the surface-adsorbed O atom is mechanically pushed into the GaN substrate by the abrasive grain. This O atom intrusion induces the dissociation of Ga-N bonds of the GaN substrate. Moreover, volatile N2 molecules and soluble Ga(OH)3 molecules are generated due to the dissociation of Ga-N bonds. Then, we suggested that the GaN CMP process efficiently proceeds by the mechanically induced chemical reactions: a surface-adsorbed O atom is generated and pushed into the GaN bulk by the abrasive grain.

  20. Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks

    SciTech Connect

    Nelson Butuk

    2004-12-01

    This is an annual technical report for the work done over the last year (period ending 9/30/2004) on the project titled ''Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks''. The aim of the project is to develop an efficient chemistry model for combustion simulations. The reduced chemistry model will be developed mathematically without the need of having extensive knowledge of the chemistry involved. To aid in the development of the model, Neural Networks (NN) will be used via a new network topology know as Non-linear Principal Components Analysis (NPCA). We report on the development of a procedure to speed up the training of NPCA. The developed procedure is based on the non-parametric statistical technique of kernel smoothing. When this smoothing technique is implemented as a Neural Network, It is know as Generalized Regression Neural Network (GRNN). We present results of implementing GRNN on a test problem. In addition, we present results of an in house developed 2-D CFD code that will be used through out the project period.

  1. PUBLISHED ONLINE: 22 JULY 2012 | DOI: 10.1038/NPHYS2373 Controlling chemical reactions of a single particle

    E-print Network

    Loss, Daniel

    LETTERS PUBLISHED ONLINE: 22 JULY 2012 | DOI: 10.1038/NPHYS2373 Controlling chemical reactions, chemical reactions have been investigated by tuning thermodynamic parameters, such as temperature on chemical reaction rates and branching ratios, and monitor the kinematics of the reaction products

  2. SUPERPOSITION OF DIFFUSION AND CHEMICAL REACTION CONTROLLED LIMITING CURRENTS - APPLICATION TO CO2 CORROSION

    Microsoft Academic Search

    Srdjan Nesic; B. F. M. Pots; John Postlethwaite; Nicolas Thevenot

    It was observed experimentally that a chemical reaction limiting current can be affected by flow. In the present study a new more general expression than the one found in literature was derived for the superposition of the diffusion and chemical reaction controlled limiting currents . It was found that their interaction in the case of CO 2 corrosion is significant

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

    ERIC Educational Resources Information Center

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

    2008-01-01

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

  4. Non-meanfield deterministic limits in chemical reaction kinetics R. E. Lee DeVille

    E-print Network

    Van Den Eijnden, Eric

    Non-meanfield deterministic limits in chemical reaction kinetics R. E. Lee DeVille Courant is demonstrated for the kinetic Monte Carlo version of the Schnakenberg reaction where we identified a scaling, and it is at the very heart of the majority of macroscopic models of physical, chemical, and biological systems

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

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

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

  6. Communications Watching photoinduced chemical reactions in solution in real time by

    E-print Network

    Kling, Matthias

    Angewandte Chemie Communications Watching photoinduced chemical reactions in solution in real time.[5,6] Photo- chemical decomposition has almost exclusively been investigated in the nanosecond of the poor time resolution, a complete mechanistic understanding of the elementary reactions of peroxide

  7. Stochastic simulation of chemical reactions with spatial resolution and single molecule detail

    Microsoft Academic Search

    Steven S. Andrews; Dennis Bray

    2004-01-01

    Methods are presented for simulating chemical reaction networks with a spatial resolution that is accurate to nearly the size scale of individual molecules. Using an intuitive picture of chemical reaction systems, each molecule is treated as a point-like particle that diffuses freely in three-dimensional space. When a pair of reactive molecules collide, such as an enzyme and its substrate, a

  8. The effect of chemical reactions of the injected gas on the aerodynamic heating of blunt bodies

    Microsoft Academic Search

    K. Karashima; K. Nakahashi

    1979-01-01

    The effects on aerodynamic heating of chemical reactions of gaseous materials injected into a shock layer flow due to ablation are examined. Assuming ablation of Teflon and equilibrium chemical reactions, a hypersonic flow past a blunt nosed axisymmetric body with surface injection of C2F4 gas is solved numerically using the VSL equations, and a comparison is made with the results

  9. Impact of organic-mineral matter interactions on thermal reaction pathways for coal model compounds

    SciTech Connect

    Buchanan, A.C. III; Britt, P.F.; Struss, J.A. [Oak Ridge National Lab., TN (United States). Chemical and Analytical Sciences Div.

    1995-07-01

    Coal is a complex, heterogeneous solid that includes interdispersed mineral matter. However, knowledge of organic-mineral matter interactions is embryonic, and the impact of these interactions on coal pyrolysis and liquefaction is incomplete. Clay minerals, for example, are known to be effective catalysts for organic reactions. Furthermore, clays such as montmorillonite have been proposed to be key catalysts in the thermal alteration of lignin into vitrinite during the coalification process. Recent studies by Hatcher and coworkers on the evolution of coalified woods using microscopy and NMR have led them to propose selective, acid-catalyzed, solid state reaction chemistry to account for retained structural integrity in the wood. However, the chemical feasibility of such reactions in relevant solids is difficult to demonstrate. The authors have begun a model compound study to gain a better molecular level understanding of the effects in the solid state of organic-mineral matter interactions relevant to both coal formation and processing. To satisfy the need for model compounds that remain nonvolatile solids at temperatures ranging to 450 C, model compounds are employed that are chemically bound to the surface of a fumed silica (Si-O-C{sub aryl}linkage). The organic structures currently under investigation are phenethyl phenyl ether (C{sub 6}H{sub 5}CH{sub 2}CH{sub 2}OC{sub 6}H{sub 5}) derivatives, which serve as models for {beta}-alkyl aryl ether units that are present in lignin and lignitic coals. The solid-state chemistry of these materials at 200--450 C in the presence of interdispersed acid catalysts such as small particle size silica-aluminas and montmorillonite clay will be reported. Initial focus will be on defining the potential impact of these interactions on coal pyrolysis and liquefaction.

  10. On the dynamics of chemical reactions of negative ions

    E-print Network

    Mikosch, Jochen; Wester, Roland

    2010-01-01

    This review discusses the dynamics of negative ion reactions with neutral molecules in the gas phase. Most anion-molecule reactions proceed via a qualitatively different interaction potential than cationic or neutral reactions. It has been and still is the goal of many experiments to understand these reaction dynamics and the different reaction mechanisms they lead to. We will show how rate coefficients and cross sections for anion-molecule reactions are measured and interpreted to yield information on the underlying dynamics. We will also present more detailed approaches that study either the transient reaction complex or the energy- and angle-resolved scattering of negative ions with neutral molecules. With the help of these different techniques many aspects of anion-molecule reaction dynamics could be unravelled in the last years. However, we are still far from a complete understanding of the complex molecular interplay that is at work during a negative ion reaction.

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

    SciTech Connect

    Qiu Minghui; Che Li; Ren Zefeng; Dai Dongxu; Wang Xiuyan; Yang Xueming [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China)

    2005-08-15

    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{sub 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.

  12. Thermal and Chemical Freeze-out in Spectator Fragmentation

    E-print Network

    W. Trautmann; R. Bassini; M. Begemann-Blaich; A. Ferrero; S. Fritz; S. J. Gaff-Ejakov; C. Gross; G. Imme; I. Iori; U. Kleinevoss

    2007-12-17

    Isotope temperatures from double ratios of hydrogen, helium, lithium, beryllium, and carbon isotopic yields, and excited-state temperatures from yield ratios of particle-unstable resonances in 4He, 5Li, and 8Be, were determined for spectator fragmentation, following collisions of 197Au with targets ranging from C to Au at incident energies of 600 and 1000 MeV per nucleon. A deviation of the isotopic from the excited-state temperatures is observed which coincides with the transition from residue formation to multi-fragment production, suggesting a chemical freeze-out prior to thermal freeze-out in bulk disintegrations.

  13. Chemical composition and thermal property of cuttlefish ( Sepia pharaonis) muscle

    Microsoft Academic Search

    Amonrat Thanonkaew; Soottawat Benjakul; Wonnop Visessanguan

    2006-01-01

    The chemical composition and thermal property of cuttlefish (Sepia pharaonis) muscle were studied. The head and mantle contained 11.9–14.9% protein, 0.5% fat, 1.2–1.3% ash, and 0.6–1.8% collagen. Lipids from the head and mantle contained phospholipid as the major component (78.6–87.8% of total lipid), with 10.6–19.5% diglyceride. Polyunsaturated fatty acids constituted 50.3–54.9% of fatty acids with a high content of DHA

  14. Thermal and chemical freeze-out in spectator fragmentation

    NASA Astrophysics Data System (ADS)

    Trautmann, W.; Bassini, R.; Begemann-Blaich, M.; Ferrero, A.; Fritz, S.; Gaff-Ejakov, S. J.; Groß, C.; Immé, G.; Iori, I.; Kleinevoß, U.; Kunde, G. J.; Kunze, W. D.; Fèvre, A. Le; Lindenstruth, V.; ?ukasik, J.; Lynen, U.; Maddalena, V.; Mahi, M.; Möhlenkamp, T.; Moroni, A.; Müller, W. F. J.; Nociforo, C.; Ocker, B.; Odeh, T.; Orth, H.; Petruzzelli, F.; Pochodzalla, J.; Raciti, G.; Riccobene, G.; Romano, F. P.; Rubehn, Th.; Saija, A.; Sann, H.; Schnittker, M.; Schüttauf, A.; Schwarz, C.; Seidel, W.; Serfling, V.; Sfienti, C.; Trzci?ski, A.; Tucholski, A.; Verde, G.; Wörner, A.; Xi, Hongfei; Zwiegli?ski, B.

    2007-12-01

    Isotope temperatures from double ratios of hydrogen, helium, lithium, beryllium, and carbon isotopic yields, and excited-state temperatures from yield ratios of particle-unstable resonances in He4, Li5, and Be8, were determined for spectator fragmentation, following collisions of Au197 with targets ranging from C to Au at incident energies of 600 and 1000 MeV per nucleon. A deviation of the isotopic from the excited-state temperatures is observed which coincides with the transition from residue formation to multi-fragment production, suggesting a chemical freeze-out prior to thermal freeze-out in bulk disintegrations.

  15. Thermal, chemical and spectral equilibration in heavy-ion collisions

    E-print Network

    Gábor András Almási; György Wolf

    2014-07-08

    We have considered the equilibration in a relativistic heavy ion collision using our transport model. We applied periodic boundary conditions to close the system in a box. We found that the thermal equilibration takes place in the first 20-40 fm/c which time is comparable to the duration of a heavy ion collision. The chemical equilibration is a much slower process and the system does not equilibrate in a heavy ion collision. We have also shown that the mass spectra of broad resonances immediately follows their in-medium spectral functions.

  16. Thermal and chemical freeze-out in spectator fragmentation

    SciTech Connect

    Trautmann, W.; Begemann-Blaich, M.; Fritz, S.; Gross, C.; Kleinevoss, U.; Kunze, W. D.; Le Fevre, A.; Lynen, U.; Mahi, M.; Mueller, W. F. J.; Odeh, T.; Orth, H.; Rubehn, Th.; Sann, H.; Schnittker, M.; Schwarz, C.; Sfienti, C.; Woerner, A.; Xi Hongfei [Gesellschaft fuer Schwerionenforschung mbH, D-64291 Darmstadt (Germany); Bassini, R. [Istituto di Scienze Fisiche, Universita degli Studi di Milano and I. N. F. N., I-20133 Milano (Italy)] (and others)

    2007-12-15

    Isotope temperatures from double ratios of hydrogen, helium, lithium, beryllium, and carbon isotopic yields, and excited-state temperatures from yield ratios of particle-unstable resonances in {sup 4}He, {sup 5}Li, and {sup 8}Be, were determined for spectator fragmentation, following collisions of {sup 197}Au with targets ranging from C to Au at incident energies of 600 and 1000 MeV per nucleon. A deviation of the isotopic from the excited-state temperatures is observed which coincides with the transition from residue formation to multi-fragment production, suggesting a chemical freeze-out prior to thermal freeze-out in bulk disintegrations.

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

    E-print Network

    Tomza, Micha?; Moszynski, Robert; Krems, Roman V

    2013-01-01

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

  18. Thermal decomposition of sodium bicarbonate and its effect on the reaction of sodium bicarbonate and sulfur dioxide in a simulated flue gas

    SciTech Connect

    Keener, T.C.

    1982-01-01

    The effect of thermally decomposing sodium bicarbonate while simultaneously reacting with SO/sub 2/, was studied. The study was performed by quantitatively determining the rate of thermal decomposition as a function of particle size in an SO/sub 2/ free gas stream. The rate of reaction of sodium carbonate (product of the thermal decomposition) with SO/sub 2/ was then studied, and the data applied to a pore-plugging model which accounts for the loss in reactivity with increased reaction time. The reaction of sodium bicarbonate with SO/sub 2/ was then studied and the results compared to that for sodium carbonate. From the analysis of the data, the activation energy for the thermal decomposition reaction, the SO/sub 2/ sodium carbonate and SO/sub 2/ sodium bicarbonate reaction were derived. The thermal decomposition reaction of sodium biocarbonate was found to be similar to that of calcium carbonate below the point where heat transfer is rate limiting. The degree of conversion of sodium bicarbonate was found to be 12-17 times greater (depending on particle size) than that of sodium carbonate in the temperature range 250/sup 0/-350/sup 0/F (120/sup 0/-177/sup 0/C). This greater conversion was qualitatively explained by hypothesizing the formation of an activated species during thermal decomposition which would be more chemically reactive.

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

    NASA Technical Reports Server (NTRS)

    1996-01-01

    The product of incomplete reaction of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants, or fuel-oxidizer reaction product (FORP), has been hypothesized as a contributory cause of an anomaly which occurred in the chamber pressure (PC) transducer tube on the Reaction Control Subsystem (RCS) aft thruster 467 on flight STS-51. A small hole was found in the titanium-alloy PC tube at the first bend below the pressure transducer. It was surmised that the hole may have been caused by heat and pressure resulting from ignition of FORP. The NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) was requested to define the chemical characteristics of FORP, characterize its reactivity, and simulate the events in a controlled environment which may have lead to the Pc-tube failure. Samples of FORP were obtained from the gas-phase reaction of MMH with NTO under laboratory conditions, the pulsed firings of RCS thrusters with modified PC tubes using varied oxidizer or fuel lead times, and the nominal RCS thruster firings at WSTF and Kaiser-Marquardt. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), ion chromatography (IC), inductively coupled plasma (ICP) spectrometry, thermogravimetric analysis (TGA) coupled to FTIR (TGA/FTIR), and mechanical impact testing were used to qualitatively and quantitatively characterize the chemical, thermal, and ignition properties of FORP. These studies showed that the composition of FORP is variable but falls within a limited range of compositions that depends on the fuel loxidizer ratio at the time of formation, composition of the post-formation atmosphere (reducing or oxidizing), and reaction or postreaction temperature. A typical composition contains methylhydrazinium nitrate (MMHN), ammonium nitrate (AN), methylammonium nitrate (MAN), and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. The thermal decomposition reactions of 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 MMH and liquid NTO in a confined space. The test hardware was constructed with pressure- and temperature-measurement devices to determine if the expected fuel oxidizer reaction would result in increased energy release when FORP, FORP constituents, or propellant-system corrosion products were present. These tests demonstrated that FORP, MMHN, AN, or Inconel corrosion products can induce a mixture of MMH and NTO to produce component-damaging energies. The simulation-test program was not extensive enough to provide statistical probabilities for these events but did show that such events can occur. Damaging events required FORP or metal salts to be present at the initial mixing of MMH and NTO. Based on the results of these studies, it is suggested that removal or mitigation of a buildup of these materials may decrease the incidence of these high-energy, potentially damaging events.

  20. Diffusion controlled instantaneous chemical reaction in a thin tube containing fine reactant particles

    Microsoft Academic Search

    Anurag Mehra; P. T. Rao; A. K. Suresh

    1997-01-01

    The instantaneous, chemical reaction between a sparingly soluble gaseous species and a liquid-phase reactant is known to occur at a moving reaction plane to which both the reacting species diffuse. This study investigates the motion of such a reaction front, in thin tubes, where the liquid-phase reactant is present as a slurry of sparingly soluble, fine particles. The movement of

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

    E-print Network

    Boyer, Edmond

    453 A comparison of reversible chemical reactions for solar thermochemical power generation O. M storage of the reaction products. A number of reactions have been proposed for solar thermochemical power to be a good choice for first generation solar thermochemical power generation. Revue Phys. Appl. 15 (1980) 453

  2. A coupled chemical burster: The chlorine dioxide-iodide reaction in two flow reactors

    E-print Network

    Epstein, Irving R.

    A coupled chemical burster: The chlorine dioxide-iodide reaction in two flow reactors Miles Dolnika-iodide reaction has been studied in a system consisting of two continuous flow stirred tank reactors (CSTRs triggered, exponentially decreasing stimulation, and alternating mass exchange. The reaction, which exhibits

  3. CHEMICAL REACTION OF SILICON CLUSTER IONS WITH ETHYLENE BY USING FT-ICR MASS SPECTROMETER

    E-print Network

    Maruyama, Shigeo

    CHEMICAL REACTION OF SILICON CLUSTER IONS WITH ETHYLENE BY USING FT-ICR MASS SPECTROMETER Masamichi transform ion cyclotron resonance (FT-ICR) mass spectrometer and monitored during chemisorption reaction with ethylene (C2H4). Through measurements of "time-dependency" of this reaction process, drastic change

  4. State to State Chemistry This research is concerned with the description of chemical reactions, photoprocesses and

    E-print Network

    State to State Chemistry This research is concerned with the description of chemical reactions are interested in are: 1.Reactions of oxygen atoms with polyatomic molecules (hydrocarbons, fluorinated hydrocarbons) We have performed extensive studies of the reaction of atomic oxygen (O(3 P)) with small

  5. STABILITY OF CHEMICAL REACTIONS IN A CSTR WITH DELAYED RECYCLE STREAM

    E-print Network

    Lehman, Brad

    STABILITY OF CHEMICAL REACTIONS IN A CSTR WITH DELAYED RECYCLE STREAM Brad Lehman' Departmentof, and hence the cost of reaction, its use is widespread in industry. For example, recycling is almost always and alcohol of cyclohexene), among many other reactions. Adifficultywithmuchof

  6. Effect of chaotic interfacial stretching on bimolecular chemical reaction in helical-coil reactors

    Microsoft Academic Search

    David R. Sawyers; Mihir Sen; Hsueh-Chia Chang

    1996-01-01

    We investigate the yield of bimolecular chemical reaction between two initially separated reactants in a tubular reactor of different coiling geometries. Laminar and steady flow with high mass Peclet number, Pe, are assumed. Asymptotic approximations for slow reactions are obtained by studying the reaction at a thin interfacial boundary layer. For a straight tube it is found that the area-averaged

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

    NASA Astrophysics Data System (ADS)

    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.

  8. Kinetic models with chemical reactions and nonequilibrium entropy in open systems

    NASA Astrophysics Data System (ADS)

    Aristov, Vladimir; Frolova, Anna; Zabelok, Sergey

    2014-12-01

    Nonuniform relaxation problems are applied to simulate complex non-equilibrium processes with chemical reactions in open systems. The present paper is a continuation of our studies at a new level, in particular, 2D flows are considered. Besides the slow chemical reactions, the so-called fast reactions are studied. A special attention is paid to studying the behavior of non-equilibrium entropy and entropy flux in such complex open systems.

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

    In this study, we investigated how students used a drawing tool to visualize their ideas of chemical reaction processes. We interviewed 30 students using thinking-aloud and retrospective methods and provided them with a drawing tool. We identified four types of connections the students made as they used the tool: drawing on existing knowledge, incorporating dynamic aspects of chemical processes, linking a visualization to the associated chemical phenomenon, and connecting between the visualization and chemistry concepts. We also compared students who were able to create dynamic visualizations with those who only created static visualizations. The results indicated a relationship between students constructing a dynamic view of chemical reaction processes and their understanding of chemical reactions. This study provides insights into the use of visualizations to support instruction and assessment to facilitate students' integrated understanding of chemical reactions.

  10. TEOS-based SiO{sub 2} chemical vapor deposition: Reaction kinetics and related surface chemistry

    SciTech Connect

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

    1995-11-01

    We have developed a comprehensive understanding of thermal TEOS (tetracthylorthosificate, Si(OCH{sub 2}CH{sub 3}){sub 4}) surface chemistry at CVD (chemical vapor deposition) temperatures and pressures. This was accomplished by examining how TEOS reaction rate are influenced by factors critical to the heterogeneous reaction. This includes determining the TEOS pressure dependence, testing if reaction by-products inhibit TEOS decomposition, identifying reaction sites on the surface, and establishing the reaction sites coverage dependencies. We evaluated the pressure dependencies and by-product inhibition with GCMS. The experiments in a cold-wall research reactor revealed that the TEOS surface reaction at 1000K (1) was first-order with respect to TEOS pressure (0.10 to 1.50Torr) and (2) was not inhibited by surface reaction by-products (ethylene, ethanol, and water). Reactivities of surface sites and their coverage dependencies were compared with FTIR. Our experiments demonstrated that two-membered siloxane ((Si-O){sub 2}) rings on the SiO{sub 2} surface were consumed almost instantaneously when exposed to TEOS. Our FTIR experiments also revealed that TEOS decomposition was zero-order with respect to coverages of hydroxyl groups and (by indirect evidence) three-membered siloxane ((Si-O){sub 3}) rings. This type of site-independent reactivity is consistent with TEOS reacting with hydroxyl groups and (Si-O){sub 3} rings via a common rate-determining step at 1000K. With respect to deposition uniformity, our results predict that deposition rates will be insensitive to the relative coverages of (Si-O){sub 3} rings and hydroxyls on SiO{sub 2} as well as the re-adsorbed by-products of the surface reaction. Therefore, it is likely that nonuniform SiO{sub 2} depositions from TEOS reactions are due to depletion of TEOS in the gas-phase and/or thermal gradients.

  11. Chemical Model Systems for Cellular Nitros(yl)ation Reactions

    PubMed Central

    Daiber, Andreas; Schildknecht, Stefan; Müller, Johanna; Bachschmid, Markus M.; Ullrich, Volker

    2014-01-01

    S-nitros(yl)ation belongs to the redox-based posttranslational modifications of proteins but the underlying chemistry is controversial. In contrast to current concepts involving the autoxidation of nitric oxide (•NO, nitrogen monoxide), we and others have proposed the formation of peroxynitrite (oxoperoxonitrate(1-)) as an essential intermediate. This requires low cellular fluxes of •NO and superoxide (•O2?), for which model systems have been introduced. We here propose two new systems for nitros(yl)ation that avoid the shortcomings of previous models. Based on the thermal decomposition of 3-morpholinosydnonimine, equal fluxes of •NO and •O2? were generated and modulated by the addition of •NO donors or Cu,Zn-superoxide dismutase. As reactants for S-nitros(yl)ation, NADP+-dependent isocitrate dehydrogenase and glutathione were employed, for which optimal S-nitros(yl)ation was observed at nanomolar fluxes of •NO and •O2? at a ratio of about 3:1. The previously used reactants phenol and diaminonaphthalene, (C- and N-nitrosation) demonstrated potential participation of multiple pathways for nitros(yl)ation. According to our data, neither peroxynitrite nor autoxidation of •NO was as efficient as the 3•NO/1•O2? system in mediating S-nitros(yl)ation. In theory this could lead to an elusive nitrosonium (nitrosyl cation)-like species in the first step and to N2O3 in the subsequent reaction. Which of these two species or whether both together will participate in biological S-nitros(yl)ation remains to be elucidated. Finally, we developed several hypothetical scenarios to which the described U flux model could apply, providing conditions that allow either direct electrophilic substitution at a thiolate or S-nitros(yl)ation via transnitrosation from S-nitrosoglutathione. PMID:19477267

  12. Regenerated fibre Bragg gratings used to map internal reaction temperatures of a modified chemical vapour deposition (MCVD) optical fibre preform lathe

    NASA Astrophysics Data System (ADS)

    Åslund, Mattias L.; Canagasabey, Albert; Liu, Yang; Cook, Kevin; Canning, John; Peng, Gang-Ding

    2011-05-01

    The temperature profile of the reaction zone inside the substrate tube of a modified chemical vapour deposition (MCVD) optical fibre perform lathe has been characterised using thermal chirp compensated ultra-high temperature stable regenerated optical fibre Bragg gratings (FBGs). Results indicate significant differences in measured internal temperatures than those predicted theoretically or measured externally.

  13. Examination of lignocellulosic fibers for chemical, thermal, and separations properties: Addressing thermo-chemical stability issues

    NASA Astrophysics Data System (ADS)

    Johnson, Carter David

    Natural fiber-plastic composites incorporate thermoplastic resins with fibrous plant-based materials, sometimes referred to as biomass. Pine wood mill waste has been the traditional source of natural fibrous feedstock. In anticipation of a waste wood shortage other fibrous biomass materials are being investigated as potential supplements or replacements. Perennial grasses, agricultural wastes, and woody biomass are among the potential source materials. As these feedstocks share the basic chemical building blocks; cellulose, hemicellulose, and lignin, they are collectively called lignocellulosics. Initial investigation of a number of lignocellulosic materials, applied to fiber-plastic composite processing and material testing, resulted in varied results, particularly response to processing conditions. Less thermally stable lignocellulosic filler materials were physically changed in observable ways: darkened color and odor. The effect of biomass materials' chemical composition on thermal stability was investigated an experiment involving determination of the chemical composition of seven lignocellulosics: corn hull, corn stover, fescue, pine, soy hull, soy stover, and switchgrass. These materials were also evaluated for thermal stability by thermogravimetric analysis. The results of these determinations indicated that both chemical composition and pretreatment of lignocellulosic materials can have an effect on their thermal stability. A second study was performed to investigate what effect different pretreatment systems have on hybrid poplar, pine, and switchgrass. These materials were treated with hot water, ethanol, and a 2:1 benzene/ethanol mixture for extraction times of: 1, 3, 6, 12, and 24 hours. This factorial experiment demonstrated that both extraction time and medium have an effect on the weight percent of extractives removed from all three material types. The extracted materials generated in the above study were then subjected to an evaluation of thermal stability by thermogravimetric analysis in a subsequent experiment. Overlay plots, combining individual weight loss curves, demonstrate that the experimental factors, solvent system and extraction time, produce effects on the thermal stability of the treated biomass samples. These data also indicated that the individual lignocellulosic materials had unique responses to the type of solvent used for pretreatment. Increasing extraction time had either no correlation with or a positive effect on thermal stability of the biomass samples.

  14. Computational Analyses of Complex Flows with Chemical Reactions

    NASA Astrophysics Data System (ADS)

    Bae, Kang-Sik

    The heat and mass transfer phenomena in micro-scale for the mass transfer phenomena on drug in cylindrical matrix system, the simulation of oxygen/drug diffusion in a three dimensional capillary network, and a reduced chemical kinetic modeling of gas turbine combustion for Jet propellant-10 have been studied numerically. For the numerical analysis of the mass transfer phenomena on drug in cylindrical matrix system, the governing equations are derived from the cylindrical matrix systems, Krogh cylinder model, which modeling system is comprised of a capillary to a surrounding cylinder tissue along with the arterial distance to veins. ADI (Alternative Direction Implicit) scheme and Thomas algorithm are applied to solve the nonlinear partial differential equations (PDEs). This study shows that the important factors which have an effect on the drug penetration depth to the tissue are the mass diffusivity and the consumption of relevant species during the time allowed for diffusion to the brain tissue. Also, a computational fluid dynamics (CFD) model has been developed to simulate the blood flow and oxygen/drug diffusion in a three dimensional capillary network, which are satisfied in the physiological range of a typical capillary. A three dimensional geometry has been constructed to replicate the one studied by Secomb et al. (2000), and the computational framework features a non-Newtonian viscosity model for blood, the oxygen transport model including in oxygen-hemoglobin dissociation and wall flux due to tissue absorption, as well as an ability to study the diffusion of drugs and other materials in the capillary streams. Finally, a chemical kinetic mechanism of JP-10 has been compiled and validated for a wide range of combustion regimes, covering pressures of 1atm to 40atm with temperature ranges of 1,200 K--1,700 K, which is being studied as a possible Jet propellant for the Pulse Detonation Engine (PDE) and other high-speed flight applications such as hypersonic missiles. The comprehensive skeletal mechanism consists of 58 species and 315 reactions including in CPD, Benzene formation process by the theory for polycyclic aromatic hydrocarbons (PAH) and soot formation process on the constant volume combustor, premixed flame characteristics.

  15. Thermal and chemical degradation of inorganic membrane materials. Topical report

    SciTech Connect

    Krishnan, G.N.; Sanjurjo, A.; Wood, B.J.; Lau, K.H.

    1994-04-01

    This report describes the results of a literature review to evaluate the long-term thermal and chemical degradation of inorganic membranes that are being developed to separate gaseous products produced by the gasification or combustion of coal in fixed-, fluidized-, and entrained-bed gasifiers, direct coal-fired turbines, and pressurized-fluidized-bed combustors. Several impurities, such as H{sub 2}S, NH{sub 3}, SO{sub 2}, NO{sub x}, and trace metal compounds are generated during coal conversion, and they must be removed from the coal gas or the combustor flue gas to meet environmental standards. The use of membranes to separate these noxious gases is an attractive alternative to their removal by sorbents such as zinc titanate or calcium oxide. Inorganic membranes that have a high separation efficiency and exhibit both thermal and chemical stability would improve the economics of power generation from coal. The U.S. Department of Energy is supporting investigations to develop inorganic membranes for separating hydrogen from coal gas streams and noxious impurities from hot coal- and flue-gas streams. Membrane materials that have been investigated in the past include glass (silica), alumina, zirconia, carbon, and metals (Pd and Pt).

  16. Selective Growth of Straight Carbon Nanotubes by Low-Pressure Thermal Chemical Vapor Deposition

    E-print Network

    Hasegawa, Shuji

    Selective Growth of Straight Carbon Nanotubes by Low-Pressure Thermal Chemical Vapor Deposition) were grown by low-pressure thermal chemical vapor deposition using pure ethylene. It was found chemical vapor deposition, ethylene, catalyst nano- particles 1. Introduction Recently, surface

  17. On the prediction of thermal stability of nitroaromatic compounds using quantum chemical calculations

    E-print Network

    Paris-Sud XI, Université de

    ranks at top of physicochemical hazards that may be feared from the use of a given chemical [11 On the prediction of thermal stability of nitroaromatic compounds using quantum chemical a new approach to predict thermal stability of nitroaromatic compounds based on quantum chemical

  18. Multistep One-Pot Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

    E-print Network

    Zhao, Huimin

    Multistep One-Pot Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis Carl A. Denard, John F. Hartwig,*, and Huimin Zhao*,,§ Department of Chemical and Biomolecular of chemical catalysts. Over the last 20 years, research in this area has provided us with proof of concept

  19. Chemical conversion of phenylethylamine into phenylacetaldehyde by carbonyl-amine reactions in model systems.

    PubMed

    Zamora, Rosario; Delgado, Rosa M; Hidalgo, Francisco J

    2012-05-30

    The chemical conversion of phenylethylamine into phenylacetaldehyde in the presence of lipid oxidation products (LOPs) was studied to investigate the possibility that biogenic amines can be converted into Strecker aldehydes upon processing. Model systems of phenylethylamine and methyl 13-hydroperoxyoctadeca-9,11-dienoate (HP), 2,4-decadienal (DD), 4,5-epoxy-2-heptenal (EH), 4,5-epoxy-2-decenal (ED), 4-oxo-2-hexenal (OH), 4-oxo-2-nonenal (ON), or 4-hydroxy-2-nonenal (HN) were heated for 1 h at 180 °C and pH 3. Although HN and EH did not produce more phenylacetaldehyde than when phenylethylamine was heated alone, all other lipid oxidation products assayed increased the amount of phenylacetaldehyde produced by 300-900%, with ON being the most reactive compound for this reaction. The reaction was mainly produced at acidic pH values (<6) and was dependent upon the concentration of the LOPs involved, and the phenylacetaldehyde produced increased linearly as a function of the time and temperature. The E(a) values for the reactions between phenylethylamine and DD and ON were 54.8 and 53.8 kJ/mol, respectively. The reaction is proposed to take place by the formation of an imine between the phenylethylamine and the LOPs, which is later converted into another imine by an electronic rearrangement. This new imine is the origin of phenylacetaldehyde by hydrolysis. These results show a new pathway for Strecker aldehyde formation. This route provides a potential way to reduce biogenic amine content in foods when they can be thermally processed before consumption. PMID:22578256

  20. Real-time quantitative investigation of photochemical reaction using thermal lens measurements: Theory and experiment

    SciTech Connect

    Pedreira, P. R. B.; Hirsch, L. R.; Pereira, J. R. D.; Medina, A. N.; Bento, A. C.; Baesso, M. L.; Rollemberg, Maria C.; Franko, Mladen; Shen Jun [Departamento de Fisica, Universidade Estadual de Maringa, Avenida Colombo 5790, 87020-900, Maringa, Parana (Brazil); Departamento de Quimica, Universidade Estadual de Maringa, 87020-900, Maringa, Parana (Brazil); Laboratory for Environmental Research, University of Nova Gorica, Vipavska 13, SI-5000 Nova Gorica (Slovenia); National Research Council of Canada, Institute for Fuel Cell Innovation, 3250 East Mall, Vancouver, British Columbia V6T 1W5 (Canada)

    2006-08-15

    In this work the time-resolved mode-mismatched thermal lens method is applied to investigate Cr(VI) species in water. An abnormal behavior of the thermal lens transient induced by a photochemical reaction was observed during optical excitation. With the purpose of better understanding this phenomenon, the existing theoretical model of thermal lens effect was generalized in order to take the time dependence of the absorbance of the sample into account due to the changes in concentration resulting from photochemical reaction and diffusion of absorbing species. Consequently, the photochemical reaction rate can be quantitatively evaluated by this technique with the generalized model. The adopted procedure demonstrates the usefulness of the time-resolved thermal lens method for the study of photochemical reactions under the presence of absorbing species diffusion with the advantage of monitoring the processes in a quantitative way and with a temporal resolution of a few milliseconds.

  1. Automatic modelling of reaction systems using genetic algorithms and its application to chemical vapour deposition processes: advanced utilizations of simulators for chemical systems

    Microsoft Academic Search

    Takahiro Takahashi; Kimito Funatsu; Yoshinori Ema

    2005-01-01

    The identification of appropriate reaction models is very helpful for developing chemical vapour deposition (CVD) processes. We introduced novel algorithms to analyse experimental data from CVD processes and identify reaction models automatically using genetic algorithms (GAs). The reaction models, which consist of various deposition species and gas-phase and surface reactions, were determined both quantitatively and qualitatively, based on chemical kinetics.

  2. L. Cao, H. Sihler, U. Platt and E. Gutheil: Chemical mechanisms for ozone depletion and halogen release: Supplement 1 1 Chemical reaction mechanisms

    E-print Network

    Meskhidze, Nicholas

    release: Supplement 1 1 Chemical reaction mechanisms: Mechanism for bromine containing species: Reaction kL. Cao, H. Sihler, U. Platt and E. Gutheil: Chemical mechanisms for ozone depletion and halogen [(molec. cm-3 )1-n s-1 ] Reaction order n Reference Reaction No. O3 +h O(1 D)+O2 4.70 10-7 1 Lehrer et al

  3. Thermally Stable Nanocatalyst for High Temperature Reactions: Pt-Mesoporous Silica Core-Shell Nanoparticles

    SciTech Connect

    Joo, Sang Hoon; Park, J.Y.; Tsung, C.-K.; Yamada, Y.; Yang, P.; Somorjai, G.A.

    2008-10-25

    Recent advances in colloidal synthesis enabled the precise control of size, shape and composition of catalytic metal nanoparticles, allowing their use as model catalysts for systematic investigations of the atomic-scale properties affecting catalytic activity and selectivity. The organic capping agents stabilizing colloidal nanoparticles, however, often limit their application in high-temperature catalytic reactions. Here we report the design of a high-temperature stable model catalytic system that consists of Pt metal core coated with a mesoporous silica shell (Pt{at}mSiO{sub 2}). While inorganic silica shells encaged the Pt cores up to 750 C in air, the mesopores directly accessible to Pt cores made the Pt{at}mSiO{sub 2} nanoparticles as catalytically active as bare Pt metal for ethylene hydrogenation and CO oxidation. The high thermal stability of Pt{at}mSiO{sub 2} nanoparticles permitted high-temperature CO oxidation studies, including ignition behavior, which was not possible for bare Pt nanoparticles because of their deformation or aggregation. The results suggest that the Pt{at}mSiO{sub 2} nanoparticles are excellent nanocatalytic systems for high-temperature catalytic reactions or surface chemical processes, and the design concept employed in the Pt{at}mSiO{sub 2} core-shell catalyst can be extended to other metal-metal oxide compositions.

  4. Heat-Of-Reaction Chemical Heat Pumps--Possible Configurations 

    E-print Network

    Kirol, L. D.

    1986-01-01

    Chemical heat pumps utilize working fluids which undergo reversible chemical changes. Mechanically driven reactive heat pump cycles or, alternatively, heat driven heat pumps in which either heat engine or heat pump working fluid is reactive...

  5. Computational thermal, chemical, fluid, and solid mechanics for geosystems management.

    SciTech Connect

    Davison, Scott; Alger, Nicholas; Turner, Daniel Zack; Subia, Samuel Ramirez; Carnes, Brian; Martinez, Mario J.; Notz, Patrick K.; Klise, Katherine A.; Stone, Charles Michael; Field, Richard V., Jr.; Newell, Pania; Jove-Colon, Carlos F.; Red-Horse, John Robert; Bishop, Joseph E.; Dewers, Thomas A.; Hopkins, Polly L.; Mesh, Mikhail; Bean, James E.; Moffat, Harry K.; Yoon, Hongkyu

    2011-09-01

    This document summarizes research performed under the SNL LDRD entitled - Computational Mechanics for Geosystems Management to Support the Energy and Natural Resources Mission. The main accomplishment was development of a foundational SNL capability for computational thermal, chemical, fluid, and solid mechanics analysis of geosystems. The code was developed within the SNL Sierra software system. This report summarizes the capabilities of the simulation code and the supporting research and development conducted under this LDRD. The main goal of this project was the development of a foundational capability for coupled thermal, hydrological, mechanical, chemical (THMC) simulation of heterogeneous geosystems utilizing massively parallel processing. To solve these complex issues, this project integrated research in numerical mathematics and algorithms for chemically reactive multiphase systems with computer science research in adaptive coupled solution control and framework architecture. This report summarizes and demonstrates the capabilities that were developed together with the supporting research underlying the models. Key accomplishments are: (1) General capability for modeling nonisothermal, multiphase, multicomponent flow in heterogeneous porous geologic materials; (2) General capability to model multiphase reactive transport of species in heterogeneous porous media; (3) Constitutive models for describing real, general geomaterials under multiphase conditions utilizing laboratory data; (4) General capability to couple nonisothermal reactive flow with geomechanics (THMC); (5) Phase behavior thermodynamics for the CO2-H2O-NaCl system. General implementation enables modeling of other fluid mixtures. Adaptive look-up tables enable thermodynamic capability to other simulators; (6) Capability for statistical modeling of heterogeneity in geologic materials; and (7) Simulator utilizes unstructured grids on parallel processing computers.

  6. A lattice gas automata model for heterogeneous chemical reactions at mineral surfaces and in pore networks

    SciTech Connect

    Wells, J.T. (Washington Univ., Seattle, WA (USA). Dept. of Geological Sciences); Janecky, D.R.; Travis, B.J. (Los Alamos National Lab., NM (USA))

    1990-01-15

    A lattice gas automata (LGA) model is described, which couples solute transport with chemical reactions at mineral surfaces and in pore networks. Chemical reactions and transport are integrated into a FHP-I LGA code as a module so that the approach is readily transportable to other codes. Diffusion in a box calculations are compared to finite element Fickian diffusion results and provide an approach to quantifying space-time ratios of the models. Chemical reactions at solid surfaces, including precipitation/dissolution, sorption, and catalytic reaction, can be examined with the model because solute diffusion and mineral surface processes are all treated explicitly. The simplicity and flexibility of the LGA approach provides the ability to study the interrelationship between fluid flow and chemical reactions in porous materials, at a level of complexity that has not previously been computationally possible. 20 refs., 8 figs.

  7. SUBSTITUTION REACTIONS FOR THE DETOXIFICATION OF HAZARDOUS CHEMICALS

    EPA Science Inventory

    Chemical Treatment is one of several treatment techniques used for the remediation of toxic and hazardous chemicals. Chemical treatment in this report is defined as substitution of halogens by hydrogens for the conversion of halogenated organic toxicant into its native hydrocarb...

  8. Heat-of-reaction chemical heat pumps: Possible configurations

    Microsoft Academic Search

    L. D. Kirol

    1986-01-01

    Chemical heat pumps utilize working fluids which undergo reversible chemical changes. Mechanically driven reactive heat pump cycles or, alternatively, heat driven heat pumps in which either heat engine or heat pump working fluid is reactive, are considered. As such, chemical heat pumps can be classified by: (1) drive (electric drive, waste heat drive, or prime energy drive), (2) operating mode

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

    PubMed

    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. PMID:24446263

  10. Accelerating chemical reactions: Exploring reactive free-energy surfaces using accelerated ab initio molecular dynamics

    PubMed Central

    Pierce, Levi C. T.; Markwick, Phineus R. L.; McCammon, J. Andrew; Doltsinis, Nikos L.

    2011-01-01

    A biased potential molecular dynamics simulation approach, accelerated molecular dynamics (AMD), has been implemented in the framework of ab initio molecular dynamics for the study of chemical reactions. Using two examples, the double proton transfer reaction in formic acid dimer and the hypothetical adiabatic ring opening and subsequent rearrangement reactions in methylenecyclopropane, it is demonstrated that ab initio AMD can be readily employed to efficiently explore the reactive potential energy surface, allowing the prediction of chemical reactions and the identification of metastable states. An adaptive variant of the AMD method is developed, which additionally affords an accurate representation of both the free-energy surface and the mechanism associated with the chemical reaction of interest and can also provide an estimate of the reaction rate. PMID:21548673

  11. Reactions of hydrazines with chemicals found in environment. Technical report

    SciTech Connect

    Judeikis, H.S.; Damschen, D.E.

    1992-01-24

    Reactions of hydrazine, monomethylhydrazine and unsymmetrical dimethylhydrazine with selected species of interest that are found in the environment have been investigated. Included are aqueous phase reactions that can occur in atmospheric aerosols, groundwater, or soils in contact with groundwater, as well as selected gas phase reactions. Reactants include oxygen and hydrogen peroxide (both reactants in the presence and absence of catalysts), ozone, nitrous acid, sulfur dioxide, and acetone (as a model for environmental ketones and aldehydes). Rate constants for the reactions have been determined, or upper limits set. In several instances, reaction products have been identified. By far, the fastest reactions measured were those involving the hydrazines and ozone with (second-order) rate constants up to 2.4 x 107 liter/mole-sec.

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

    NASA Technical Reports Server (NTRS)

    Leonard, Andy D.; Hill, James C.

    1992-01-01

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

  13. FT-ICR Study of Chemical Reaction of Precursor Clusters of SWNT Masamichi Kohno, Shuhei Inoue and Shigeo Maruyama

    E-print Network

    Maruyama, Shigeo

    FT-ICR Study of Chemical Reaction of Precursor Clusters of SWNT Masamichi Kohno, Shuhei Inoue and Shigeo Maruyama Chemical reaction of carbon clusters and metal-carbon binary clusters (MCn , M = Ni or Co

  14. Reduction of detonating liquid nitromethane's chemical reaction-zone length by chemical sensitization

    NASA Astrophysics Data System (ADS)

    Engelke, Ray; Sheffield, Stephen A.; Stacy, Howard L.; Quintana, John P.

    2005-09-01

    We examine the effect of the addition of small amounts of the organic base diethylenetriamine [NH2(CH2CH2)NH(CH2CH2)NH2] on the chemical reaction-zone length (CRZ) of detonating liquid nitromethane (CH3NO2). This is done by making accurate measurements of the detonating materials' diameter-effect curves (i.e., detonation speed versus lateral charge size) as a function of the amount of chemical sensitizer added. Detonation speed experiments were performed with additions of the organic base in amounts between 0.00 and 0.25wt%. Reductions in the CRZ of as much as 25% were produced by base addition. Most of the reduction in length is produced by very small amounts of base addition—i.e., ca. 0.05wt% of base or less (i.e., 1 molecule of the base per 3300 nitromethane molecules or less). Measured detonation speeds are given for five compositions of nitromethane and base as a function of charge internal diameter. Absolute CRZs are estimated using a value of liquid nitromethane's CRZ obtained by other means. Earlier work has determined a relationship between the failure diameter of sensitized nitromethane compositions and the amount of base addition. Here we have found a relationship between relative CRZ and the amount of base addition. By eliminating the base parameterization, we give a phenomenological relationship between the failure diameter of such materials and their steady one-dimensional CRZs.

  15. Rapid microfluidic thermal cycler for polymerase chain reaction nucleic acid amplification

    Microsoft Academic Search

    Shadi Mahjoob; Kambiz Vafai; N. Reginald Beer

    2008-01-01

    Polymerase chain reaction (PCR) is widely used in biochemical analysis to amplify DNA and RNA in vitro. The PCR process is highly temperature sensitive, and thermal management has an important role in PCR operation in reaching the required temperature set points at each step of the process. The goal of this research is to achieve a thermal technique to rapidly

  16. Kinetics of thermal regeneration reaction of activated carbons used in waste water treatment

    Microsoft Academic Search

    Kenji Hashimoto; Kouichi Miura; Tsuneo Watanabe

    1982-01-01

    The kinetics of the thermal regeneration of activated carbons used in the waste water treatment was analyzed on the basis of a model that the regeneration reaction consists of a set of many first-order reactions each of which has different activation energy and frequency factor. The frequency factors were correlated approximately by a function of the activation energy. The difference

  17. Helium production in copper by a thermal three-stage reaction

    Microsoft Academic Search

    D. W. Kneff; L. R. Greenwood; B. M. Oliver; R. P. Skowronski; E. L. Callis

    1986-01-01

    A three-stage reaction process has been identified in copper that produces significant He concentrations at high thermal neutron fluences. Cross sections have been determined for four reactions that allow us to calculate the total He production in copper for high-fluence irradiations in HFIR.

  18. Product-state control of bi-alkali-metal chemical reactions

    SciTech Connect

    Meyer, Edmund R.; Bohn, John L. [JILA, NIST, and University of Colorado, Department of Physics, Boulder, Colorado 80309-0440 (United States)

    2010-10-15

    We consider ultracold, chemically reactive scattering collisions of the diatomic molecules KRb. When two such molecules collide in an ultracold gas, we find that they are energetically forbidden from reacting to form the trimer species K{sub 2}Rb or Rb{sub 2}K, and hence can only react via the bond-swapping reaction 2KRb{yields}K{sub 2}+Rb{sub 2}. Moreover, the tiny energy released in this reaction can in principle be set to zero by applying electric or microwave fields, implying a means of controlling the available reaction channels in a chemical reaction.

  19. Thermal Decomposition of NCN: Shock-Tube Study, Quantum Chemical Calculations, and Master-Equation Modeling.

    PubMed

    Busch, Anna; González-García, Núria; Lendvay, György; Olzmann, Matthias

    2015-07-16

    The thermal decomposition of cyanonitrene, NCN, was studied behind reflected shock waves in the temperature range 1790-2960 K at pressures near 1 and 4 bar. Highly diluted mixtures of NCN3 in argon were shock-heated to produce NCN, and concentration-time profiles of C atoms as reaction product were monitored with atomic resonance absorption spectroscopy at 156.1 nm. Calibration was performed with methane pyrolysis experiments. Rate coefficients for the reaction (3)NCN + M ? (3)C + N2 + M (R1) were determined from the initial slopes of the C atom concentration-time profiles. Reaction R1 was found to be in the low-pressure regime at the conditions of the experiments. The temperature dependence of the bimolecular rate coefficient can be expressed with the following Arrhenius equation: k1(bim) = (4.2 ± 2.1) × 10(14) exp[-242.3 kJ mol(-1)/(RT)] cm(3) mol(-1) s(-1). The rate coefficients were analyzed by using a master equation with specific rate coefficients from RRKM theory. The necessary molecular data and energies were calculated with quantum chemical methods up to the CCSD(T)/CBS//CCSD/cc-pVTZ level of theory. From the topography of the potential energy surface, it follows that reaction R1 proceeds via isomerization of NCN to CNN and subsequent C-N bond fission along a collinear reaction coordinate without a tight transition state. The calculations reproduce the magnitude and temperature dependence of the rate coefficient and confirm that reaction R1 is in the low-pressure regime under our experimental conditions. PMID:25853321

  20. CHEMICAL REACTIONS OF AQUATIC HUMIC MATERIALS WITH SELECTED OXIDANTS

    EPA Science Inventory

    A study was conducted to identify the specific organic reaction products of natural aquatic humic materials with selected oxidants (KMnO4, HOCl, Cl02, O3 and monochloramine). Reaction products were identified by GC/MS after solvent extraction and derivatization. The two most reac...