Science.gov

Sample records for oscillating chemical reaction

  1. Concentration fluctuations in a mesoscopic oscillating chemical reaction system

    NASA Astrophysics Data System (ADS)

    Qian, Hong; Saffarian, Saveez; Elson, Elliot L.

    2002-08-01

    Under sustained pumping, kinetics of macroscopic nonlinear biochemical reaction systems far from equilibrium either can be in a stationary steady state or can execute sustained oscillations about a fixed mean. For a system of two dynamic species X and Y, the concentrations nx and ny will be constant or will repetitively trace a closed loop in the (nx, ny) phase plane, respectively. We study a mesoscopic system with nx and ny very small; hence the occurrence of random fluctuations modifies the deterministic behavior and the law of mass action is replaced by a stochastic model. We show that nx and ny execute cyclic random walks in the (nx, ny) plane whether or not the deterministic kinetics for the corresponding macroscopic system represents a steady or an oscillating state. Probability distributions and correlation functions for nx(t) and ny(t) show quantitative but not qualitative differences between states that would appear as either oscillating or steady in the corresponding macroscopic systems. A diffusion-like equation for probability P(nx, ny, t) is obtained for the two-dimensional Brownian motion in the (nx, ny) phase plane. In the limit of large nx, ny, the deterministic nonlinear kinetics derived from mass action is recovered. The nature of large fluctuations in an oscillating nonequilibrium system and the conceptual difference between "thermal stochasticity" and "temporal complexity" are clarified by this analysis. This result is relevant to fluorescence correlation spectroscopy and metabolic reaction networks. fluorescence correlation spectroscopy | limit cycle | nanobiochemistry | nonequilibrium steady state | random walk

  2. Oscillating Reactions: Two Analogies

    ERIC Educational Resources Information Center

    Petruševski, Vladimir M.; Stojanovska, Marina I.; Šoptrajanov, Bojan T.

    2007-01-01

    Oscillating chemical reactions are truly spectacular phenomena, and demonstrations are always appreciated by the class. However, explaining such reactions to high school or first-year university students is problematic, because it may seem that no acceptable explanation is possible unless the students have profound knowledge of both physical…

  3. Mixed-mode oscillations and chaos in return maps of an oscillatory chemical reaction

    NASA Astrophysics Data System (ADS)

    Blagojević, S. N.; Čupić, Ž.; Ivanović-Šašić, A.; Kolar-Anić, Lj.

    2015-12-01

    The return maps, as an element of mathematical phenomenology appropriate for general examinations of complex dynamic states of the oscillatory systems were used to detect and explain the evolution of mixed-mode oscillations and chaos in a six-dimensional nonlinear reaction system of the Bray-Liebhafsky (BL) reaction, a well-studied nonlinear chemical reaction system that exhibits complex dynamic behavior. For this purpose principally different Poincaré sections were applied and different transition scenarios between periodic and aperiodic states were examined by numerical simulations. It is shown that emergence of new periodic patterns can be detected by return maps already within chaotic windows. Besides, we also show that the higher dimensionality of manifold gives the impression of having several layers of manifolds.

  4. Periodic change of viscosity and density in an oscillating chemical reaction.

    PubMed

    Yoshimoto, Minoru; Shirahama, Hiroyuki; Kurosawa, Shigeru; Naito, Masayoshi

    2004-04-15

    It was found that the periodic change of the solution viscosity and density was generated in the Belousov-Zhabotinsky (BZ) reaction. This rhythmic phenomenon was observed in both the iron catalyst [[Fe(Phen)(3)](2+)-[Fe(Phen)(3)](3+)] and the cerium catalyst [Ce(III)-Ce(IV)] system, where the solution viscosity and density were synchronized with the redox potential in the in-phase mode. However, the time delay existed between the redox potential and the solution viscosity and density. The behavior of the BZ reaction was also monitored in the presence of the nonionic surfactant. This experiment revealed that, beyond the critical micelle concentration, the phase between the redox potential and the solution viscosity and density was synchronized into the antiphase mode. We suggested that the variation of the catalyst drove the oscillation of the solution viscosity and density in the BZ reaction. PMID:15267609

  5. Periodic change of viscosity and density in an oscillating chemical reaction

    NASA Astrophysics Data System (ADS)

    Yoshimoto, Minoru; Shirahama, Hiroyuki; Kurosawa, Shigeru; Naito, Masayoshi

    2004-04-01

    It was found that the periodic change of the solution viscosity and density was generated in the Belousov-Zhabotinsky (BZ) reaction. This rhythmic phenomenon was observed in both the iron catalyst {[Fe(Phen)3]2+-[Fe(Phen)3]3+} and the cerium catalyst [Ce(III)-Ce(IV)] system, where the solution viscosity and density were synchronized with the redox potential in the in-phase mode. However, the time delay existed between the redox potential and the solution viscosity and density. The behavior of the BZ reaction was also monitored in the presence of the nonionic surfactant. This experiment revealed that, beyond the critical micelle concentration, the phase between the redox potential and the solution viscosity and density was synchronized into the antiphase mode. We suggested that the variation of the catalyst drove the oscillation of the solution viscosity and density in the BZ reaction.

  6. Effect of gravity field on the nonequilibrium/nonlinear chemical oscillation reactions

    NASA Astrophysics Data System (ADS)

    Fujieda, S.; Mori, Y.; Nakazawa, A.; Mogami, Y.

    2001-01-01

    Biological systems have evolved for a long time under the normal gravity. The Belousov-Zhabotinsky (BZ) reaction is a nonlinear chemical system far from the equilibrium that may be considered as a simplified chemical model of the biological systems so as to study the effect of gravity. The reaction solution is comprised of bromate in sulfuric acid as an oxidizing agent, 1,4-cyclohexanedione as an organic substrate, and ferroin as a metal catalyst. Chemical waves in the BZ reaction-diffusion system are visualized as blue and red patterns of ferriin and ferroin, respectively. After an improvement to the tubular reaction vessels in the experimental setup, the traveling velocity of chemical waves in aqueous solutions was measured in time series under normal gravity, microgravity, hyper-gravity, and normal gravity using the free-fall facility of JAMIC (Japan Microgravity Center), Hokkaido, Japan. Chemical patterns were collected as image data via CCD camera and analyzed by the software of NIH image after digitization. The estimated traveling velocity increased with increasing gravity as expected. It was clear experimentally that the traveling velocity of target patterns in reaction diffusion system was influenced by the effect of convection and correlated closely with the gravity field.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    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 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.

  8. 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

  9. Oscillations and multiscale dynamics in a closed chemical reaction system: Second law of thermodynamics and temporal complexity

    NASA Astrophysics Data System (ADS)

    Li, Yongfeng; Qian, Hong; Yi, Yingfei

    2008-10-01

    We investigate the oscillatory reaction dynamics in a closed isothermal chemical system: the reversible Lotka-Volterra model. The second law of thermodynamics dictates that the system ultimately reaches an equilibrium. Quasistationary oscillations are analyzed while the free energy of the system serves as a global Lyapunov function of the dissipative dynamics. A natural distinction between regions near and far from equilibrium in terms of the free energy can be established. The dynamics is analogous to a nonlinear mechanical system with time-dependent increasing damping. Near equilibrium, no oscillation is possible as dictated by Onsager's reciprocal symmetry relation. We observe that while the free energy decreases in the closed system's dynamics, it does not follow the steepest descending path.

  10. Communication: Transition state trajectory stability determines barrier crossing rates in chemical reactions induced by time-dependent oscillating fields

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    When a chemical reaction is driven by an external field, the transition state that the system must pass through as it changes from reactant to product—for example, an energy barrier—becomes time-dependent. We show that for periodic forcing the rate of barrier crossing can be determined through stability analysis of the non-autonomous transition state. Specifically, strong agreement is observed between the difference in the Floquet exponents describing stability of the transition state trajectory, which defines a recrossing-free dividing surface [G. T. Craven, T. Bartsch, and R. Hernandez, "Persistence of transition state structure in chemical reactions driven by fields oscillating in time," Phys. Rev. E 89, 040801(R) (2014)], and the rates calculated by simulation of ensembles of trajectories. This result opens the possibility to extract rates directly from the intrinsic stability of the transition state, even when it is time-dependent, without requiring a numerically expensive simulation of the long-time dynamics of a large ensemble of trajectories.

  11. Arrays of coupled chemical oscillators.

    PubMed

    Forrester, Derek Michael

    2015-01-01

    Oscillating chemical reactions result from complex periodic changes in the concentration of the reactants. In spatially ordered ensembles of candle flame oscillators the fluctuations in the ratio of oxygen atoms with respect to that of carbon, hydrogen and nitrogen produces an oscillation in the visible part of the flame related to the energy released per unit mass of oxygen. Thus, the products of the reaction vary in concentration as a function of time, giving rise to an oscillation in the amount of soot and radiative emission. Synchronisation of interacting dynamical sub-systems occurs as arrays of flames that act as master and slave oscillators, with groups of candles numbering greater than two, creating a synchronised motion in three-dimensions. In a ring of candles the visible parts of each flame move together, up and down and back and forth, in a manner that appears like a "worship". Here this effect is shown for rings of flames which collectively empower a central flame to pulse to greater heights. In contrast, situations where the central flames are suppressed are also found. The phenomena leads to in-phase synchronised states emerging between periods of anti-phase synchronisation for arrays with different columnar sizes of candle and positioning. PMID:26582365

  12. Arrays of coupled chemical oscillators

    NASA Astrophysics Data System (ADS)

    Forrester, Derek Michael

    2015-11-01

    Oscillating chemical reactions result from complex periodic changes in the concentration of the reactants. In spatially ordered ensembles of candle flame oscillators the fluctuations in the ratio of oxygen atoms with respect to that of carbon, hydrogen and nitrogen produces an oscillation in the visible part of the flame related to the energy released per unit mass of oxygen. Thus, the products of the reaction vary in concentration as a function of time, giving rise to an oscillation in the amount of soot and radiative emission. Synchronisation of interacting dynamical sub-systems occurs as arrays of flames that act as master and slave oscillators, with groups of candles numbering greater than two, creating a synchronised motion in three-dimensions. In a ring of candles the visible parts of each flame move together, up and down and back and forth, in a manner that appears like a “worship”. Here this effect is shown for rings of flames which collectively empower a central flame to pulse to greater heights. In contrast, situations where the central flames are suppressed are also found. The phenomena leads to in-phase synchronised states emerging between periods of anti-phase synchronisation for arrays with different columnar sizes of candle and positioning.

  13. Arrays of coupled chemical oscillators

    PubMed Central

    Forrester, Derek Michael

    2015-01-01

    Oscillating chemical reactions result from complex periodic changes in the concentration of the reactants. In spatially ordered ensembles of candle flame oscillators the fluctuations in the ratio of oxygen atoms with respect to that of carbon, hydrogen and nitrogen produces an oscillation in the visible part of the flame related to the energy released per unit mass of oxygen. Thus, the products of the reaction vary in concentration as a function of time, giving rise to an oscillation in the amount of soot and radiative emission. Synchronisation of interacting dynamical sub-systems occurs as arrays of flames that act as master and slave oscillators, with groups of candles numbering greater than two, creating a synchronised motion in three-dimensions. In a ring of candles the visible parts of each flame move together, up and down and back and forth, in a manner that appears like a “worship”. Here this effect is shown for rings of flames which collectively empower a central flame to pulse to greater heights. In contrast, situations where the central flames are suppressed are also found. The phenomena leads to in-phase synchronised states emerging between periods of anti-phase synchronisation for arrays with different columnar sizes of candle and positioning. PMID:26582365

  14. Effect of temperature oscillation on chemical reaction rates in the atmosphere

    NASA Technical Reports Server (NTRS)

    Eberstein, I. J.

    1974-01-01

    The effect of temperature fluctuations on atmospheric ozone chemistry is examined by considering the Chapman photochemical theory of ozone transport to calculate globally averaged ozone production rates from mean reaction rates, activation energies, and recombination processes.

  15. Enhancing chemical reactions

    DOEpatents

    Morrey, John R.

    1978-01-01

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

  16. Rayleigh-type parametric chemical oscillation

    SciTech Connect

    Ghosh, Shyamolina; Ray, Deb Shankar

    2015-09-28

    We consider a nonlinear chemical dynamical system of two phase space variables in a stable steady state. When the system is driven by a time-dependent sinusoidal forcing of a suitable scaling parameter at a frequency twice the output frequency and the strength of perturbation exceeds a threshold, the system undergoes sustained Rayleigh-type periodic oscillation, wellknown for parametric oscillation in pipe organs and distinct from the usual forced quasiperiodic oscillation of a damped nonlinear system where the system is oscillatory even in absence of any external forcing. Our theoretical analysis of the parametric chemical oscillation is corroborated by full numerical simulation of two well known models of chemical dynamics, chlorite-iodine-malonic acid and iodine-clock reactions.

  17. Rayleigh-type parametric chemical oscillation.

    PubMed

    Ghosh, Shyamolina; Ray, Deb Shankar

    2015-09-28

    We consider a nonlinear chemical dynamical system of two phase space variables in a stable steady state. When the system is driven by a time-dependent sinusoidal forcing of a suitable scaling parameter at a frequency twice the output frequency and the strength of perturbation exceeds a threshold, the system undergoes sustained Rayleigh-type periodic oscillation, wellknown for parametric oscillation in pipe organs and distinct from the usual forced quasiperiodic oscillation of a damped nonlinear system where the system is oscillatory even in absence of any external forcing. Our theoretical analysis of the parametric chemical oscillation is corroborated by full numerical simulation of two well known models of chemical dynamics, chlorite-iodine-malonic acid and iodine-clock reactions. PMID:26429035

  18. Rayleigh-type parametric chemical oscillation

    NASA Astrophysics Data System (ADS)

    Ghosh, Shyamolina; Ray, Deb Shankar

    2015-09-01

    We consider a nonlinear chemical dynamical system of two phase space variables in a stable steady state. When the system is driven by a time-dependent sinusoidal forcing of a suitable scaling parameter at a frequency twice the output frequency and the strength of perturbation exceeds a threshold, the system undergoes sustained Rayleigh-type periodic oscillation, wellknown for parametric oscillation in pipe organs and distinct from the usual forced quasiperiodic oscillation of a damped nonlinear system where the system is oscillatory even in absence of any external forcing. Our theoretical analysis of the parametric chemical oscillation is corroborated by full numerical simulation of two well known models of chemical dynamics, chlorite-iodine-malonic acid and iodine-clock reactions.

  19. Microfluidic chemical reaction circuits

    DOEpatents

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

    2012-06-26

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

  20. Use of pruned computational neural networks for processing the response of oscillating chemical reactions with a view to analyzing nonlinear multicomponent mixtures.

    PubMed

    Hervás, C; Toledo, R; Silva, M

    2001-01-01

    The suitability of pruned computational neural networks (CNNs) for resolving nonlinear multicomponent systems involving synergistic effects by use of oscillating chemical reaction-based methods implemented using the analyte pulse perturbation technique is demonstrated. The CNN input data used for this purpose are estimates provided by the Levenberg-Marquardt method in the form of a three-parameter Gaussian curve associated with the singular profile obtained when the oscillating system is perturbed by an analyte mixture. The performance of the proposed method was assessed by applying it to the resolution of mixtures of pyrogallol and gallic acid based on their perturbating effect on a classical oscillating chemical system, viz. the Belousov-Zhabotinskyi reaction. A straightforward network topology (3:3:2, with 18 connections after pruning) allowed the resolution of mixtures of the two analytes in concentration ratios from 1:7 to 6:2 with a standard error of prediction for the testing set of 4.01 and 8.98% for pyrogallol and gallic acid, respectively. The reduced dimensions of the selected CNN architecture allowed a mathematical transformation of the input vector into the output one that can be easily implemented via software. Finally, the suitability of response surface analysis as an alternative to CNNs was also tested. The results were poor (relative errors were high), which confirms that properly selected pruned CNNs are effective tools for solving the analytical problem addressed in this work. PMID:11500128

  1. Chemical oscillations in closed macromolecular systems.

    PubMed Central

    Di Cera, E; Phillipson, P E; Wyman, J

    1988-01-01

    A cycle of irreversible, first-order, autocatalytic reactions among different states of a polyfunctional macromolecule, subject to the conservation of mass, can display stable chemical oscillations. This introduces a class of nonlinear dynamic models for energy transduction in closed macromolecular systems. PMID:3413066

  2. The Strange World of Chemical Oscillations.

    ERIC Educational Resources Information Center

    MOSAIC, 1978

    1978-01-01

    Describes an oscillating chemical reaction, and discusses numerous parallels to it in research, such as in fibrillation of the heart, body-clock rhythms of animals and plants, the self-assembly of multicellular organisms, and certain stripes in volcanic rock. (GA)

  3. Nanomotor dynamics in a chemically oscillating medium

    NASA Astrophysics Data System (ADS)

    Robertson, Bryan; Kapral, Raymond

    2015-04-01

    Synthetic nanomotors powered by chemical reactions have potential uses as cargo transport vehicles in both in vivo and in vitro applications. In many situations, motors will have to operate in out-of-equilibrium complex chemically reacting media, which supply fuel to the motors and remove the products they produce. Using molecular simulation and mean-field theory, this paper describes some of the new features that arise when a chemically powered nanomotor, operating through a diffusiophoretic mechanism, moves in an environment that supports an oscillatory chemical reaction network. It is shown how oscillations in the concentrations in chemical species in the environment give rise to oscillatory motor dynamics. More importantly, since the catalytic reactions on the motor that are responsible for its propulsion couple to the bulk phase reaction network, the motor can change its local environment. This process can give rise to distinctive spatiotemporal structures in reaction-diffusion media that occur as a result of active motor motion. Such locally induced nonequilibrium structure will play an important role in applications that involve motor dynamics in complex chemical media.

  4. Nanomotor dynamics in a chemically oscillating medium

    SciTech Connect

    Robertson, Bryan Kapral, Raymond

    2015-04-21

    Synthetic nanomotors powered by chemical reactions have potential uses as cargo transport vehicles in both in vivo and in vitro applications. In many situations, motors will have to operate in out-of-equilibrium complex chemically reacting media, which supply fuel to the motors and remove the products they produce. Using molecular simulation and mean-field theory, this paper describes some of the new features that arise when a chemically powered nanomotor, operating through a diffusiophoretic mechanism, moves in an environment that supports an oscillatory chemical reaction network. It is shown how oscillations in the concentrations in chemical species in the environment give rise to oscillatory motor dynamics. More importantly, since the catalytic reactions on the motor that are responsible for its propulsion couple to the bulk phase reaction network, the motor can change its local environment. This process can give rise to distinctive spatiotemporal structures in reaction-diffusion media that occur as a result of active motor motion. Such locally induced nonequilibrium structure will play an important role in applications that involve motor dynamics in complex chemical media.

  5. Chemical oscillations in the 4-aminophenol bromate photoreaction

    NASA Astrophysics Data System (ADS)

    Harati, Mohammad; Amiralaei, Sheida; Green, James; Wang, Jichang

    2007-05-01

    Chemical oscillations have been uncovered in the photo-mediated 4-aminophenol-bromate reaction. The presence of light is found essential both to the extent of the reaction and the oscillatory behavior, where turning-off (on) the light results in an immediate disappearance (revival) of the oscillation. The long induction time in this photochemical oscillator shows an exponential dependence on the light intensity. Phase diagrams show that illumination with intense light allows the otherwise non-oscillatory system to exhibit oscillations over broad 4-aminophenol, bromate and sulfuric acid concentrations. Preliminary mechanistic studies suggest that the reaction involves the production of N-bromo-1,4-benzoquinone-4-imine.

  6. Chemical Reaction Problem Solving.

    ERIC Educational Resources Information Center

    Veal, William

    1999-01-01

    Discusses the role of chemical-equation problem solving in helping students predict reaction products. Methods for helping students learn this process must be taught to students and future teachers by using pedagogical skills within the content of chemistry. Emphasizes that solving chemical reactions should involve creative cognition where…

  7. Chemical burn or reaction

    MedlinePlus

    ... this page: //medlineplus.gov/ency/article/000059.htm Chemical burn or reaction To use the sharing features on this page, please enable JavaScript. Chemicals that touch skin can lead to a reaction on the skin, throughout the body, or both. ...

  8. Superconductivity in nonclassical superconductors as a periodical (oscillating) redox reaction

    SciTech Connect

    Kostikova, G.P.; Korol`kov, D.V.; Kostikov, Yu.P.

    1995-10-20

    Comparison of the properties of high-temperature superconductors with those of chemical systems where a periodical (oscillating) redox reaction is realized suggests that the high-temperature superconducting of nonclassical superconductors (in particular, ternary oxides) results from activation of a periodical redox reaction within a single compounds containing heterovalent forms of each of two dissimilar elements. In this redox reaction, reversible converison of the corresponding heterovalent forms occur. 37 refs., 1 fig., 1 tab.

  9. Active Emulsions: Synchronization of Chemical Oscillators

    NASA Astrophysics Data System (ADS)

    Fraden, Seth

    2012-02-01

    We explore the dynamical behavior of emulsions consisting of nanoliter volume droplets of the oscillatory Belousov-Zhabotinsky (BZ) reaction separated by a continuous oil phase. Some of the aqueous BZ reactants partition into the oil leading to chemical coupling of the drops. We use microfluidics to vary the size, composition and topology of the drops in 1D and 2D. Addition of a light sensitive catalyst to the drops and illumination with a computer projector allows each drop to be individually perturbed. A variety of synchronous regimes are found that systematically vary with the coupling strength and whether coupling is dominated by activatory or inhibitory species. In 1D we observe in- and anti-phase oscillations, stationary Turing patterns in which drops stop oscillating, but form spatially periodic patterns of drops in the oxidized and reduced states, and more complex combinations of stationary and oscillatory drops. In 2D, the attractors are more complex and vary with network topology and coupling strength. For hexagonal lattices as a function of increasing coupling strength we observe right and left handed rotating oscillations, mixed oscillatory and Turing states and finally full Turing states. Reaction -- diffusion models based on a simplified description of the BZ chemistry and diffusion of messenger species reproduce a number of the experimental results. For a range of parameters, a simplified phase oscillator model provides an intuitive understanding of the complex synchronization patterns. [4pt] ``Coupled oscillations in a 1D emulsion of Belousov--Zhabotinsky droplets,'' Jorge Delgado, Ning Li, Marcin Leda, Hector O. Gonzalez-Ochoa, Seth Fraden and Irving R. Epstein, Soft Matter, 7, 3155 (2011).

  10. Synchronization Dynamics of Coupled Chemical Oscillators

    NASA Astrophysics Data System (ADS)

    Tompkins, Nathan

    The synchronization dynamics of complex networks have been extensively studied over the past few decades due to their ubiquity in the natural world. Prominent examples include cardiac rhythms, circadian rhythms, the flashing of fireflies, predator/prey population dynamics, mammalian gait, human applause, pendulum clocks, the electrical grid, and of the course the brain. Detailed experiments have been done to map the topology of many of these systems and significant advances have been made to describe the mathematics of these networks. Compared to these bodies of work relatively little has been done to directly test the role of topology in the synchronization dynamics of coupled oscillators. This Dissertation develops technology to examine the dynamics due to topology within networks of discrete oscillatory components. The oscillatory system used here consists of the photo-inhibitable Belousov-Zhabotinsky (BZ) reaction water-in-oil emulsion where the oscillatory drops are diffusively coupled to one another and the topology is defined by the geometry of the diffusive connections. Ring networks are created from a close-packed 2D array of drops using the Programmable Illumination Microscope (PIM) in order to test Turing's theory of morphogenesis directly. Further technology is developed to create custom planar networks of BZ drops in more complicated topologies which can be individually perturbed using illumination from the PIM. The work presented here establishes the validity of using the BZ emulsion system with a PIM to study the topology induced effects on the synchronization dynamics of coupled chemical oscillators, tests the successes and limitations of Turing's theory of morphogenesis, and develops new technology to further probe the effects of network topology on a system of coupled oscillators. Finally, this Dissertation concludes by describing ongoing experiments which utilize this new technology to examine topology induced transitions of synchronization

  11. 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.

  12. Chemical sensor with oscillating cantilevered probe

    DOEpatents

    Adams, Jesse D

    2013-02-05

    The invention provides a method of detecting a chemical species with an oscillating cantilevered probe. A cantilevered beam is driven into oscillation with a drive mechanism coupled to the cantilevered beam. A free end of the oscillating cantilevered beam is tapped against a mechanical stop coupled to a base end of the cantilevered beam. An amplitude of the oscillating cantilevered beam is measured with a sense mechanism coupled to the cantilevered beam. A treated portion of the cantilevered beam is exposed to the chemical species, wherein the cantilevered beam bends when exposed to the chemical species. A second amplitude of the oscillating cantilevered beam is measured, and the chemical species is determined based on the measured amplitudes.

  13. Desynchronization of stochastically synchronized chemical oscillators

    SciTech Connect

    Snari, Razan; Tinsley, Mark R. E-mail: kshowalt@wvu.edu; Faramarzi, Sadegh; Showalter, Kenneth E-mail: kshowalt@wvu.edu; Wilson, Dan; Moehlis, Jeff; Netoff, Theoden Ivan

    2015-12-15

    Experimental and theoretical studies are presented on the design of perturbations that enhance desynchronization in populations of oscillators that are synchronized by periodic entrainment. A phase reduction approach is used to determine optimal perturbation timing based upon experimentally measured phase response curves. The effectiveness of the perturbation waveforms is tested experimentally in populations of periodically and stochastically synchronized chemical oscillators. The relevance of the approach to therapeutic methods for disrupting phase coherence in groups of stochastically synchronized neuronal oscillators is discussed.

  14. Desynchronization of stochastically synchronized chemical oscillators.

    PubMed

    Snari, Razan; Tinsley, Mark R; Wilson, Dan; Faramarzi, Sadegh; Netoff, Theoden Ivan; Moehlis, Jeff; Showalter, Kenneth

    2015-12-01

    Experimental and theoretical studies are presented on the design of perturbations that enhance desynchronization in populations of oscillators that are synchronized by periodic entrainment. A phase reduction approach is used to determine optimal perturbation timing based upon experimentally measured phase response curves. The effectiveness of the perturbation waveforms is tested experimentally in populations of periodically and stochastically synchronized chemical oscillators. The relevance of the approach to therapeutic methods for disrupting phase coherence in groups of stochastically synchronized neuronal oscillators is discussed. PMID:26723155

  15. Desynchronization of stochastically synchronized chemical oscillators

    NASA Astrophysics Data System (ADS)

    Snari, Razan; Tinsley, Mark R.; Wilson, Dan; Faramarzi, Sadegh; Netoff, Theoden Ivan; Moehlis, Jeff; Showalter, Kenneth

    2015-12-01

    Experimental and theoretical studies are presented on the design of perturbations that enhance desynchronization in populations of oscillators that are synchronized by periodic entrainment. A phase reduction approach is used to determine optimal perturbation timing based upon experimentally measured phase response curves. The effectiveness of the perturbation waveforms is tested experimentally in populations of periodically and stochastically synchronized chemical oscillators. The relevance of the approach to therapeutic methods for disrupting phase coherence in groups of stochastically synchronized neuronal oscillators is discussed.

  16. A Lattice Boltzmann Model for Oscillating Reaction-Diffusion

    NASA Astrophysics Data System (ADS)

    Rodríguez-Romo, Suemi; Ibañez-Orozco, Oscar; Sosa-Herrera, Antonio

    2016-07-01

    A computational algorithm based on the lattice Boltzmann method (LBM) is proposed to model reaction-diffusion systems. In this paper, we focus on how nonlinear chemical oscillators like Belousov-Zhabotinsky (BZ) and the chlorite-iodide-malonic acid (CIMA) reactions can be modeled by LBM and provide with new insight into the nature and applications of oscillating reactions. We use Gaussian pulse initial concentrations of sulfuric acid in different places of a bidimensional reactor and nondiffusive boundary walls. We clearly show how these systems evolve to a chaotic attractor and produce specific pattern images that are portrayed in the reactions trajectory to the corresponding chaotic attractor and can be used in robotic control.

  17. 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.

  18. Chemical Reactions in DSMC

    SciTech Connect

    Bird, G. A.

    2011-05-20

    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.

  19. Mass Transfer with Chemical Reaction.

    ERIC Educational Resources Information Center

    DeCoursey, W. J.

    1987-01-01

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

  20. Creation and perturbation of planar networks of chemical oscillators

    PubMed Central

    Tompkins, Nathan; Cambria, Matthew Carl; Wang, Adam L.; Heymann, Michael; Fraden, Seth

    2015-01-01

    Methods for creating custom planar networks of diffusively coupled chemical oscillators and perturbing individual oscillators within the network are presented. The oscillators consist of the Belousov-Zhabotinsky (BZ) reaction contained in an emulsion. Networks of drops of the BZ reaction are created with either Dirichlet (constant-concentration) or Neumann (no-flux) boundary conditions in a custom planar configuration using programmable illumination for the perturbations. The differences between the observed network dynamics for each boundary condition are described. Using light, we demonstrate the ability to control the initial conditions of the network and to cause individual oscillators within the network to undergo sustained period elongation or a one-time phase delay. PMID:26117136

  1. Parametric spatiotemporal oscillation in reaction-diffusion systems.

    PubMed

    Ghosh, Shyamolina; Ray, Deb Shankar

    2016-03-01

    We consider a reaction-diffusion system in a homogeneous stable steady state. On perturbation by a time-dependent sinusoidal forcing of a suitable scaling parameter the system exhibits parametric spatiotemporal instability beyond a critical threshold frequency. We have formulated a general scheme to calculate the threshold condition for oscillation and the range of unstable spatial modes lying within a V-shaped region reminiscent of Arnold's tongue. Full numerical simulations show that depending on the specificity of nonlinearity of the models, the instability may result in time-periodic stationary patterns in the form of standing clusters or spatially localized breathing patterns with characteristic wavelengths. Our theoretical analysis of the parametric oscillation in reaction-diffusion system is corroborated by full numerical simulation of two well-known chemical dynamical models: chlorite-iodine-malonic acid and Briggs-Rauscher reactions. PMID:27078346

  2. Parametric spatiotemporal oscillation in reaction-diffusion systems

    NASA Astrophysics Data System (ADS)

    Ghosh, Shyamolina; Ray, Deb Shankar

    2016-03-01

    We consider a reaction-diffusion system in a homogeneous stable steady state. On perturbation by a time-dependent sinusoidal forcing of a suitable scaling parameter the system exhibits parametric spatiotemporal instability beyond a critical threshold frequency. We have formulated a general scheme to calculate the threshold condition for oscillation and the range of unstable spatial modes lying within a V-shaped region reminiscent of Arnold's tongue. Full numerical simulations show that depending on the specificity of nonlinearity of the models, the instability may result in time-periodic stationary patterns in the form of standing clusters or spatially localized breathing patterns with characteristic wavelengths. Our theoretical analysis of the parametric oscillation in reaction-diffusion system is corroborated by full numerical simulation of two well-known chemical dynamical models: chlorite-iodine-malonic acid and Briggs-Rauscher reactions.

  3. Chemical reactions at aqueous interfaces

    NASA Astrophysics Data System (ADS)

    Vecitis, Chad David

    2009-12-01

    ) 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.

  4. Coupled chemical oscillators and emergent system properties.

    PubMed

    Epstein, Irving R

    2014-09-25

    We review recent work on a variety of systems, from the nanometre to the centimetre scale, including microemulsions, microfluidic droplet arrays, gels and flow reactors, in which chemical oscillators interact to generate novel spatiotemporal patterns and/or mechanical motion. PMID:24835430

  5. Chemical burn or reaction

    MedlinePlus

    ... different products that contain toxic chemicals such as ammonia and bleach. The mixture can give off hazardous ... chemicals immediately after use. Use paints, petroleum products, ammonia, bleach, and other products that give off fumes ...

  6. More on Chemical Reaction Balancing.

    ERIC Educational Resources Information Center

    Swinehart, D. F.

    1985-01-01

    A previous article stated that only the matrix method was powerful enough to balance a particular chemical equation. Shows how this equation can be balanced without using the matrix method. The approach taken involves writing partial mathematical reactions and redox half-reactions, and combining them to yield the final balanced reaction. (JN)

  7. Speeding chemical reactions by focusing

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  8. Reduction of chemical reaction models

    NASA Technical Reports Server (NTRS)

    Frenklach, Michael

    1991-01-01

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

  9. Chemiluminescent Oscillating Demonstrations: The Chemical Buoy, the Lighting Wave, and the Ghostly Cylinder

    ERIC Educational Resources Information Center

    Prypsztejn, Hernan E.; Mulford, Douglas R.; Stratton, Doug

    2005-01-01

    Oscillating reactions have been extensively used in chemical demonstrations. They involve several chemical concepts about kinetics, catalysts, and thermodynamics. The spontaneous cyclic color change of a solution is an attraction in any educational-level course. Chemiluminescent reactions are also among the most fascinating demonstrations and have…

  10. Programmability of Chemical Reaction Networks

    NASA Astrophysics Data System (ADS)

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

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

  11. Nonequilibrium / nonlinear chemical oscillation in the virtual absence of gravity.

    PubMed

    Fujieda, S; Mogami, Y; Moriyasu, K; Mori, Y

    1999-01-01

    The Belousov-Zhabotinsky (BZ) reactions were used as typical examples of a nonlinear system far from equilibrium in connection with biological evolution. The virtual absence of gravity in the present work was given from the free-fall facility of Japan Microgravity Center (JAMIC) in Hokkaido. The reaction solution of BZ reaction was composed of bromate in sulfuric acid, 1,4-cyclohexanedione and ferroin to visualize the time development of patterns of chemical oscillations in the reaction-diffusion system. It is a bubble-free constitution in the aging of the reaction. Therefore, the setup constructed to collect image data via CCD cameras was simplified. The operation sequences of necessary devices were comprised of simple solid state relays which were started by a command from the operation room of JAMIC. The propagation profile of chemical patterns under microgravity of 10(-5) g was collected as image data for 9.8 s, and processed by a software of STM-STS2. In the aqueous solutions, propagation velocity of chemical patterns under microgravity was decreased to 80.9 % of that under normal gravity, owing to suppression of convection. On the other hand, in gel matrix, gravity did not influence the propagation velocity. PMID:11712549

  12. Nonequilibrium / nonlinear chemical oscillation in the virtual absence of gravity

    NASA Astrophysics Data System (ADS)

    Fujieda, S.; Mogami, Y.; Moriyasu, K.; Mori, Y.

    1999-01-01

    The Belousov-Zhabotinsky (BZ) reactions were used as typical examples of a nonlinear system far from equilibrium in connection with biological evolution. The virtual absence of gravity in the present work was given from the free-fall facility of Japan Microgravity Center (JAMIC) in Hokkaido. The reaction solution of BZ reaction was composed of bromate in sulfuric acid, 1,4-cyclohexanedione and ferroin to visualize the time development of patterns of chemical oscillations in the reaction-diffusion system. It is a bubble-free constitution in the aging of the reaction. Therefore, the setup constructed to collect image data via CCD cameras was simplified. The operation sequences of necessary devices were comprised of simple solid state relays which were started by a command from the operation room of JAMIC. The propagation profile of chemical patterns under microgravity of 10-5 g was collected as image data for 9.8 s, and processed by a software of STM-STS2. In the aqueous solutions, propagation velocity of chemical patterns under microgravity was decreased to 80.9 % of that under normal gravity, owing to suppression of convection. On the other hand, in gel matrix, gravity did not influence the propagation velocity.

  13. Molecular noise induces concentration oscillations in chemical systems with stable node steady states

    NASA Astrophysics Data System (ADS)

    Toner, D. L. K.; Grima, R.

    2013-02-01

    It is well known that internal or molecular noise induces concentration oscillations in chemical systems whose deterministic models exhibit damped oscillations. In this article we show, using the linear-noise approximation of the chemical master equation, that noise can also induce oscillations in systems whose deterministic descriptions admit no damped oscillations, i.e., systems with a stable node. This non-intuitive phenomenon is remarkable since, unlike noise-induced oscillations in systems with damped deterministic oscillations, it cannot be explained by noise excitation of the deterministic resonant frequency of the system. We here prove the following general properties of stable-node noise-induced oscillations for systems with two species: (i) the upper bound of their frequency is given by the geometric mean of the real eigenvalues of the Jacobian of the system, (ii) the upper bound of the Q-factor of the oscillations is inversely proportional to the distance between the real eigenvalues of the Jacobian, and (iii) these oscillations are not necessarily exhibited by all interacting chemical species in the system. The existence and properties of stable-node oscillations are verified by stochastic simulations of the Brusselator, a cascade Brusselator reaction system, and two other simple chemical systems involving auto-catalysis and trimerization. It is also shown how external noise induces stable node oscillations with different properties than those stimulated by internal noise.

  14. Bray-Liebhafsky and non-catalysed Briggs-Rauscher oscillating reactions

    NASA Astrophysics Data System (ADS)

    Schmitz, Guy; Furrow, Stanley D.

    2016-02-01

    In order to propose mechanisms of complicated chemical systems, it is necessary to study simpler subsystems. The mechanism we have proposed for the Bray-Liebhafsky (BL) oscillating reaction is based on kinetic studies of several reactions of iodine compounds between them and with hydrogen peroxide. Because the reactants of the non-catalysed Briggs-Rauscher (BR) oscillating reaction are the same as those of the BL reaction plus malonic acid, we propose now to extend the mechanism of the BL reaction to the BR reaction. With this aim, we add radical reactions of iodine compounds and of malonic acid. The choice of these reactions is based on our recent study of the unusual kinetics of the iodate reduction by high concentrations of hydrogen peroxide.

  15. Beating polymer gels coupled with a nonlinear chemical reaction

    NASA Astrophysics Data System (ADS)

    Yoshida, Ryo; Kokufuta, Etsuo; Yamaguchi, Tomohiko

    1999-06-01

    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 BZ reaction, is covalently bonded to the polymer chain. The poly[NIPAAm-co-Ru(bpy)3] gel provides an open system where the BZ reaction proceeds, when immersed in an aqueous solution containing the reactants of the BZ reaction (with the exception of a catalyst). The chemical oscillation in the BZ reaction generates the periodical changes of the charge of Ru(bpy)3 in the gel network between reduced [Ru(II)] and oxidized [Ru(III)] states. The gel swells at the oxidized state because the hydrophilicity of the polymer chains increases, while at the reduced state the gel deswells. Thus, the chemical energy is transduced into the mechanical energy to drive the polymer gel oscillation with a period of about 5 min, depending on the composition of the surrounding solution. The oscillation mode of the gel depends on its size scaled by the wavelength of the BZ pattern. Sufficiently small bead-like gels demonstrate isotropic beating. A large rectangular gel shows mechanical oscillation with a peristaltic motion coupled with the propagating chemical waves. The dynamic behavior of the chemical and mechanical oscillations have been analyzed with a model simulation.

  16. Influence of molecular structure on the properties of out-of-equilibrium oscillating enzymatic reaction networks.

    PubMed

    Wong, Albert S Y; Postma, Sjoerd G J; Vialshin, Ilia N; Semenov, Sergey N; Huck, Wilhelm T S

    2015-09-30

    Our knowledge of the properties and dynamics of complex molecular reaction networks, for example those found in living systems, considerably lags behind the understanding of elementary chemical reactions. In part, this is because chemical reactions networks are nonlinear systems that operate under conditions far from equilibrium. Of particular interest is the role of individual reaction rates on the stability of the network output. In this research we use a rational approach combined with computational methods, to produce complex behavior (in our case oscillations) and show that small changes in molecular structure are sufficient to impart large changes in network behavior. PMID:26352485

  17. Self-Organized Traveling Chemo-Hydrodynamic Fingers Triggered by a Chemical Oscillator.

    PubMed

    Escala, D M; Budroni, M A; Carballido-Landeira, J; De Wit, A; Muñuzuri, A P

    2014-02-01

    Pulsatile chemo-hydrodynamic patterns due to a coupling between an oscillating chemical reaction and buoyancy-driven hydrodynamic flows can develop when two solutions of separate reactants of the Belousov-Zhabotinsky reaction are put in contact in the gravity field and conditions for chemical oscillations are met in the contact zone. In regular oscillatory conditions, localized periodic changes in the concentration of intermediate species induce pulsatile density gradients, which, in turn, generate traveling convective fingers breaking the transverse symmetry. These patterns are the self-organized result of a genuine coupling between chemical and hydrodynamic modes. PMID:26276584

  18. 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…

  19. Coupling among three chemical oscillators: Synchronization, phase death, and frustration

    NASA Astrophysics Data System (ADS)

    Yoshimoto, Minoru; Yoshikawa, Kenichi; Mori, Yoshihito

    1993-02-01

    Various modes in three coupled chemical oscillators in a triangular arrangement were observed. As a well-defined nonlinear oscillator, the Belousov-Zhabotinsky reaction was studied in a continuous-flow stirred tank reactor (CSTR). Coupling among CSTR's was performed by mass exchange. The coupling strength was quantitatively controlled by changing the flow rate of reacting solutions among the three CSTR's using peristaltic pumps between each pair of the reactors. As a key parameter to control the model of coupling, we changed the symmetry of the interaction between the oscillators. In the case of the symmetric coupling, a quasiperiodic state or a biperiodic mode, an all-death mode and two kinds of synchronized modes appeared, depending on the coupling strength. On the other hand, under the asymmetric coupling, a quasiperiodic state or a biperiodic mode, an all death mode and four kinds of synchronized modes appeared. Those modes have been discussed in relation to the idea of ``frustration'' in the Ising spin system, where the three-phase mode appears as a transition from the Ising spin system to the XY spin system.

  20. The role of Ce(III) in BZ oscillating reactions

    NASA Astrophysics Data System (ADS)

    Nogueira, Paulo A.; Varela, Hamilton; Faria, Roberto B.

    2012-03-01

    Herein we present results on the oscillatory dynamics in the bromate-oxalic acid-acetone-Ce(III)/Ce(IV) system in batch and also in a CSTR. We show that Ce(III) is the necessary reactant to allow the emergence of oscillations. In batch, oscillations occur with Ce(III) and also with Ce(IV), but no induction period is observed with Ce(III). In a CSTR, no oscillations were found using a freshly prepared Ce(IV), but only when the cerium-containing solution was aged, allowing partial conversion of Ce(IV) to Ce(III) by reaction with acetone.

  1. (Laser enhanced chemical reaction studies)

    SciTech Connect

    Not Available

    1992-01-01

    Experimental studies of dynamic molecular processes are described with particular emphasis on the use of a powerful infrared diode laser probe technique developed in our laboratory. This technique allows us to determine the final states of CO{sub 2} (and other molecules) produced by collisions, photofragmentation, or chemical reactions with a spectral resolution of 0.0003 cm{sup {minus}1} and a time resolution of 10{sup {minus}7} sec. Such high spectral resolution provides a detailed picture of the vibrational and rotational states of molecules produced by these dynamic events. We have used this experimental method to probe collisions between hot hydrogen/deuterium atoms and CO{sub 2}, between O({sup 1}D) atoms and CO{sub 2}, to study the final states of DC1 molecules produced as a result of the reactions of hot Cl atoms, and to investigate the dynamics of the reaction between OH and CO molecules. Advances in our techniques over the past two years have allowed us to identify and study more than 200 final rotational states in ten different vibrational levels of CO{sub 2} encompassing all 3 normal modes, many overtones, and combination states of the molecule. We have extended the technique to probe a variety of new molecules such as OCS, N{sub 2}O, DCl, and CS{sub 2}. All of this work is aimed at providing experimental tests for polyatomic molecule potential energy surfaces, chemical transition states in complex systems, and theories of reaction dynamic in molecules with more than 3 atoms.

  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. 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

  4. Learning to predict chemical reactions.

    PubMed

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

    2011-09-26

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

  5. Role of substrate inhibition kinetics in enzymatic chemical oscillations.

    PubMed Central

    Shen, P; Larter, R

    1994-01-01

    Two chemical kinetic models are investigated using standard nonlinear dynamics techniques to determine the conditions under which substrate inhibition kinetics can lead to oscillations. The first model is a classical substrate inhibition scheme based on Michaelis-Menten kinetics and involves a single substrate. Only when this reaction takes place in a flow reactor (i.e., both substrate and product are taken to follow reversible flow terms) are oscillations observed; however, the range of parameter values over which such oscillations occur is so narrow it is experimentally unobservable. A second model based on a general mechanism applied to the kinetics of many pH-dependent enzymes is also studied. This second model includes both substrate inhibition kinetics as well as autocatalysis through the activation of the enzyme by hydrogen ion. We find that it is the autocatalysis that is always responsible for oscillatory behavior in this scheme. The substrate inhibition terms affect the steady-state behavior but do not lead to oscillations unless product inhibition or multiple substrates are present; this is a general conclusion we can draw from our studies of both the classical substrate inhibition scheme and the pH-dependent enzyme mechanism. Finally, an analysis of the nullclines for these two models allows us to prove that the nullcline slopes must have a negative value for oscillatory behavior to exist; this proof can explain our results. From our analysis, we conclude with a brief discussion of other enzymes that might be expected to produce oscillatory behavior based on a pH-dependent substrate inhibition mechanism. Images FIGURE 8 FIGURE 10 PMID:7819481

  6. Reaction efficiency effects on binary chemical reactions

    NASA Astrophysics Data System (ADS)

    Lazaridis, Filippos; Savara, Aditya; Argyrakis, Panos

    2014-09-01

    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 γ, where γ is in the range 0 < γ < 1. Our results show that at small γ values the system is reaction limited, but as γ increases it crosses over to a diffusion limited behavior. At early times, for small γ values, the particle density falls slower than for larger γ values. This fall-off goes over a crossover point, around the value of γ = 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 γ 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.

  7. Chemical reactions in endoreversible thermodynamics

    NASA Astrophysics Data System (ADS)

    Wagner, Katharina; Hoffmann, Karl Heinz

    2016-01-01

    Endoreversible thermodynamics is a theory for the (approximate) description of thermodynamic non-equilibrium systems, which allows us to capture the ever present irreversibilities of real processes. For instance in heat engines the dissipation due to finite heat transport capabilities, as well as the resulting limitations in the energy fluxes, can be incorporated into the theory. It has thus been very successful in closing the gap between observed and theoretically predicted efficiencies. Here an extension of the theory is provided, with which chemical reactions can be included in the formalism. This opens up a wide field of applications for endoreversible modeling and the investigation of dissipative processes, for instance in fuel cells or batteries.

  8. Sustained large-amplitude chemomechanical oscillations induced by the Landolt clock reaction.

    PubMed

    Horváth, Judit

    2014-07-24

    Synergetic chemomechanical oscillators represent a fundamentally new class of oscillators, where a clock reaction, owning no oscillatory chemical kinetics, generates shrinking-swelling cycles in a chemoresponsive gel under appropriate fixed nonequilibrium boundary conditions. Sufficiently large size-changes are a condition for continually switching between a reacted and an unreacted chemical state in the gel through sufficiently large differences in the diffusion time between the environment and the core of the gel. Two former experimental demonstrations with acid autocatalytic reactions were frustrated either by complex behaviors (chlorite-tetrathionate system) or by side reactions with the gel matrix (bromate-sulfite system). With the Landolt (iodate-sulfite) reaction, regular large-amplitude chemomechanical oscillations can be sustained for more than a week. This enabled a fine study of the temperature and stoichiometry range of operation. I have identified several key steps that are experimentally essential to the systematic design of further synergetic oscillators. The robust realization of this type of self-organization in artificial systems is currently unique. PMID:24988549

  9. Uncovering Oscillations, Complexity, and Chaos in Chemical Kinetics Using Mathematica

    NASA Astrophysics Data System (ADS)

    Ferreira, M. M. C.; Ferreira, W. C., Jr.; Lino, A. C. S.; Porto, M. E. G.

    1999-06-01

    Unlike reactions with no peculiar temporal behavior, in oscillatory reactions concentrations can rise and fall spontaneously in a cyclic or disorganized fashion. In this article, the software Mathematica is used for a theoretical study of kinetic mechanisms of oscillating and chaotic reactions. A first simple example is introduced through a three-step reaction, called the Lotka model, which exhibits a temporal behavior characterized by damped oscillations. The phase plane method of dynamic systems theory is introduced for a geometric interpretation of the reaction kinetics without solving the differential rate equations. The equations are later numerically solved using the built-in routine NDSolve and the results are plotted. The next example, still with a very simple mechanism, is the Lotka-Volterra model reaction, which oscillates indefinitely. The kinetic process and rate equations are also represented by a three-step reaction mechanism. The most important difference between this and the former reaction is that the undamped oscillation has two autocatalytic steps instead of one. The periods of oscillations are obtained by using the discrete Fourier transform (DFT)-a well-known tool in spectroscopy, although not so common in this context. In the last section, it is shown how a simple model of biochemical interactions can be useful to understand the complex behavior of important biological systems. The model consists of two allosteric enzymes coupled in series and activated by its own products. This reaction scheme is important for explaining many metabolic mechanisms, such as the glycolytic oscillations in muscles, yeast glycolysis, and the periodic synthesis of cyclic AMP. A few of many possible dynamic behaviors are exemplified through a prototype glycolytic enzymatic reaction proposed by Decroly and Goldbeter. By simply modifying the initial concentrations, limit cycles, chaos, and birhythmicity are computationally obtained and visualized.

  10. 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.

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

    ERIC Educational Resources Information Center

    Schultz, Emeric

    2008-01-01

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

  12. Analysis of precision in chemical oscillators: implications for circadian clocks

    NASA Astrophysics Data System (ADS)

    d'Eysmond, Thomas; De Simone, Alessandro; Naef, Felix

    2013-10-01

    Biochemical reaction networks often exhibit spontaneous self-sustained oscillations. An example is the circadian oscillator that lies at the heart of daily rhythms in behavior and physiology in most organisms including humans. While the period of these oscillators evolved so that it resonates with the 24 h daily environmental cycles, the precision of the oscillator (quantified via the Q factor) is another relevant property of these cell-autonomous oscillators. Since this quantity can be measured in individual cells, it is of interest to better understand how this property behaves across mathematical models of these oscillators. Current theoretical schemes for computing the Q factors show limitations for both high-dimensional models and in the vicinity of Hopf bifurcations. Here, we derive low-noise approximations that lead to numerically stable schemes also in high-dimensional models. In addition, we generalize normal form reductions that are appropriate near Hopf bifurcations. Applying our approximations to two models of circadian clocks, we show that while the low-noise regime is faithfully recapitulated, increasing the level of noise leads to species-dependent precision. We emphasize that subcomponents of the oscillator gradually decouple from the core oscillator as noise increases, which allows us to identify the subnetworks responsible for robust rhythms.

  13. Butterfly effect in a chemical oscillator

    NASA Astrophysics Data System (ADS)

    Budroni, M. A.; Wodlei, F.; Rustici, M.

    2014-07-01

    The strong sensitivity of aperiodic dynamics to initial conditions is one of the fingerprinting features of chaotic systems. While this dependence can be directly verified by means of numerical approaches, it is quite elusive and difficult to be isolated in real experimental systems. In this paper, we discuss a didactic and self-consistent method to show the divergent behaviour between two infinitesimally different solutions of the famous Belousov-Zhabotinsky oscillator simultaneously undergoing a transition to a chaotic regime. Experimental data are also used to give an intuitive visualization of the essential meaning of a Lyapunov exponent, which allows for a more quantitative characterization of the chaotic transient.

  14. Microfabricated electrochemiluminescence cell for chemical reaction detection

    DOEpatents

    Northrup, M. Allen; Hsueh, Yun-Tai; Smith, Rosemary L.

    2003-01-01

    A detector cell for a silicon-based or non-silicon-based sleeve type chemical reaction chamber that combines heaters, such as doped polysilicon for heating, and bulk silicon for convection cooling. The detector cell is an electrochemiluminescence cell constructed of layers of silicon with a cover layer of glass, with spaced electrodes located intermediate various layers forming the cell. The cell includes a cavity formed therein and fluid inlets for directing reaction fluid therein. The reaction chamber and detector cell may be utilized in any chemical reaction system for synthesis or processing of organic, inorganic, or biochemical reactions, such as the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction, which are examples of a synthetic, thermal-cycling-based reaction. The ECL cell may also be used in synthesis instruments, particularly those for DNA amplification and synthesis.

  15. 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.

  16. '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...

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

    PubMed

    Vogt-Geisse, Stefan; Toro-Labbé, Alejandro

    2016-07-15

    In symmetry controlled reactions, orbital degeneracies among orbitals of different symmetries can occur along a reaction coordinate. In such case Koopmans' theorem and the finite difference approximation provide a chemical potential profile with nondifferentiable points. This results in an ill-defined reaction electronic flux (REF) profile, since it is defined as the derivative of the chemical potential with respect to the reaction coordinate. To overcome this deficiency, we propose a new way for the calculation of the chemical potential based on a many orbital approach, suitable for reactions in which symmetry is preserved. This new approach gives rise to a new descriptor: symmetry adapted chemical potential (SA-CP), which is the chemical potential corresponding to a given irreducible representation of a symmetry group. A corresponding symmetry adapted reaction electronic flux (SA-REF) is also obtained. Using this approach smooth chemical potential profiles and well defined REFs are achieved. An application of SA-CP and SA-REF is presented by studying the Cs enol-keto tautomerization of thioformic acid. Two SA-REFs are obtained, JA'(ξ) and JA'' (ξ). It is found that the tautomerization proceeds via an in-plane delocalized 3-center 4-electron O-H-S hypervalent bond which is predicted to exist only in the transition state (TS) region. © 2016 Wiley Periodicals, Inc. PMID:27237470

  18. Relaxation oscillations and diffusion chaos in the Belousov reaction

    NASA Astrophysics Data System (ADS)

    Glyzin, S. D.; Kolesov, A. Yu.; Rozov, N. Kh.

    2011-08-01

    Asymptotic and numerical analysis of relaxation self-oscillations in a three-dimensional system of Volterra ordinary differential equations that models the well-known Belousov reaction is carried out. A numerical study of the corresponding distributed model-the parabolic system obtained from the original system of ordinary differential equations with the diffusive terms taken into account subject to the zero Neumann boundary conditions at the endpoints of a finite interval is attempted. It is shown that, when the diffusion coefficients are proportionally decreased while the other parameters remain intact, the distributed model exhibits the diffusion chaos phenomenon; that is, chaotic attractors of arbitrarily high dimension emerge.

  19. Microfabricated sleeve devices for chemical reactions

    DOEpatents

    Northrup, M. Allen

    2003-01-01

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

  20. 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.

  1. Chemical Reactions at Surfaces. Final Progress Report

    SciTech Connect

    2003-02-21

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

  2. Kinetic studies of elementary chemical reactions

    SciTech Connect

    Durant, J.L. Jr.

    1993-12-01

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

  3. 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.

  4. 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…

  5. Entropy Generation in a Chemical Reaction

    ERIC Educational Resources Information Center

    Miranda, E. N.

    2010-01-01

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

  6. 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.

  7. Clustering in delay-coupled smooth and relaxational chemical oscillators

    NASA Astrophysics Data System (ADS)

    Blaha, Karen; Lehnert, Judith; Keane, Andrew; Dahms, Thomas; Hövel, Philipp; Schöll, Eckehard; Hudson, John L.

    2013-12-01

    We investigate cluster synchronization in networks of nonlinear systems with time-delayed coupling. Using a generic model for a system close to the Hopf bifurcation, we predict the order of appearance of different cluster states and their corresponding common frequencies depending upon coupling delay. We may tune the delay time in order to ensure the existence and stability of a specific cluster state. We qualitatively and quantitatively confirm these results in experiments with chemical oscillators. The experiments also exhibit strongly nonlinear relaxation oscillations as we increase the voltage, i.e., go further away from the Hopf bifurcation. In this regime, we find secondary cluster states with delay-dependent phase lags. These cluster states appear in addition to primary states with delay-independent phase lags observed near the Hopf bifurcation. Extending the theory on Hopf normal-form oscillators, we are able to account for realistic interaction functions, yielding good agreement with experimental findings.

  8. 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).

  9. Chemical reactions confined within carbon nanotubes.

    PubMed

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

    2016-08-22

    In this critical review, we survey the wide range of chemical reactions that have been confined within carbon nanotubes, particularly emphasising how the pairwise interactions between the catalysts, reactants, transition states and products of a particular molecular transformation with the host nanotube can be used to control the yields and distributions of products of chemical reactions. We demonstrate that nanoscale confinement within carbon nanotubes enables the control of catalyst activity, morphology and stability, influences the local concentration of reactants and products thus affecting equilibria, rates and selectivity, pre-arranges the reactants for desired reactions and alters the relative stability of isomeric products. We critically evaluate the relative advantages and disadvantages of the confinement of chemical reactions inside carbon nanotubes from a chemical perspective and describe how further developments in the controlled synthesis of carbon nanotubes and the incorporation of multifunctionality are essential for the development of this ever-expanding field, ultimately leading to the effective control of the pathways of chemical reactions through the rational design of multi-functional carbon nanoreactors. PMID:27301444

  10. Anatomy of an Elementary Chemical Reaction

    NASA Astrophysics Data System (ADS)

    Alexander, Andrew J.; Zare, Richard N.

    1998-09-01

    The alchemists of old sought the knowledge to transform one material to another-for example, base metals into gold-as a path to the elixir of life. As chemists have concerned themselves with the transformation from compound to compound, so they have become involved in trying to uncover the structures of molecules and the pathways that reactions follow. Classically, the study of reaction mechanisms in chemistry encompasses reaction kinetics, the study of velocities or rates of reactions, and reaction dynamics, the study of the nanoscopic motion and rearrangement of atoms during a reactive event. An essential aim of this article is to bring the reader to a favorable vantage point with a brief introduction to reactive dynamics, and from there to describe some examples of recent strategies that have been employed to promote a fundamental understanding of the anatomy of elementary chemical reactions. In the final section we ponder future directions for this rapidly evolving field of research.

  11. Memory Switches in Chemical Reaction Space

    PubMed Central

    Ramakrishnan, Naren; Bhalla, Upinder S.

    2008-01-01

    Just as complex electronic circuits are built from simple Boolean gates, diverse biological functions, including signal transduction, differentiation, and stress response, frequently use biochemical switches as a functional module. A relatively small number of such switches have been described in the literature, and these exhibit considerable diversity in chemical topology. We asked if biochemical switches are indeed rare and if there are common chemical motifs and family relationships among such switches. We performed a systematic exploration of chemical reaction space by generating all possible stoichiometrically valid chemical configurations up to 3 molecules and 6 reactions and up to 4 molecules and 3 reactions. We used Monte Carlo sampling of parameter space for each such configuration to generate specific models and checked each model for switching properties. We found nearly 4,500 reaction topologies, or about 10% of our tested configurations, that demonstrate switching behavior. Commonly accepted topological features such as feedback were poor predictors of bistability, and we identified new reaction motifs that were likely to be found in switches. Furthermore, the discovered switches were related in that most of the larger configurations were derived from smaller ones by addition of one or more reactions. To explore even larger configurations, we developed two tools: the “bistabilizer,” which converts almost-bistable systems into bistable ones, and frequent motif mining, which helps rank untested configurations. Both of these tools increased the coverage of our library of bistable systems. Thus, our systematic exploration of chemical reaction space has produced a valuable resource for investigating the key signaling motif of bistability. PMID:18636099

  12. Aerosol simulation including chemical and nuclear reactions

    SciTech Connect

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

    1985-01-01

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

  13. Theoretical study of chemical reactions in solution

    SciTech Connect

    Yokogawa, D.

    2015-12-31

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

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

    NASA Astrophysics Data System (ADS)

    Wright, Stephen W.

    2002-01-01

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

  15. 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…

  16. 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…

  17. Chemical reactions in reverse micelle systems

    DOEpatents

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

    1993-08-24

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

  18. Chemical computing with reaction-diffusion processes.

    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

  19. Computer simulation of spatial coupling in chemical oscillations of CO oxidation on two Pd(110) single crystals

    NASA Astrophysics Data System (ADS)

    Park, I. J.; Woo, S. I.

    1993-09-01

    Gas-phase coupling between two Pd(110) single crystals in a UHV CO oxidation reaction in a continuous stirred tank reactor (CSTR) has been simulated by solving gas-phase mass balance equations with kinetic rate equations. This work was motivated by the experimental results which show that the frequency of partial pressure change in carbon monoxide is the same as the frequency of the work function change in the oscillation region and that the coupling between the two crystals occurred entirely via CO partial pressure. The computer simulation described here gives qualitative agreement with the experimental results. The change in the oscillatory region originating from the coupling of chemical oscillators which are slightly different to each other is successfully demonstrated by this model. The coupling of two oscillators having a simple periodic oscillation to produce mixed-mode oscillation was also successfully simulated.

  20. 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.

  1. Theoretical studies of chemical reaction dynamics

    SciTech Connect

    Schatz, G.C.

    1993-12-01

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

  2. 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

  3. Suppression of Ostwald Ripening by Chemical Reactions

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  4. Tuning Bimolecular Chemical Reactions by Electric Fields

    NASA Astrophysics Data System (ADS)

    Tscherbul, Timur V.; Krems, Roman V.

    2015-07-01

    We develop a theoretical method for solving the quantum mechanical reactive scattering problem in the presence of external fields based on a hyperspherical coordinate description of the reaction complex combined with the total angular momentum representation for collisions in external fields. The method allows us to obtain converged results for the chemical reaction LiF +H →Li +HF in an electric field. Our calculations demonstrate that, by inducing couplings between states of different total angular momenta, electric fields with magnitudes <150 kV /cm give rise to resonant scattering and a significant modification of the total reaction probabilities, product state distributions, and the branching ratios for reactive versus inelastic scattering.

  5. Tuning Bimolecular Chemical Reactions by Electric Fields.

    PubMed

    Tscherbul, Timur V; Krems, Roman V

    2015-07-10

    We develop a theoretical method for solving the quantum mechanical reactive scattering problem in the presence of external fields based on a hyperspherical coordinate description of the reaction complex combined with the total angular momentum representation for collisions in external fields. The method allows us to obtain converged results for the chemical reaction LiF+H→Li+HF in an electric field. Our calculations demonstrate that, by inducing couplings between states of different total angular momenta, electric fields with magnitudes <150  kV/cm give rise to resonant scattering and a significant modification of the total reaction probabilities, product state distributions, and the branching ratios for reactive versus inelastic scattering. PMID:26207466

  6. Photochemical reactions of anthropogenic chemicals in seawater

    SciTech Connect

    Toole, A.P.; Crosby, D.G. )

    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.

  7. Stochastic flux analysis of chemical reaction networks

    PubMed Central

    2013-01-01

    Background Chemical reaction networks provide an abstraction scheme for a broad range of models in biology and ecology. The two common means for simulating these networks are the deterministic and the stochastic approaches. The traditional deterministic approach, based on differential equations, enjoys a rich set of analysis techniques, including a treatment of reaction fluxes. However, the discrete stochastic simulations, which provide advantages in some cases, lack a quantitative treatment of network fluxes. Results We describe a method for flux analysis of chemical reaction networks, where flux is given by the flow of species between reactions in stochastic simulations of the network. Extending discrete event simulation algorithms, our method constructs several data structures, and thereby reveals a variety of statistics about resource creation and consumption during the simulation. We use these structures to quantify the causal interdependence and relative importance of the reactions at arbitrary time intervals with respect to the network fluxes. This allows us to construct reduced networks that have the same flux-behavior, and compare these networks, also with respect to their time series. We demonstrate our approach on an extended example based on a published ODE model of the same network, that is, Rho GTP-binding proteins, and on other models from biology and ecology. Conclusions We provide a fully stochastic treatment of flux analysis. As in deterministic analysis, our method delivers the network behavior in terms of species transformations. Moreover, our stochastic analysis can be applied, not only at steady state, but at arbitrary time intervals, and used to identify the flow of specific species between specific reactions. Our cases study of Rho GTP-binding proteins reveals the role played by the cyclic reverse fluxes in tuning the behavior of this network. PMID:24314153

  8. Scattering Resonances in the Simplest Chemical Reaction

    NASA Astrophysics Data System (ADS)

    Fernandez-Alonso, Felix; Zare, Richard N.

    2002-10-01

    Recent studies of state-resolved angular distributions show the participation of reactive scattering resonances in the simplest chemical reaction. This review is intended for those who wish to learn about the state-of-the-art in the study of the H + H2 reaction family that has made this breakthrough possible. This review is also intended for those who wish to gain insight into the nature of reactive scattering resonances. Following a tour across several fields of physics and chemistry where the concept of resonance has been crucial for the understanding of new phenomena, we offer an operational definition and taxonomy of reactive scattering resonances. We introduce simple intuitive models to illustrate each resonance type. We focus next on the last decade of H + H2 reaction dynamics. Emphasis is placed on the various experimental approaches that have been applied to the search for resonance behavior in the H + H2 reaction family. We conclude by sketching the road ahead in the study of H + H2 reactive scattering resonances.

  9. Quantum dynamics of fast chemical reactions

    SciTech Connect

    Light, J.C.

    1993-12-01

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

  10. [Laser enhanced chemical reaction studies]. [Progress report

    SciTech Connect

    Not Available

    1992-04-01

    Experimental studies of dynamic molecular processes are described with particular emphasis on the use of a powerful infrared diode laser probe technique developed in our laboratory. This technique allows us to determine the final states of CO{sub 2} (and other molecules) produced by collisions, photofragmentation, or chemical reactions with a spectral resolution of 0.0003 cm{sup {minus}1} and a time resolution of 10{sup {minus}7} sec. Such high spectral resolution provides a detailed picture of the vibrational and rotational states of molecules produced by these dynamic events. We have used this experimental method to probe collisions between hot hydrogen/deuterium atoms and CO{sub 2}, between O({sup 1}D) atoms and CO{sub 2}, to study the final states of DC1 molecules produced as a result of the reactions of hot Cl atoms, and to investigate the dynamics of the reaction between OH and CO molecules. Advances in our techniques over the past two years have allowed us to identify and study more than 200 final rotational states in ten different vibrational levels of CO{sub 2} encompassing all 3 normal modes, many overtones, and combination states of the molecule. We have extended the technique to probe a variety of new molecules such as OCS, N{sub 2}O, DCl, and CS{sub 2}. All of this work is aimed at providing experimental tests for polyatomic molecule potential energy surfaces, chemical transition states in complex systems, and theories of reaction dynamic in molecules with more than 3 atoms.

  11. Chemical Reaction Dynamics in Nanoscle Environments

    SciTech Connect

    Evelyn M. Goldfield

    2006-09-26

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

  12. Law of Localization in Chemical Reaction Networks

    NASA Astrophysics Data System (ADS)

    Okada, Takashi; Mochizuki, Atsushi

    2016-07-01

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

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

    ERIC Educational Resources Information Center

    Qian Xie; Tinker, Robert

    2006-01-01

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

  14. Kinetics investigations of atmospheric chemical reactions

    SciTech Connect

    Hills, A.J.

    1987-01-01

    Two separate gas-phase kinetics investigations were performed using a low-pressure fast-flow system with mass spectrometer detection. The first part of this research was a study of the atmospheric reactivity of diatomic sulfur, S/sub 2/. Rates of the reactions of sulfur with O, O/sub 2/, O/sub 3/, N/sub 2/O, NO, and NO/sub 2/ were investigated at 409 K and low pressure (0.89-3.0 Torr) in a discharge-flow system with mass spectrometric detection. The second investigation involves a study of the synergistic coupling of atmospheric bromine and chlorine chemistry. Recent measurements of ozone in the stratosphere over Antarctica have shown that the springtime ozone column decreased by 40% from 1960 to 1985. Both dynamical and chemical theories have been advanced to explain the formation of the Antarctic ozone hole. Prominent among these theories is that a synergistic interaction between gas-phase BrO and ClO radicals may be responsible for springtime ozone loss. The overall rate constant for the reaction, BrO + ClO ..-->.. Br + OClO ..-->.. Br + Cl + O/sub 2/ ..-->.. BrCl + O/sub 2/, has been measured over the temperature range 241-408 K. The rate constant for the overall reaction equals (8.2 +/- 1.0) 10/sup -12/ cm/sup 3//molecule s, independent of temperature.

  15. Chimera and phase-cluster states in populations of coupled chemical oscillators

    NASA Astrophysics Data System (ADS)

    Tinsley, Mark R.; Nkomo, Simbarashe; Showalter, Kenneth

    2012-09-01

    Populations of coupled oscillators may exhibit two coexisting subpopulations, one with synchronized oscillations and the other with unsynchronized oscillations, even though all of the oscillators are coupled to each other in an equivalent manner. This phenomenon, discovered about ten years ago in theoretical studies, was then further characterized and named the chimera state after the Greek mythological creature made up of different animals. The highly counterintuitive coexistence of coherent and incoherent oscillations in populations of identical oscillators, each with an equivalent coupling structure, inspired great interest and a flurry of theoretical activity. Here we report on experimental studies of chimera states and their relation to other synchronization states in populations of coupled chemical oscillators. Our experiments with coupled Belousov-Zhabotinsky oscillators and corresponding simulations reveal chimera behaviour that differs significantly from the behaviour found in theoretical studies of phase-oscillator models.

  16. Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system.

    PubMed

    Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

    2016-01-01

    The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion-fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies. PMID:26786848

  17. Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system

    NASA Astrophysics Data System (ADS)

    Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

    2016-01-01

    The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion-fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies.

  18. Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system

    PubMed Central

    Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

    2016-01-01

    The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion–fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies. PMID:26786848

  19. Systematic Error Estimation for Chemical Reaction Energies.

    PubMed

    Simm, Gregor N; Reiher, Markus

    2016-06-14

    For a theoretical understanding of the reactivity of complex chemical systems, accurate relative energies between intermediates and transition states are required. Despite its popularity, density functional theory (DFT) often fails to provide sufficiently accurate data, especially for molecules containing transition metals. Due to the huge number of intermediates that need to be studied for all but the simplest chemical processes, DFT is, to date, the only method that is computationally feasible. Here, we present a Bayesian framework for DFT that allows for error estimation of calculated properties. Since the optimal choice of parameters in present-day density functionals is strongly system dependent, we advocate for a system-focused reparameterization. While, at first sight, this approach conflicts with the first-principles character of DFT that should make it, in principle, system independent, we deliberately introduce system dependence to be able to assign a stochastically meaningful error to the system-dependent parametrization, which makes it nonarbitrary. By reparameterizing a functional that was derived on a sound physical basis to a chemical system of interest, we obtain a functional that yields reliable confidence intervals for reaction energies. We demonstrate our approach on the example of catalytic nitrogen fixation. PMID:27159007

  20. Oscillations in the reaction rate of nitric oxide reduction by ammonia over polycrystalline platinum foil catalysts

    SciTech Connect

    Katona, T. |; Somorjai, G.A.

    1992-06-25

    Self-sustained oscillations were obtained in the No + NH{sub 3} reaction at atmospheric pressure with reactant partial pressures of 133-600 Pa (1-4.5 Torr), in the temperature range of 603-673 K. The effects of reaction parameters, temperature, partial pressure, and reactant gas velocity were studied. The onset temperature of the oscillations (603 K) was slightly dependent on the partial pressure of nitric oxide in the feed gas. Near this temperature the oscillations were uncontrolled (chaotic), while increasing the temperature resulted in periodic oscillations in the reaction rates. The oscillation phenomena were studied in both isothermic and adiabatic modes. The oscillations, when initiated by a temperature increase, start up only after an induction period during which the rates of NO consumption and N{sub 2} formation sharply increase as opposed to the slow enhancement of the rate of N{sub 2}O formation. The two reaction branches found at the high- and low-temperature regimes in the batch mode have product distributions which are similar to those found at the extremes of the amplitudes of rate oscillations. 36 refs., 13 figs.

  1. Chemical attenuation reactions of selenium; Final report

    SciTech Connect

    Zachara, J.M.; Rai, D.; Moore, D.A.; Turner, G.D.; Felmy, A.R.

    1994-02-01

    This report summarizes research on the geochemical behavior of Se present in utility coal-combustion wastes. Laboratory experiments quantified select geochemical reactions that control the concentrations of selenite (SeO{sub 3}{sup 2{minus}}) and selenate (SeO{sub 4}{sup 2{minus}}) in soil solutions and groundwater and determined the magnitude and mechanisms of chemical attenuation of these species in soils and subsurface materials. Thermodynamic data, equilibrium constants, and modeling procedures were developed that to utilities to make improved predictions of the mobility of Se species from ponded and dry landfill sites. An adsorption-constant database for selenite and selenate on common soil minerals was developed. The database, which can be used to estimate the extent of Se attenuation by adsorption in utility soils, was used to determine the specific mineral phases control the adsorption of selenite (Fe oxides) and selenate (Al oxides). Solubility studies were performed with two Se solid phases that may form in the environment [BaSeO{sub 4}(c) and Fe{sub 2}(SeO{sub 3}){sub 3}{lg_bullet}6H{sub 2}0(c)] to establish upper limits on Se concentrations. New thermodynamic data were developed to allow prediction of aqueous Se concentrations where these phases may exist. Eleven soil and subsurface materials, collected nationally and representative of properties frequently encountered at waste sites, were used in experiments involving adsorption of selenite and selenate to assess their potential for Se chemical attenuation and to determine chemical and mineralogic factors that control Se adsorption. Selenite was far more strongly adsorbed by the geologic materials than the selenate. The adsorption of both Se species depended on the type of natural materials and showed positive correlation with Fe and Al oxides associated with particle surfaces. Procedures were developed to predict Se adsorption from comprehensive chemical and mineralogic characterization data.

  2. 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.

  3. Enzyme oscillation can enhance the thermodynamic efficiency of cellular metabolism: consequence of anti-phase coupling between reaction flux and affinity

    NASA Astrophysics Data System (ADS)

    Himeoka, Yusuke; Kaneko, Kunihiko

    2016-04-01

    Cells generally convert nutrient resources to products via energy transduction. Accordingly, the thermodynamic efficiency of this conversion process is one of the most essential characteristics of living organisms. However, although these processes occur under conditions of dynamic metabolism, most studies of cellular thermodynamic efficiency have been restricted to examining steady states; thus, the relevance of dynamics to this efficiency has not yet been elucidated. Here, we develop a simple model of metabolic reactions with anabolism–catabolism coupling catalyzed by enzymes. Through application of external oscillation in the enzyme abundances, the thermodynamic efficiency of metabolism was found to be improved. This result is in strong contrast with that observed in the oscillatory input, in which the efficiency always decreased with oscillation. This improvement was effectively achieved by separating the anabolic and catabolic reactions, which tend to disequilibrate each other, and taking advantage of the temporal oscillations so that each of the antagonistic reactions could progress near equilibrium. In this case, anti-phase oscillation between the reaction flux and chemical affinity through oscillation of enzyme abundances is essential. This improvement was also confirmed in a model capable of generating autonomous oscillations in enzyme abundances. Finally, the possible relevance of the improvement in thermodynamic efficiency is discussed with respect to the potential for manipulation of metabolic oscillations in microorganisms.

  4. Silicon-based sleeve devices for chemical reactions

    DOEpatents

    Northrup, M.A.; Mariella, R.P. Jr.; Carrano, A.V.; Balch, J.W.

    1996-12-31

    A silicon-based sleeve type chemical reaction chamber is described that combines heaters, such as doped polysilicon for heating, and bulk silicon for convection cooling. The reaction chamber combines a critical ratio of silicon and silicon nitride to the volume of material to be heated (e.g., a liquid) in order to provide uniform heating, yet low power requirements. The reaction chamber will also allow the introduction of a secondary tube (e.g., plastic) into the reaction sleeve that contains the reaction mixture thereby alleviating any potential materials incompatibility issues. The reaction chamber may be utilized in any chemical reaction system for synthesis or processing of organic, inorganic, or biochemical reactions, such as the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction, which are examples of a synthetic, thermal-cycling-based reaction. The reaction chamber may also be used in synthesis instruments, particularly those for DNA amplification and synthesis. 32 figs.

  5. Silicon-based sleeve devices for chemical reactions

    DOEpatents

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

    1996-01-01

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

  6. Long-lived oscillations in the chlorite-iodide-malonic acid reaction in batch

    SciTech Connect

    Noszticzius, Z.; Ouyang, Qi; McCormick, W.D.; Swinney, H.L.

    1992-05-20

    The title reaction is the subject of current interest because the first experimental Turing patterns were observed recently in this system. Here, the authors report the first observation of oscillations that are long lived (over 1 h) in this system in a batch reactor; even after cessation the oscillations can be restarted several times by adding ClO{sub 2} to the exhausted system. These low-frequency low-amplitude (LL) oscillations were detected with both platinum and iodide-selective electrodes in the chlorite-iodide-malonic acid (original CIMA) reaction and in the closely related chlorine dioxide-iodide-malonic acid (minimal CIMA) system. The LL oscillations follow after the already known high frequency oscillations, sometimes separated by a second induction period. LL oscillations can appear without any induction period if appropriate concentrations of chlorine dioxide, iodomalonic acid, and chloride (CIMA-Cl system) are established in a dilute sulfuric acid medium. In this case neither iodine, iodide, nor malonic acid is needed. Some suggestions are made regarding the mechanism of these newly discovered oscillations. 33 refs., 6 figs., 1 tab.

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

    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.

  8. 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

  9. Heterogeneous chemical reactions: Preparation of monodisperse latexes

    NASA Technical Reports Server (NTRS)

    Vanderhoff, J. W.; Micale, F. J.; El-Aasser, M. S.; Sterk, A. A.; Bethke, G. W.

    1977-01-01

    It is demonstrated that a photoinitiated emulsion polymerization can be carried out to a significant conversion in a SPAR rocket prototype polymerization vessel within the six minutes allowed for the experiment. The percentage of conversion was determined by both dilatometry and gravimetric methods with good agreement. The experimental results lead to the following conclusions: (1) emulsion polymerizations can be carried out to conversions as high as 75%, using a stable micellized styrene-SLS system plus photoinitiator; (2) dilatometry can be used to accurately determine both the rate and conversion of polymerization; (3) thermal expansion due to the light source and heat of reaction is small and can be corrected for if necessary; (4) although seeded emulsion polymerizations are unfavorable in photoinitiation, as opposed to chemical initiation, polymerizations can be carried out to at least 15% conversion using 7940A seed particles, with 0.05% solids; and (5) photoinitiation should be used to initiate polymerization in the SPAR rocket experiments because of the mechanical simplicity of the experiment.

  10. Reaction rate oscillations during catalytic CO oxidation: A brief overview

    NASA Technical Reports Server (NTRS)

    Tsotsis, T. T.; Sane, R. C.

    1987-01-01

    It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

  11. 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.

  12. 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...

  13. 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)

  14. Incidents of chemical reactions in cell equipment

    SciTech Connect

    Baldwin, N.M.; Barlow, C.R.

    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.

  15. Deterministic Function Computation with Chemical Reaction Networks*

    PubMed Central

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

    2013-01-01

    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 : ℕk → ℕl by a count of some molecular species, i.e., if the CRN starts with x1, …, xk molecules of some “input” species X1, …, Xk, the CRN is guaranteed to converge to having f(x1, …, xk) molecules of the “output” species Y1, …, Yl. We show that a function f : ℕk → ℕl is deterministically computed by a CRN if and only if its graph {(x, y) ∈ ℕk × ℕl ∣ 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

  16. Semiclassical methods in chemical reaction dynamics

    SciTech Connect

    Keshavamurthy, S.

    1994-12-01

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

  17. Computed potential energy surfaces for chemical reactions

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1990-01-01

    The objective was to obtain accurate potential energy surfaces (PES's) for a number of reactions which are important in the H/N/O combustion process. The interest in this is centered around the design of the SCRAM jet engine for the National Aerospace Plane (NASP), which was envisioned as an air-breathing hydrogen-burning vehicle capable of reaching velocities as large as Mach 25. Preliminary studies indicated that the supersonic flow in the combustor region of the scram jet engine required accurate reaction rate data for reactions in the H/N/O system, some of which was not readily available from experiment. The most important class of combustion reactions from the standpoint of the NASP project are radical recombinaton reactions, since these reactions result in most of the heat release in the combustion process. Theoretical characterizations of the potential energy surfaces for these reactions are presented and discussed.

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

    NASA Astrophysics Data System (ADS)

    Suzuki, Yasuhiro

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

  19. 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

    2014-03-01

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

  20. Stereodynamics: From elementary processes to macroscopic chemical reactions

    SciTech Connect

    Kasai, Toshio; Che, Dock-Chil; Tsai, Po-Yu; Lin, King-Chuen; Palazzetti, Federico; Aquilanti, Vincenzo

    2015-12-31

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

  1. Chemical kinetics computer program for static and flow reactions

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.; Scullin, V. J.

    1972-01-01

    General chemical kinetics computer program for complex gas mixtures has been developed. Program can be used for any homogeneous reaction in either one dimensional flow or static system. It is flexible, accurate, and easy to use. It can be used for any chemical system for which species thermodynamic data and reaction rate constant data are known.

  2. 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

  3. 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)

  4. Demonstrating Energy Migration in Coupled Oscillators: A Central Concept in the Theory of Unimolecular Reactions

    ERIC Educational Resources Information Center

    Marcotte, Ronald E.

    2005-01-01

    This physical chemistry lecture demonstration is designed to aid the understanding of intramolecular energy transfer processes as part of the presentation of the theory of unimolecular reaction rates. Coupled pendulums are used to show the rate of migration of energy between oscillators under resonant and nonresonant conditions with varying…

  5. An Analysis of the Algebraic Method for Balancing Chemical Reactions.

    ERIC Educational Resources Information Center

    Olson, John A.

    1997-01-01

    Analyzes the algebraic method for balancing chemical reactions. Introduces a third general condition that involves a balance between the total amount of oxidation and reduction. Requires the specification of oxidation states for all elements throughout the reaction. Describes the general conditions, the mathematical treatment, redox reactions, and…

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

    SciTech Connect

    Baker, L. Jr.

    1986-01-01

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

  7. FACILITATED CHEMICAL SYNTHESIS UNDER ALTERNATE REACTION CONDITIONS

    EPA Science Inventory

    The chemical research in the late 1990's witnessed a paradigm shift towards "environmentally-friendly chemistry" more popularly known as "green chemistry" due to the increasing environmental concerns and legislative requirements to curb the release of chemical waste into the atmo...

  8. 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…

  9. Insights into collective cell behaviour from populations of coupled chemical oscillators.

    PubMed

    Taylor, Annette F; Tinsley, Mark R; Showalter, Kenneth

    2015-08-21

    Biological systems such as yeast show coordinated activity driven by chemical communication between cells. Here, we show how experiments with coupled chemical oscillators can provide insights into collective behaviour in cellular systems. Two methods of coupling the oscillators are described: exchange of chemical species with the surrounding solution and computer-controlled illumination of a light-sensitive catalyst. The collective behaviour observed includes synchronisation, dynamical quorum sensing (a density dependent transition to population-wide oscillations), and chimera states, where oscillators spontaneously split into coherent and incoherent groups. At the core of the different types of behaviour lies an intracellular autocatalytic signal and an intercellular communication mechanism that influences the autocatalytic growth. PMID:26195263

  10. Chemical Reaction Experiment for the Undergraduate Laboratory.

    ERIC Educational Resources Information Center

    Kwon, K. C.; And Others

    1987-01-01

    Provides an overview of an experiment on reaction kinetics of the anthracene-hydrogen system. Includes a description of the laboratory equipment, procedures, and data analysis requirements. Points out the advantages of the recommended technique. (ML)

  11. Kinetics of Chemical Reactions in Flames

    NASA Technical Reports Server (NTRS)

    Zeldovich, Y.; Semenov, N.

    1946-01-01

    In part I of the paper the theory of flame propagation is developed along the lines followed by Frank-Kamenetsky and one of the writers. The development of chain processes in flames is considered. A basis is given for the application of the method of stationary concentrations to reactions in flames; reactions with branching chains are analyzed. The case of a diffusion coefficient different from the coefficient of temperature conductivity is considered.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  13. Dynamical regimes of four almost identical chemical oscillators coupled via pulse inhibitory coupling with time delay.

    PubMed

    Vanag, Vladimir K; Smelov, Pavel S; Klinshov, Vladimir V

    2016-02-21

    The dynamic regimes in networks of four almost identical spike oscillators with pulsatile coupling via inhibitor are systematically studied. We used two models to describe individual oscillators: a phase-oscillator model and a model for the Belousov-Zhabotinsky reaction. A time delay τ between a spike in one oscillator and the spike-induced inhibitory perturbation of other oscillators is introduced. Diagrams of all rhythms found for three different types of connectivities (unidirectional on a ring, mutual on a ring, and all-to-all) are built in the plane C(inh)-τ, where C(inh) is the coupling strength. It is shown analytically and numerically that only four regular rhythms are stable for unidirectional coupling: walk (phase shift between spikes of neighbouring oscillators equals the quarter of the global period T), walk-reverse (the same as walk but consecutive spikes take place in the direction opposite to the direction of connectivity), anti-phase (any two neighbouring oscillators are anti-phase), and in-phase oscillations. In the case of mutual on the ring coupling, an additional in-phase-anti-phase mode emerges. For all-to-all coupling, two new asymmetrical patterns (two-cluster and three-cluster modes) have been found. More complex rhythms are observed at large C(inh), when some oscillators are suppressed completely or generate smaller number of spikes than others. PMID:26863079

  14. Synchronization of Cell Cycle Oscillator by Multi-pulse Chemical Perturbations

    NASA Astrophysics Data System (ADS)

    Lin, Yihan; Li, Ying; Dinner, Aaron; Scherer, Norbert

    2011-03-01

    Oscillators underlie biological rhythms in various organisms and provide a timekeeping mechanism. Cell cycle oscillator, for example, controls the progression of cell cycle stage and drives cyclic reproduction in both prokaryotes and eukaryotes. The understanding of the underlying nonlinear regulatory network allows experimental design of external perturbations to interact and control cell cycle oscillation. We have previously demonstrated in experiment and in simulation that the cell cycle coherence of a model bacterium can be progressively tuned by the level of a histidine kinase. Here, we present our recent effort to synchronize the division of a population of bacterium cells by external pulsatile chemical perturbations. We were able to synchronize the cell population by phase-locking approach: the external oscillator (i.e. periodic perturbation) entrains the internal cell cycle oscillator which is in analogous to the phase-locking of circadian clock to external light/dark oscillator. We explored the ranges of frequencies for two external oscillators of different amplitudes where phase-locking occurred. To our surprise, non-periodic chemical perturbations could also cause synchronization of a cell population, suggesting a Markovian cell cycle oscillation dynamics.

  15. Dynamic control and information processing in chemical reaction systems by tuning self-organization behavior

    NASA Astrophysics Data System (ADS)

    Lebiedz, Dirk; Brandt-Pollmann, Ulrich

    2004-09-01

    Specific external control of chemical reaction systems and both dynamic control and signal processing as central functions in biochemical reaction systems are important issues of modern nonlinear science. For example nonlinear input-output behavior and its regulation are crucial for the maintainance of the life process that requires extensive communication between cells and their environment. An important question is how the dynamical behavior of biochemical systems is controlled and how they process information transmitted by incoming signals. But also from a general point of view external forcing of complex chemical reaction processes is important in many application areas ranging from chemical engineering to biomedicine. In order to study such control issues numerically, here, we choose a well characterized chemical system, the CO oxidation on Pt(110), which is interesting per se as an externally forced chemical oscillator model. We show numerically that tuning of temporal self-organization by input signals in this simple nonlinear chemical reaction exhibiting oscillatory behavior can in principle be exploited for both specific external control of dynamical system behavior and processing of complex information.

  16. Synchronization: from pendulum clocks to chaotic lasers and chemical oscillators

    NASA Astrophysics Data System (ADS)

    Rosenblum, Michael; Pikovsky, Arkady

    2003-05-01

    Many natural and human-made nonlinear oscillators exhibit the ability to adjust their rhythms due to weak interaction: two lasers, being coupled, start to generate with a common frequency; cardiac pacemaker cells fire simultaneously; violinists in an orchestra play in unison. Such coordination of rhythms is a manifestation of a fundamental nonlinear phenomenon--synchronization. Discovered in the 17th century by Christiaan Huygens, it was observed in physics, chemistry, biology and even social behaviour, and found practical applications in engineering and medicine. The notion of synchronization has been recently extended to cover the adjustment of rhythms in chaotic systems, large ensembles of oscillating units, rotating objects, continuous media, etc. In spite of essential progress in theoretical and experimental studies, synchronization remains a challenging problem of nonlinear sciences.

  17. 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.

  18. CW CO2 Laser Induced Chemical Reactions

    NASA Astrophysics Data System (ADS)

    Pola, Joseph

    1989-05-01

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

  19. 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.

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

    NASA Astrophysics Data System (ADS)

    Deshmukh, Shivaraj D.; Tsori, Yoav

    2016-05-01

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

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

    PubMed

    Deshmukh, Shivaraj D; Tsori, Yoav

    2016-05-21

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

  2. Visualizing chemical reactions confined under graphene.

    PubMed

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

    2012-05-14

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

  3. Flow-distributed oscillations: Stationary chemical waves in a reacting flow

    NASA Astrophysics Data System (ADS)

    Kærn, Mads; Menzinger, Michael

    1999-10-01

    A recent prediction of stationary waves in open, reacting flows is experimentally verified. We show that stationary waves are generated by a mechanism whereby the flow carries a time-oscillating subelement, behaving like a batch reactor, through space while a fixed boundary condition at the inflow locks the phase of the oscillation. This mechanism can generate stationary patterns when all diffusion coefficients are equal. The experimental system is the ferroin-catalyzed Belousov-Zhabotinsky reaction in a tubular reactor, fed by the outflow of a continuous flow stirred tank reactor (CSTR). Parameter conditions are such that the concentrations are constant in the CSTR while they oscillate in the flow tube.

  4. 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)

  5. Experiments on Rate of Chemical Reactions.

    ERIC Educational Resources Information Center

    United Nations Educational, Scientific, and Cultural Organization, Bangkok (Thailand).

    This laboratory manual, part of a series of instruction books on basic experimental chemistry, is designed to provide the secondary school students of developing countries in Asia with laboratory experiences that bring out the fundamental concepts and ideas of chemical kinetics. Taking into consideration the possibility of limited facilities of…

  6. 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.

  7. Fluid flow and chemical reaction kinetics in metamorphic systems

    SciTech Connect

    Lasaga, A.C.; Rye, D.M. )

    1993-05-01

    The treatment and effects of chemical reaction kinetics during metamorphism are developed along with the incorporation of fluid flow, diffusion, and thermal evolution. The interplay of fluid flow and surface reaction rates, the distinction between steady state and equilibrium, and the possible overstepping of metamorphic reactions are discussed using a simple analytic model. This model serves as an introduction to the second part of the paper, which develops a reaction model that solves the coupled temperature-fluid flow-chemical composition differential equations relevant to metamorphic processes. Consideration of stable isotopic evidence requires that such a kinetic model be considered for the chemical evolution of a metamorphic aureole. A general numerical scheme is discussed to handle the solution of the model. The results of this kinetic model allow us to reach several important conclusions regarding the factors controlling the chemical evolution of mineral assemblages during a metamorphic event. 41 refs., 19 figs., 5 tabs.

  8. 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

  9. 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.

  10. A chemometric method to identify enzymatic reactions leading to the transition from glycolytic oscillations to waves

    NASA Astrophysics Data System (ADS)

    Zimányi, László; Khoroshyy, Petro; Mair, Thomas

    2010-06-01

    In the present work we demonstrate that FTIR-spectroscopy is a powerful tool for the time resolved and noninvasive measurement of multi-substrate/product interactions in complex metabolic networks as exemplified by the oscillating glycolysis in a yeast extract. Based on a spectral library constructed from the pure glycolytic intermediates, chemometric analysis of the complex spectra allowed us the identification of many of these intermediates. Singular value decomposition and multiple level wavelet decomposition were used to separate drifting substances from oscillating ones. This enabled us to identify slow and fast variables of glycolytic oscillations. Most importantly, we can attribute a qualitative change in the positive feedback regulation of the autocatalytic reaction to the transition from homogeneous oscillations to travelling waves. During the oscillatory phase the enzyme phosphofructokinase is mainly activated by its own product ADP, whereas the transition to waves is accompanied with a shift of the positive feedback from ADP to AMP. This indicates that the overall energetic state of the yeast extract determines the transition between spatially homogeneous oscillations and travelling waves.

  11. 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

  12. Accelerated Chemical Reactions and Organic Synthesis in Leidenfrost Droplets.

    PubMed

    Bain, Ryan M; Pulliam, Christopher J; Thery, Fabien; Cooks, R Graham

    2016-08-22

    Leidenfrost levitated droplets can be used to accelerate chemical reactions in processes that appear similar to reaction acceleration in charged microdroplets produced by electrospray ionization. Reaction acceleration in Leidenfrost droplets is demonstrated for a base-catalyzed Claisen-Schmidt condensation, hydrazone formation from precharged and neutral ketones, and for the Katritzky pyrylium into pyridinium conversion under various reaction conditions. Comparisons with bulk reactions gave intermediate acceleration factors (2-50). By keeping the volume of the Leidenfrost droplets constant, it was shown that interfacial effects contribute to acceleration; this was confirmed by decreased reaction rates in the presence of a surfactant. The ability to multiplex Leidenfrost microreactors, to extract product into an immiscible solvent during reaction, and to use Leidenfrost droplets as reaction vessels to synthesize milligram quantities of product is also demonstrated. PMID:27465311

  13. 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.

  14. Chemical reactions driven by concentrated solar energy

    NASA Astrophysics Data System (ADS)

    Levy, Moshe

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

  15. Limit-cycle oscillations and chaos in reaction networks subject to conservation of mass.

    PubMed Central

    Di Cera, E; Phillipson, P E; Wyman, J

    1989-01-01

    A cyclic network of autocatalytic reactions involving an unbuffered cofactor and a number of components subject to conservation of mass displays a surprising richness of dynamical behaviors. Limit-cycle oscillations are possible over a wide range of parameter values. Additionally, a cascade of period-doubling bifurcations leading to chaos can coexist with a multiplicity of stable steady states. These results draw attention to the role of unbuffering as a feedback in biochemical systems. PMID:2911564

  16. Is the simplest chemical reaction really so simple?

    PubMed Central

    Jankunas, Justin; Sneha, Mahima; Zare, Richard N.; Bouakline, Foudhil; Althorpe, Stuart C.; Herráez-Aguilar, Diego; Aoiz, F. Javier

    2014-01-01

    Modern computational methods have become so powerful for predicting the outcome for the H + H2 → H2 + H bimolecular exchange reaction that it might seem further experiments are not needed. Nevertheless, experiments have led the way to cause theorists to look more deeply into this simplest of all chemical reactions. The findings are less simple. PMID:24367084

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

    ERIC Educational Resources Information Center

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

    2011-01-01

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

  18. Laser cutting with chemical reaction assist

    DOEpatents

    Gettemy, Donald J.

    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.

  19. 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.

  20. Laser cutting with chemical reaction assist

    SciTech Connect

    Gettemy, D.J.

    1991-04-08

    This invention is comprised of 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.

  1. 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

  2. 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

  3. 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…

  4. Exact stochastic simulation of coupled chemical reactions with delays

    NASA Astrophysics Data System (ADS)

    Cai, Xiaodong

    2007-03-01

    Gillespie's exact stochastic simulation algorithm (SSA) [J. Phys. Chem. 81, 2350 (1977)] has been widely used to simulate the stochastic dynamics of chemically reacting systems. In this algorithm, it is assumed that all reactions occur instantly. While this is true in many cases, it is also possible that some chemical reactions, such as gene transcription and translation in living cells, take certain time to finish after they are initiated. Thus, the product of such reactions will emerge after certain delays. Apparently, Gillespie's SSA is not an exact algorithm for chemical reaction systems with delays. In this paper, the author develops an exact SSA for chemical reaction systems with delays, based upon the same fundamental premise of stochastic kinetics used by Gillespie in the development of his SSA. He then shows that an algorithm modified from Gillespie's SSA by Barrio et al. [PLOS Comput. Biol. 2, 1017 (2006)] is also an exact SSA for chemical reaction systems with delays, but it needs to generate more random variables than the author's algorithm.

  5. 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.

  6. Numerical simulation of rising bubble with chemical reaction

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  7. 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

  8. Chemical reactions and gas transfer in natural waters

    SciTech Connect

    O`Connor, D.J. |

    1998-02-01

    Many chemical reactions of environmental significance involve reactants or end products that exchange with the atmosphere. The transferable constituents are the atmospheric gases--oxygen, carbon dioxide, and, to a more limited degree, nitrogen--and volatile substances that are not usually present in the atmosphere, such as ammonia, sulfur dioxide, and hydrogen sulfide. Reactions of this type have many applications in natural water systems, as well as water and waste treatment processes. It is the general purpose of this paper to present a mathematical approach to the analysis of these reactions and to demonstrate the application to various environmental problems. Both variable and constant pH conditions are addressed. The latter frequently characterizes laboratory experiments in batch reactions, in which a constant pH is maintained. The former is commonly present in natural waters, in which the pH changes through the course of the chemical reaction.

  9. 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.

  10. Modulation of mechanical resonance by chemical potential oscillation in graphene

    NASA Astrophysics Data System (ADS)

    Chen, Changyao; Deshpande, Vikram V.; Koshino, Mikito; Lee, Sunwoo; Gondarenko, Alexander; MacDonald, Allan H.; Kim, Philip; Hone, James

    2016-03-01

    The classical picture of the force on a capacitor assumes a large density of electronic states, such that the electrochemical potential of charges added to the capacitor is given by the external electrostatic potential and the capacitance is determined purely by geometry. Here we consider capacitively driven motion of a nano-mechanical resonator with a low density of states, in which these assumptions can break down. We find three leading-order corrections to the classical picture: the first of which is a modulation in the static force due to variation in the internal chemical potential; the second and third are changes in the static force and dynamic spring constant due to the rate of change of chemical potential, expressed as the quantum (density of states) capacitance. As a demonstration, we study capacitively driven graphene mechanical resonators, where the chemical potential is modulated independently of the gate voltage using an applied magnetic field to manipulate the energy of electrons residing in discrete Landau levels. In these devices, we observe large periodic frequency shifts consistent with the three corrections to the classical picture. In devices with extremely low strain and disorder, the first correction term dominates and the resonant frequency closely follows the chemical potential. The theoretical model fits the data with only one adjustable parameter representing disorder-broadening of the Landau levels. The underlying electromechanical coupling mechanism is not limited by the particular choice of material, geometry, or mechanism for variation in the chemical potential, and can thus be extended to other low-dimensional systems.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. Phase Entrainment of Human Delta Oscillations Can Mediate the Effects of Expectation on Reaction Speed

    PubMed Central

    Stefanics, Gábor; Hangya, Balázs; Hernádi, István; Winkler, István; Lakatos, Péter; Ulbert, István

    2015-01-01

    The more we anticipate a response to a predictable stimulus, the faster we react. This empirical observation has been confirmed and quantified by many investigators suggesting that the processing of behaviorally relevant stimuli is facilitated by probability-based confidence of anticipation. However, the exact neural mechanisms underlying this phenomenon are largely unknown. Here we show that performance changes related to different levels of expectancy originate in dynamic modulation of delta oscillation phase. Our results obtained in rhythmic auditory target detection tasks indicated significant entrainment of the EEG delta rhythm to the onset of the target tones with increasing phase synchronization at higher levels of predictability. Reaction times correlated with the phase of the delta band oscillation at target onset. The fastest reactions occurred during the delta phase that most commonly coincided with the target event in the high expectancy conditions. These results suggest that low-frequency oscillations play a functional role in human anticipatory mechanisms, presumably by modulating synchronized rhythmic fluctuations in the excitability of large neuronal populations and by facilitating efficient task-related neuronal communication among brain areas responsible for sensory processing and response execution. PMID:20943899

  16. Asymmetric chemical reactions by polarized quantum beams

    NASA Astrophysics Data System (ADS)

    Takahashi, Jun-Ichi; Kobayashi, Kensei

    One of the most attractive hypothesis for the origin of homochirality in terrestrial bio-organic compounds (L-amino acid and D-sugar dominant) is nominated as "Cosmic Scenario"; a chiral impulse from asymmetric excitation sources in space triggered asymmetric reactions on the surfaces of such space materials as meteorites or interstellar dusts prior to the existence of terrestrial life. 1) Effective asymmetric excitation sources in space are proposed as polarized quantum beams, such as circularly polarized light and spin polarized electrons. Circularly polarized light is emitted as synchrotron radiation from tightly captured electrons by intense magnetic field around neutron stars. In this case, either left-or right-handed polarized light can be observed depending on the direction of observation. On the other hand, spin polarized electrons is emitted as beta-ray in beta decay from radioactive nuclei or neutron fireballs in supernova explosion. 2) The spin of beta-ray electrons is longitudinally polarized due to parity non-conservation in the weak interaction. The helicity (the the projection of the spin onto the direction of kinetic momentum) of beta-ray electrons is universally negative (left-handed). For the purpose of verifying the asymmetric structure emergence in bio-organic compounds by polarized quantum beams, we are now carrying out laboratory simulations using circularly polarized light from synchrotron radiation facility or spin polarized electron beam from beta-ray radiation source. 3,4) The target samples are solid film or aqueous solution of racemic amino acids. 1) K.Kobayashi, K.Kaneko, J.Takahashi, Y.Takano, in Astrobiology: from simple molecules to primitive life; Ed. V.Basiuk; American Scientific Publisher: Valencia, 2008. 2) G.A.Gusev, T.Saito, V.A.Tsarev, A.V.Uryson, Origins Life Evol. Biosphere. 37, 259 (2007). 3) J.Takahashi, H.Shinojima, M.Seyama, Y.Ueno, T.Kaneko, K.Kobayashi, H.Mita, M.Adachi, M.Hosaka, M.Katoh, Int. J. Mol. Sci. 10, 3044

  17. Incorporation of Chemical Reactions into Building-scale Flow

    SciTech Connect

    Humphreys, T D; Jayaweera, T M; Lee, R L

    2003-10-30

    Many hazardous atmospheric releases involve chemical reactions that occur within a few kilometers of the source. Reactions with commonly occurring atmospheric compounds such as the OH radical, can transform and potentially neutralize original release compounds. Especially in these cases, accurately resolving flow around nearby structures and over surrounding topography can be critical to correctly predicting material dispersion, and thus, the extent of any hazard. Accurate prediction of material dispersion around complex geometries near the source of an atmospheric release requires high-resolution computation. Further complications arise if the compounds released undergo chemical reactions which could alter the extent of the main plume. The reaction products form dispersion patterns separate from, and often more complicated than, the original plume. Directions for future work include expanding the library of chemical reaction mechanisms, adding capabilities for aqueous and heterogeneous reactions, and integrating this model within larger-scale models. We plan that the larger-scale models will provide meteorological and chemical boundary conditions, and that this model could provide a source term in larger-scale models, both for momentum and for dispersed compounds.

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

    PubMed

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

    2015-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2007-11-01

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

  1. The state space of a model for the Bray-Liebhafsky oscillating reaction

    NASA Astrophysics Data System (ADS)

    Schmitz, G.; Kolar-Anić, Lj.

    2007-09-01

    It has been known for a long time that the decomposition of hydrogen peroxide catalyzed by hydrogen and iodate ions, the Bray-Liebhafsky reaction, can generate oscillations in a batch reactor. Recently, mixed-mode oscillations and chaos have also been observed in a CSTR. The model we had previously proposed to explain the kinetics in a batch reactor can also simulate these new complex behaviors. Time series give only a limited view of the features of the calculated behaviors and more information is obtained studying the properties of the state space. We use projections of the trajectories, calculation of the correlation dimension of the attractor, Poincaré sections, and return maps. As the state space of the model is six-dimensional, we try to answer the questions of whether the projections into a 3D subspace give correct pictures of the real trajectories and whether we have reasons to prefer a special subspace.

  2. Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol

    SciTech Connect

    Kale, Seyit; Sode, Olaseni; Weare, Jonathan; Dinner, Aaron R.

    2014-11-07

    Finding transition paths for chemical reactions can be computationally costly owing to the level of quantum-chemical theory needed for accuracy. Here, we show that a multilevel preconditioning scheme that was recently introduced (Tempkin et al. J. Chem. Phys. 2014, 140, 184114) can be used to accelerate quantum-chemical string calculations. We demonstrate the method by finding minimum-energy paths for two well-characterized reactions: tautomerization of malonaldehyde and Claissen rearrangement of chorismate to prephanate. For these reactions, we show that preconditioning density functional theory (DFT) with a semiempirical method reduces the computational cost for reaching a converged path that is an optimum under DFT by several fold. In conclusion, the approach also shows promise for free energy calculations when thermal noise can be controlled.

  3. Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol

    DOE PAGESBeta

    Kale, Seyit; Sode, Olaseni; Weare, Jonathan; Dinner, Aaron R.

    2014-11-07

    Finding transition paths for chemical reactions can be computationally costly owing to the level of quantum-chemical theory needed for accuracy. Here, we show that a multilevel preconditioning scheme that was recently introduced (Tempkin et al. J. Chem. Phys. 2014, 140, 184114) can be used to accelerate quantum-chemical string calculations. We demonstrate the method by finding minimum-energy paths for two well-characterized reactions: tautomerization of malonaldehyde and Claissen rearrangement of chorismate to prephanate. For these reactions, we show that preconditioning density functional theory (DFT) with a semiempirical method reduces the computational cost for reaching a converged path that is an optimum undermore » DFT by several fold. In conclusion, the approach also shows promise for free energy calculations when thermal noise can be controlled.« less

  4. Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol

    PubMed Central

    2015-01-01

    Finding transition paths for chemical reactions can be computationally costly owing to the level of quantum-chemical theory needed for accuracy. Here, we show that a multilevel preconditioning scheme that was recently introduced (Tempkin et al. J. Chem. Phys.2014, 140, 184114) can be used to accelerate quantum-chemical string calculations. We demonstrate the method by finding minimum-energy paths for two well-characterized reactions: tautomerization of malonaldehyde and Claissen rearrangement of chorismate to prephanate. For these reactions, we show that preconditioning density functional theory (DFT) with a semiempirical method reduces the computational cost for reaching a converged path that is an optimum under DFT by several fold. The approach also shows promise for free energy calculations when thermal noise can be controlled. PMID:25516726

  5. Maximum Probability Reaction Sequences in Stochastic Chemical Kinetic Systems

    PubMed Central

    Salehi, Maryam; Perkins, Theodore J.

    2010-01-01

    The detailed behavior of many molecular processes in the cell, such as protein folding, protein complex assembly, and gene regulation, transcription and translation, can often be accurately captured by stochastic chemical kinetic models. We investigate a novel computational problem involving these models – that of finding the most-probable sequence of reactions that connects two or more states of the system observed at different times. We describe an efficient method for computing the probability of a given reaction sequence, but argue that computing most-probable reaction sequences is EXPSPACE-hard. We develop exact (exhaustive) and approximate algorithms for finding most-probable reaction sequences. We evaluate these methods on test problems relating to a recently-proposed stochastic model of folding of the Trp-cage peptide. Our results provide new computational tools for analyzing stochastic chemical models, and demonstrate their utility in illuminating the behavior of real-world systems. PMID:21629860

  6. 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

  7. 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.

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

    DOEpatents

    Skorpik, James R.; Dodson, Michael G.

    1999-01-01

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

  9. A network dynamics approach to chemical reaction networks

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  10. Nucleic Acid Templated Chemical Reaction in a Live Vertebrate

    PubMed Central

    2016-01-01

    Nucleic acid templated reactions are enabled by the hybridization of probe-reagent conjugates resulting in high effective reagent concentration and fast chemical transformation. We have developed a reaction that harnesses cellular microRNA (miRNA) to yield the cleavage of a linker releasing fluorogenic rhodamine in a live vertebrate. The reaction is based on the catalytic photoreduction of an azide by a ruthenium complex. We showed that this system reports specific expression of miRNA in living tissues of a vertebrate. PMID:27413783

  11. Chemical pathways in ultracold reactions of SrF molecules

    SciTech Connect

    Meyer, Edmund R.; Bohn, John L.

    2011-03-15

    We present a theoretical investigation of the chemical reaction SrF + SrF {yields} products, focusing on reactions at ultralow temperatures. We find that bond swapping SrF + SrF {yields} Sr{sub 2} + F{sub 2} is energetically forbidden at these temperatures. Rather, the only energetically allowed reaction is SrF + SrF {yields} SrF{sub 2} + Sr, and even then only singlet states of the SrF{sub 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.

  12. 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.

  13. Modeling Second-Order Chemical Reactions using Cellular Automata

    NASA Astrophysics Data System (ADS)

    Hunter, N. E.; Barton, C. C.; Seybold, P. G.; Rizki, M. M.

    2012-12-01

    Cellular automata (CA) are discrete, agent-based, dynamic, iterated, mathematical computational models used to describe complex physical, biological, and chemical systems. Unlike the more computationally demanding molecular dynamics and Monte Carlo approaches, which use "force fields" to model molecular interactions, CA models employ a set of local rules. The traditional approach for modeling chemical reactions is to solve a set of simultaneous differential rate equations to give deterministic outcomes. CA models yield statistical outcomes for a finite number of ingredients. The deterministic solutions appear as limiting cases for conditions such as a large number of ingredients or a finite number of ingredients and many trials. Here we present a 2-dimensional, probabilistic CA model of a second-order gas phase reaction A + B → C, using a MATLAB basis. Beginning with a random distribution of ingredients A and B, formation of C emerges as the system evolves. The reaction rate can be varied based on the probability of favorable collisions of the reagents A and B. The model permits visualization of the conversion of reagents to products, and allows one to plot concentration vs. time for A, B and C. We test hypothetical reaction conditions such as: limiting reagents, the effects of reaction probabilities, and reagent concentrations on the reaction kinetics. The deterministic solutions of the reactions emerge as statistical averages in the limit of the large number of cells in the array. Modeling results for dynamic processes in the atmosphere will be presented.

  14. 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.

  15. 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...

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    PubMed

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

    2016-03-31

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

  18. 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.

  19. WATER AS A REACTION MEDIUM FOR CLEAN CHEMICAL PROCESSES.

    EPA Science Inventory

    Green chemistry is a rapid developing new field that provides us a pro-active avenue for the sustainable development of future science and technologies. When designed properly, clean chemical technology can be developed in water as a reaction media. The technologies generated f...

  20. 2011 Chemical Reactions at Surfaces Gordon Research Conference

    SciTech Connect

    Peter Stair

    2011-02-11

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

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

    ERIC Educational Resources Information Center

    Dudukovic, M. P.

    1987-01-01

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

  2. Quantum and semiclassical theories of chemical reaction rates

    SciTech Connect

    Miller, W.H. |

    1995-09-01

    A rigorous quantum mechanical theory (and a semiclassical approximation thereto) is described for calculating chemical reaction rates ``directly``, i.e., without having to solve the complete state-to-state reactive scattering problem. The approach has many vestiges of transition state theory, for which it may be thought of as the rigorous generalization.

  3. Prediction of Rate Constants for Catalytic Reactions with Chemical Accuracy.

    PubMed

    Catlow, C Richard A

    2016-08-01

    Ex machina: A computational method for predicting rate constants for reactions within microporous zeolite catalysts with chemical accuracy has recently been reported. A key feature of this method is a stepwise QM/MM approach that allows accuracy to be achieved while using realistic models with accessible computer resources. PMID:27329206

  4. Do nuclear reactions take place under chemical stimulation?

    SciTech Connect

    Bockris, J.O.; Lin, G.H.; Bush, R.T.

    1996-09-01

    Several examples of nuclear reactions occurring under the stimulation of chemical type energies are given. The production of tritium from deuterium in Pd has more than 100 published confirmations. Three models suggest circumstances such that barriers between nucleii may become transparent. 24 refs.

  5. Mapping students' ideas about chemical reactions at different educational levels

    NASA Astrophysics Data System (ADS)

    Yan, Fan

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

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

    PubMed

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

    2011-09-01

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

  7. The role of chemical reactions in the Chernobyl accident

    SciTech Connect

    Grishanin, E. I.

    2010-12-15

    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 Degree-Sign 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. 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.

  9. Identification of dynamical models of chemical reaction networks

    NASA Astrophysics Data System (ADS)

    Haber, Aleksandar

    Current first-principles models of complex chemistry, such as combustion reaction networks, often give inaccurate predictions of the time variation of chemical species. Moreover, the high complexity and dimensionality of these models render them impractical for real-time prediction and control of chemical network processes. These limitations have motivated us to search for an alternative paradigm that is able to both identify the correct model from the observed dynamical data and reduce complexity while preserving the underlying network structure. In this talk, I will present one such modeling paradigm under the scenarios of complete and incomplete observability of the dynamics. The proposed approach is applicable to combustion chemistry and a range of other chemical reaction networks. Research supported by ARO Grant W911NF-14-1-0359.

  10. 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; Jakubec, I

    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)

  11. 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)

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

    PubMed

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

    2016-03-01

    Currently, the incidence of tattooing is on the rise compared to the past, especially among adolescents, and it leads to the urgency of monitoring the security status of tattooing centers, as well as to inform people about the risks of tattoo practice. In our clinical experience, 20% of tattooed patients presented adverse reactions, like allergic contact dermatitis, psoriasis with Koebner's phenomena and granulomatous reactions, with the latter most prevalent and most often related to red pigment. Adverse reactions to tattoo pigments, especially the red one, are well known and described in literature. Great attention has to be focused on the pigments used, especially for the presence of new substances, often not well known. For this reason, we decided to perform a study on 12 samples of red tattoo ink, obtained by patients affected by different cutaneous reactions in the site of tattoo, to analyze their chemical composition. PMID:26934738

  13. Photo-induced chemical reaction of trans-resveratrol.

    PubMed

    Zhao, Yue; Shi, Meng; Ye, Jian-Hui; Zheng, Xin-Qiang; Lu, Jian-Liang; Liang, Yue-Rong

    2015-03-15

    Photo-induced chemical reaction of trans-resveratrol has been studied. UV B, liquid state and sufficient exposure time are essential conditions to the photochemical change of trans-resveratrol. Three principal compounds, cis-resveratrol, 2,4,6-phenanthrenetriol and 2-(4-hydroxyphenyl)-5,6-benzofurandione, were successively generated in the reaction solution of trans-resveratrol (0.25 mM, 100% ethanol) under 100 μW cm(-2) UV B radiation for 4h. cis-Resveratrol, originated from isomerization of trans-resveratrol, resulted in 2,4,6-phenanthrenetriol through photocyclisation reaction meanwhile loss of 2 H. 2,4,6-Phenanthrenetriol played a role of photosensitizer producing singlet oxygen in the reaction pathway. The singlet oxygen triggered [4+2] cycloaddition reaction of trans-resveratrol, and then resulted in the generation of 2-(4-hydroxyphenyl)-5,6-benzofurandione through photorearrangement and oxidation reaction. The singlet oxygen reaction was closely related to the substrate concentration of trans-resveratrol in solution. PMID:25308653

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

    NASA Astrophysics Data System (ADS)

    Ziegler, U.

    2016-02-01

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

  15. Cooperative action of coherent groups in broadly heterogeneous populations of interacting chemical oscillators

    PubMed Central

    Mikhailov, A. S.; Zanette, D. H.; Zhai, Y. M.; Kiss, I. Z.; Hudson, J. L.

    2004-01-01

    We present laboratory experiments on the effects of global coupling in a population of electrochemical oscillators with a multimodal frequency distribution. The experiments show that complex collective signals are generated by this system through spontaneous emergence and joint operation of coherently acting groups representing hierarchically organized resonant clusters. Numerical simulations support these experimental findings. Our results suggest that some forms of internal self-organization, characteristic for complex multiagent systems, are already possible in simple chemical systems. PMID:15263084

  16. Investigation of chemical reactions in solution using API-MS

    NASA Astrophysics Data System (ADS)

    Santos, Leonardo Silva; Knaack, Larissa; Metzger, Jürgen O.

    2005-11-01

    The general concepts, advantages, and applications of on-line and off-line screening to organic reaction mechanistic studies applying API-MS are reviewed. An overview is presented of the development and the present stage of connected microreactors to API ion-sources. Examples of the successful application of API in revealing, elucidating, and helping to consolidate several proposed mechanisms of organic reactions are summarized. Finally, a variety of outstanding features and advantages that make API-MS the most suitable tool for the fast screening of intermediates directly from solution, and the exceptional gains in chemical information for organic chemists are also emphasized.

  17. Laser studies of chemical reaction and collision processes

    SciTech Connect

    Flynn, G.

    1993-12-01

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

  18. Chemical Accelerator Studies of Ion-Molecule Reaction Dynamics

    NASA Astrophysics Data System (ADS)

    Zhang, Jingfeng

    1995-01-01

    A chemical accelerator instrument has been used to study the dynamics of ion-molecule reaction processes in the gas phase. Specifically, the following reactions are investigated: eqalign{rm CO^+ + H_2&longrightarrowrm HCO ^+ + Hcrrm CO^+ + D_2& longrightarrowrm DCO^+ + Dcrrm CO^+ + HDlongrightarrow &rm HCO ^+ (DCO^+) + D (H)cr} . Both angular and velocity distributions of reactively scattered product ions are measured, as well as reaction cross sections as a function of reactant relative translational energy. Formation of HCO^+ ion from rm CO^+ + H_2 over the collision energy range from 0.35 to 3.02 eV (c.m.) follows closely the predictions of the spectator stripping model, and results in highly excited HCO^+ product ions. This reaction is found to proceed via a direct impulsive mechanism, without any long-lived intermediate complexes involved. The reaction cross section is proportional to E_{T} ^{-1/2}, where E_ {rm T} is the reactant ion relative translational energy. Deuterium atom transfer from D_2 to CO^+ over the collision energy range from 0.41 to 5.14 eV (c.m.) occurs also in a direct process. Reaction cross section is proportional to rm E_{T}^{ -1/2}. The results are very similar to those of the reaction rm CO^+ + H_2. The reaction CO^+ + HD has two product channels, leading to the formation of HCO ^+ and DCO^+, respectively. The reaction is studied over the energy range from 0.88 to 5.00 eV (c.m.). It is found that the production of HCO^+ is consistently the slightly favored reaction channel, which is attributed to the orientation isotope effect. The translational exoergicity for both reaction channels follows closely the prediction of spectator stripping model. Product DCO^+ ions are in higher excited states than HCO ^+ ions. Product velocity distribution contour maps indicate that, at the lowest energies, the DCO ^+ production channel has a longer reaction duration than the HCO^+ production channel, but both reaction channels are dominated by direct

  19. Crossed molecular beam studies of atmospheric chemical reaction dynamics

    SciTech Connect

    Zhang, Jingsong

    1993-04-01

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

  20. Chemical reaction fouling model for single-phase heat transfer

    SciTech Connect

    Panchal, C.B.; Watkinson, A.P.

    1993-08-01

    A fouling model was developed on the premise that the chemical reaction for generation of precursor can take place in the bulk fluid, in the thermalboundary layer, or at the fluid/wall interface, depending upon the interactive effects of flu id dynamics, heat and mass transfer, and the controlling chemical reaction. The analysis was used to examine the experimental data for fouling deposition of polyperoxides produced by autoxidation of indene in kerosene. The effects of fluid and wall temperatures for two flow geometries were analyzed. The results showed that the relative effects of physical parameters on the fouling rate would differ for the three fouling mechanisms; therefore, it is important to identify the controlling mechanism in applying the closed-flow-loop data to industrial conditions.

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

  3. 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.

  4. Solution of Chemical Master Equations for Nonlinear Stochastic Reaction Networks

    PubMed Central

    Smadbeck, Patrick; Kaznessis, Yiannis N.

    2014-01-01

    Stochasticity in the dynamics of small reacting systems requires discrete-probabilistic models of reaction kinetics instead of traditional continuous-deterministic ones. The master probability equation is a complete model of randomly evolving molecular populations. Because of its ambitious character, the master equation remained unsolved for all but the simplest of molecular interaction networks. With the first solution of chemical master equations, a wide range of experimental observations of small-system interactions may be mathematically conceptualized. PMID:25215268

  5. 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.

  6. Magnetic Resonance Current Density Imaging of Chemical Processes and Reactions

    NASA Astrophysics Data System (ADS)

    Beravs, Katarina; Demš Ar, Alojz; Demsar, Franci

    1999-03-01

    Electric current density imaging was used to image conductivity changes that occur as a chemical process or reaction progresses. Feasibility was assessed in two models representing the dissolving of an ionic solid and the formation of an insoluble precipitate. In both models, temporal and spatial changes in ionic concentrations were obtained on current density images. As expected, the images showed significant signal enhancement along the ionization/dissociation sites.

  7. Separation of the isotopes of boron by chemical exchange reactions

    DOEpatents

    McCandless, F.P.; Herbst, R.S.

    1995-05-30

    The isotopes of boron, {sup 10}B and {sup 11}B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF{sub 3} and a liquid BF{sub 3} donor molecular addition complex formed between BF{sub 3} gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone. 1 Fig.

  8. Separation of the isotopes of boron by chemical exchange reactions

    DOEpatents

    McCandless, Frank P.; Herbst, Ronald S.

    1995-01-01

    The isotopes of boron, .sup.10 B and .sup.11 B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF.sub.3 and a liquid BF.sub.3 . donor molecular addition complex formed between BF.sub.3 gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone.

  9. Shock induced chemical reactions in energetic structural materials

    NASA Astrophysics Data System (ADS)

    Reding, Derek J.

    Energetic structural materials (ESMs) constitute a new class of materials that provide dual functions of strength and energetic characteristics. ESMs are typically composed of micron-scale or nano-scale intermetallic mixtures or mixtures of metals and metal oxides, polymer binders, and structural reinforcements. Voids are included to produce a composite with favorable chemical reaction characteristics. In this thesis, a continuum approach is used to simulate gas-gun or explosive loading experiments where a strong shock is induced in the ESM by an impacting plate. Algorithms are developed to obtain equations of state of mixtures. It is usually assumed that the shock loading increases the energy of the ESM and causes the ESM to reach the transition state. It is also assumed that the activation energy needed to reach the transition state is a function of the temperature of the mixture. In this thesis, it is proposed that the activation energy is a function of temperature and the stress state of the mixture. The incorporation of such an activation energy is selected in this thesis. Then, a multi-scale chemical reaction model for a heterogeneous mixture is introduced. This model incorporates reaction initiation, propagation, and extent of completed reaction in spatially heterogeneous distributions of reactants. A new model is proposed for the pore collapse of mixtures. This model is formulated by modifying the Carol, Holt, and Nesterenko spherically symmetric model to include mixtures and compressibility effects. Uncertainties in the model result from assumptions in formulating the models for continuum relationships and chemical reactions in mixtures that are distributed heterogeneously in space and in numerical integration of the resulting equations. It is important to quantify these uncertainties. In this thesis, such an uncertainty quantification is investigated by systematically identifying the physical processes that occur during shock compression of ESMs which are

  10. Computational Study on Chemical Reaction Mechanisms of Octafluorocarbon Molecules

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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