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1

Thermal energy storage. [by means of chemical reactions  

NASA Technical Reports Server (NTRS)

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

Grodzka, P. G.

1975-01-01

2

Method of operating a thermal engine powered by a chemical reaction  

DOEpatents

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

Ross, J.; Escher, C.

1988-06-07

3

Method of operating a thermal engine powered by a chemical reaction  

DOEpatents

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

Ross, John (Stanford, CA); Escher, Claus (Nieder-Ronstadt, DE)

1988-01-01

4

Chemical Reactions  

NSDL National Science Digital Library

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

National Science Teachers Association (NSTA)

2009-05-01

5

Solar photo-thermal catalytic reactions to produce high value chemicals  

SciTech Connect

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

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

1992-04-01

6

Microfluidic chemical reaction circuits  

DOEpatents

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.

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

2012-06-26

7

Growth and characterization of zinc oxide nano\\/micro-fibers by thermal chemical reactions and vapor transport deposition in air  

Microsoft Academic Search

Zinc oxide (ZnO) crystal fibers were prepared on silicon (100) substrate via a simple thermal chemical reactions vapor transport deposition method in air with a mixture of ZnO and carbon powders as reactants. The growth process was carried out at 1100°C in a quartz tube with one side opened to the air. There is no other metal catalyst and carrier

B. J. Chen; X. W. Sun; C. X. Xu; B. K. Tay

2004-01-01

8

Chemical Reactions (Netorials)  

NSDL National Science Digital Library

Chemical Reactions: this is a resource in the collection "Netorials". The Netorials cover selected topics in first-year chemistry including: Chemical Reactions, Stoichiometry, Thermodynamics, Intermolecular Forces, Acids & Bases, Biomolecules, and Electrochemistry.

9

Chemical Reactions and Stoichiometry  

NSDL National Science Digital Library

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

The Concord Consortium

2011-12-11

10

Oscillating Chemical Reactions  

ERIC Educational Resources Information Center

Describes several oscillating chemical reactions which can be used in undergraduate chemistry laboratories. In one such reaction, ferroin oscillates from red (reducing solution) to blue (oxidizing solution) for about an hour at a frequency which can readily be shown to depend on such factors as the temperature, type of solvent, and concentration…

Hawkins, M. D.; And Others

1975-01-01

11

Method and apparatus for obtaining enhanced production rate of thermal chemical reactions  

DOEpatents

Reactors and processes are disclosed that can utilize high heat fluxes to obtain fast, steady-state reaction rates. Porous catalysts used in conjunction with microchannel reactors to obtain high rates of heat transfer are also disclosed. Reactors and processes that utilize short contact times, high heat flux and low pressure drop are described. Improved methods of steam reforming are also provided.

Tonkovich, Anna Lee Y. (Pasco, WA); Wang, Yong (Richland, WA); Wegeng, Robert S. (Richland, WA); Gao, Yufei (Kennewick, WA)

2006-05-16

12

Chemical Reactions at Surfaces  

SciTech Connect

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.

Michael Henderson and Nancy Ryan Gray

2010-04-14

13

Chemical Reactions in DSMC  

SciTech Connect

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.

Bird, G. A. [GAB Consulting Pty Ltd, 144/110 Sussex Street, Sydney NSW 2000 (Australia)

2011-05-20

14

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

E-print Network

A combined quantum-classical dynamics method for calculating thermal rate constants of chemical February 1992) We present a combined quantum-classical-stochastic dynamics method based on the flux to combine classical and quantum dynamics have been pro- posed and have shown some encouraging results

Truong, Thanh N.

15

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

NASA Technical Reports Server (NTRS)

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

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

1989-01-01

16

Microfabricated electrochemiluminescence cell for chemical reaction detection  

DOEpatents

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.

Northrup, M. Allen (Berkeley, CA); Hsueh, Yun-Tai (Davis, CA); Smith, Rosemary L. (Davis, CA)

2003-01-01

17

Chemical Reactions: Investigating Exothermic and Endothermic Reactions  

NSDL National Science Digital Library

This activity is an inquiry-based investigation where students discover the indicators of chemical reactions (endothermic and exothermic) by collecting data and using that data to develop a testable question for further experimentation.

18

More on Chemical Reaction Balancing.  

ERIC Educational Resources Information Center

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)

Swinehart, D. F.

1985-01-01

19

Chemical burn or reaction  

MedlinePLUS

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

20

Chemical and Thermal Analysis  

NASA Technical Reports Server (NTRS)

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

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

1994-01-01

21

Critical phenomena in a system with two competing exothermic and endothermic reactions. Part I. Thermal explosion  

Microsoft Academic Search

This article examines the laws of thermal explosion for chemical reactions in which heat is absorbed and liberated simultaneously. The thermal equilibration time is much less than the characteristic times of the chemical reactions if the heats of reaction and activation energies are large. It is determined that the reaction rates vary during the establishment of thermal equilibrium, which alters

M. B. Borovikov; U. I. Gol'dshleger; I. A. Burovoi

1984-01-01

22

LEGO® Chemical Reactions  

NSDL National Science Digital Library

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

2014-09-29

23

Solar-thermal reaction processing  

DOEpatents

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

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

2014-03-18

24

Effects of Soret Dufour, chemical reaction and thermal radiation on MHD non-Darcy unsteady mixed convective heat and mass transfer over a stretching sheet  

NASA Astrophysics Data System (ADS)

A study has been carried out to analyze the combined effects of Soret (thermal-diffusion) and Dufour (diffusion-thermo) on unsteady MHD non-Darcy mixed convection over a stretching sheet embedded in a saturated porous medium in the presence of thermal radiation, viscous dissipation and first-order chemical reaction. Energy equation takes into account of viscous dissipation, thermal radiation and Soret effects. The governing differential equations are transformed into a set of non-linear coupled ordinary differential equations and solved using similarity analysis with numerical technique using appropriate boundary conditions for various physical parameters. The numerical solution for the governing nonlinear boundary value problem is based on shooting algorithm with Runge-Kutta-Fehlberg integration scheme over the entire range of physical parameters. The effects of various physical parameters on the dimensionless velocity, temperature and concentration profiles are depicted graphically and analyzed in detail. Favorable comparisons with previously published work on various special cases of the problem are obtained. Numerical results for local skin-friction, local Nusselt number, and local Sherwood number are tabulated for different physical parameters.

Pal, Dulal; Mondal, Hiranmoy

2011-04-01

25

Influence of fluctuating thermal and mass diffusion on unsteady MHD buoyancy-driven convection past a vertical surface with chemical reaction and Soret effects  

NASA Astrophysics Data System (ADS)

The influence of thermal radiation and first-order chemical reaction on unsteady MHD convective flow, heat and mass transfer of a viscous incompressible electrically conducting fluid past a semi-infinite vertical flat plate in the presence of transverse magnetic field under oscillatory suction and heat source in slip-flow regime is studied. The dimensionless governing equations for this investigation are formulated and solved analytically using two-term harmonic and non-harmonic functions. Comparisons with previously published work on special cases of the problem are performed and results are found to be in excellent agreement. A parametric study illustrating the effects of various physical parameters on the fluid velocity, temperature and concentration fields as well as skin-friction coefficient, the Nusselt and Sherwood numbers in terms of amplitude and phase is conducted. The numerical results of this parametric study are presented graphically and in tabular form to highlight the physical aspects of the problem.

Pal, Dulal; Talukdar, Babulal

2012-04-01

26

Experimental Demonstrations in Teaching Chemical Reactions.  

ERIC Educational Resources Information Center

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

Hugerat, Muhamad; Basheer, Sobhi

2001-01-01

27

Theoretical studies of chemical reaction dynamics  

SciTech Connect

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.

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

1993-12-01

28

Silicon-based sleeve devices for chemical reactions  

DOEpatents

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.

Northrup, M. Allen (Berkeley, CA); Mariella, Jr., Raymond P. (Danville, CA); Carrano, Anthony V. (Livermore, CA); Balch, Joseph W. (Livermore, CA)

1996-01-01

29

Homeostasis in Chemical Reaction Pathways  

E-print Network

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

Malyshev, V A; Zamyatin, A A

2011-01-01

30

Homeostasis in Chemical Reaction Pathways  

E-print Network

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

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

2011-12-25

31

Spin uncoupling in chemical reactions  

Microsoft Academic Search

Spin pairing is the main attribute of the covalent chemical bond. Exchange repulsion between closed shell molecules being responsible for activation barriers in bimolecular reactions can be explained by a high weight of the intermolecular triplet spin pairing. Intermolecular exchange interaction switches to a strong attraction when the molecules are in excited triplet states. This is the reason for that

Boris F. Minaev; Hans Ågren

2001-01-01

32

Thermal reactions of brushite cements.  

PubMed

The thermal reactions of a brushite cement made of beta-tricalcium phosphate (beta-TCP), monocalcium phosphate monohydrate (MCPM), and an aqueous solution were followed in situ with an isothermal calorimeter at 37 degrees C. The investigated parameters were the beta-TCP/MCPM weight ratio, the liquid-to-powder ratio, the synthesis route and milling duration of the beta-TCP powder, as well as the presence of sulfate, citrate, and pyrophosphate ions in the mixing liquid. The thermograms were complex, particularly for mixtures containing an excess of MCPM or additives in the mixing solution. Results suggested that the endothermic MCPM dissolution and the highly exothermic beta-TCP dissolution occurred simultaneously, thereby leading to the formation of a large exothermic peak at early reaction time. Both reactions were followed by the exothermic crystallization of brushite and in the presence of an excess of MCPM by the endothermic crystallization of monetite. Additives generally widened the main exothermic reaction peak, or in some cases with pyrophosphate ions postponed the main exothermic peak at late reaction time. Generally, the results could be well explained and understood based on thermodynamic and solubility data. PMID:17618509

Bohner, M; Gbureck, U

2008-02-01

33

The lepidocrocite-maghemite-haematite reaction chain-I. Acquisition of chemical remanent magnetization by maghemite, its magnetic properties and thermal stability  

NASA Astrophysics Data System (ADS)

We report on the magnetic properties and the acquisition of a chemical remanent magnetization (CRM) in a field of 100 ?T as a function of temperature and time during the lepidocrocite-maghemite-haematite reaction chain. The development of CRM was monitored at a series of 13 temperatures ranging from 175 to 550 °C data acquisition was done at the specific formation temperatures for durations of up to 500 hr. Up to acquisition temperatures of 200 °C it takes a considerable time (up to 7 hr) before the CRM is measurable. This time decreases with increasing temperature, reflecting the activation energy of the reaction to form the first maghemite. During the lepidocrocite conversion, formation of two types of maghemite is suggested by two peaks in the CRM versus time curves. Magnetic properties were analysed after various stages in the reaction. They indicate a mixture of superparamagnetic and single-domain maghemite. The first reaction product (obtained after annealing at 200 °C) is a fine-grained yet crystalline maghemite (labelled type A). Before massive maghemite formation occurs, the coercive and remanent coercive forces go through a minimum at intermediate temperatures of 250-300 °C (annealing for 2.5 hr). This minimum lowers to 200-250 °C with increasing annealing time (500 hr). This is probably the result of two processes acting simultaneously-formation of superparamagnetic maghemite particles of a second less crystalline maghemite type (labelled type B) and removal of stacking faults in type A maghemite. The second process is suggested by analogy to the behaviour of natural magnetite/maghemite systems on annealing. Removal of stacking faults is reported to result in a magnetic softening of the grain assemblage. Annealing at 300-350 °C removes most of the lepidocrocite and the second maghemite type, type B, becomes prominent. Haematite formation sets in at slightly higher temperatures, yet the type B maghemite is in part thermally stable up to 600 °C enabling Thellier-Thellier experiments. This stability is also inferred from Arrhenius fitting that shows a comparatively high activation energy for the maghemite to haematite reaction. In Thellier-Thellier experiments the CRM showed a markedly downward convex Arai-Nagata plot while a second thermoremanent magnetization (TRM) showed perfect linear behaviour as expected. This feature may be used to recognize CRM in natural rocks.

Gendler, T. S.; Shcherbakov, V. P.; Dekkers, M. J.; Gapeev, A. K.; Gribov, S. K.; McClelland, E.

2005-03-01

34

Binary counting with chemical reactions.  

PubMed

This paper describes a scheme for implementing a binary counter with chemical reactions. The value of the counter is encoded by logical values of "0" and "1" that correspond to the absence and presence of specific molecular types, respectively. It is incremented when molecules of a trigger type are injected. Synchronization is achieved with reactions that produce a sustained three-phase oscillation. This oscillation plays a role analogous to a clock signal in digital electronics. Quantities are transferred between molecular types in different phases of the oscillation. Unlike all previous schemes for chemical computation, this scheme is dependent only on coarse rate categories for the reactions ("fast" and "slow"). Given such categories, the computation is exact and independent of the specific reaction rates. Although conceptual for the time being, the methodology has potential applications in domains of synthetic biology such as biochemical sensing and drug delivery. We are exploring DNA-based computation via strand displacement as a possible experimental chassis. PMID:21121058

Kharam, Aleksandra; Jiang, Hua; Riedel, Marc; Parhi, Keshab

2011-01-01

35

Chemical and Thermal Analysis  

NASA Technical Reports Server (NTRS)

Work during the past three years has included significant research in several areas aimed at further clarification of the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) for pipes. Among the areas investigated were the crystallinity changes associated with both the Coflon and Tefzel after various simulated environmental exposures using X-Ray diffraction analysis. We have found that significant changes in polymer crystallinity levels occur as a function of the exposures. These crystallinity changes may have important consequences on the fracture, fatigue, tensile, and chemical resistance of the materials. We have also noted changes in the molecular weight distribution and the increased crosslinking of the Coflon material using Gel Permeation Chromatographic Analysis. Again these changes may result in variations in the mechanical and chemical properties in the material. We conducted numerous analytical studies with methods including X-ray Diffraction, Gel Permeation Chromatography, Fourier Transform Infrared Spectroscopy, and Differential Scanning Calorimetry. We investigated a plethora of aged samples of both Tefzel and Coflon that were forwarded from MERL. Pressurized tests were performed on powdered PVDF in a modified Fluid A, which we will call A-2. In this case the ethylene diamine concentration was increased to 3 percent in methanol. Coflon pipe sections and powdered Coflon were exposed in pressure cells at 1700 psi at three separate test temperatures.

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

1997-01-01

36

Chemical and Thermal Analysis  

NASA Technical Reports Server (NTRS)

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

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

1995-01-01

37

MHD MIXED-CONVECTION INTERACTION WITH THERMAL RADIATION AND nTH ORDER CHEMICAL REACTION PAST A VERTICAL POROUS PLATE EMBEDDED IN A POROUS MEDIUM  

Microsoft Academic Search

This article investigates the hydromagnetic mixed convection heat and mass transfer flow of an incompressible Boussinesq fluid past a vertical porous plate with constant heat flux in the presence of radiative heat transfer in an optically thin environment, viscous dissipation, and an nth order homogeneous chemical reaction between the fluid and the diffusing species. The dimensionless governing equations for this

O. D. Makinde

2010-01-01

38

Dynamic Reaction Figures: An Integrative Vehicle for Understanding Chemical Reactions  

ERIC Educational Resources Information Center

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…

Schultz, Emeric

2008-01-01

39

Classes of Chemical Reactions Reactions in aqueous media  

E-print Network

acid, HBr Phosphoric acid, H3PO4 Hydroiodic acid, HI Acetic acid, CH3CO2H Nitric acid, HNO3 CarbonicClasses of Chemical Reactions Reactions in aqueous media · Precipitation reactions · Acid + electrolytes: a substance that conducts an electric current when dissolved in water Acids are donors of H

Zakarian, Armen

40

2005 Chemical Reactions at Surfaces  

SciTech Connect

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.

Cynthia M. Friend

2006-03-14

41

Thermodynamic performance for a chemical reactions model  

NASA Astrophysics Data System (ADS)

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.

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

2015-01-01

42

Thermal, chemical, and mechanical cookoff modeling  

SciTech Connect

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

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

1994-08-01

43

Chemical Kinetics: Rate of Reaction  

NSDL National Science Digital Library

This site offers an interactive tutorial that emphasizes graphical interpretation of chemical kinetics. The stoichiometric coefficients for a chemical equation are determined by comparing the slopes of concentration-time plots for the reactants and products. This tutorial is coupled to others to further guide the student to a better understanding of chemical kinetics.

Blauch, David N.

44

Method and apparatus for controlling gas evolution from chemical reactions  

DOEpatents

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.

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

1999-01-01

45

Method and apparatus for controlling gas evolution from chemical reactions  

DOEpatents

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.

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

1999-05-25

46

Controlling chemical reactions of a single particle  

NASA Astrophysics Data System (ADS)

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

Ratschbacher, Lothar; Zipkes, Christoph; Sias, Carlo; Köhl, Michael

2012-09-01

47

Tracking thermal fronts with temperature-sensitive, chemically reactive tracers  

SciTech Connect

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

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

1987-01-01

48

Kinetic studies of elementary chemical reactions  

SciTech Connect

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.

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

1993-12-01

49

Chemical Principles Revisited: Annotating Reaction Equations.  

ERIC Educational Resources Information Center

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…

Tykodi, R. J.

1987-01-01

50

Chemical Reactions in Supercritical Carbon Dioxide  

NASA Astrophysics Data System (ADS)

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.

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

1998-12-01

51

Chemical preconcentrator with integral thermal flow sensor  

DOEpatents

A chemical preconcentrator with integral thermal flow sensor can be used to accurately measure fluid flow rate in a microanalytical system. The thermal flow sensor can be operated in either constant temperature or constant power mode and variants thereof. The chemical preconcentrator with integral thermal flow sensor can be fabricated with the same MEMS technology as the rest of the microanlaytical system. Because of its low heat capacity, low-loss, and small size, the chemical preconcentrator with integral thermal flow sensor is fast and efficient enough to be used in battery-powered, portable microanalytical systems.

Manginell, Ronald P. (Albuquerque, NM); Frye-Mason, Gregory C. (Cedar Crest, NM)

2003-01-01

52

Chemical Changes in Carbohydrates Produced by Thermal Processing.  

ERIC Educational Resources Information Center

Discusses chemical changes that occur in the carbohydrates found in food products when these products are subjected to thermal processing. Topics considered include browning reactions, starch found in food systems, hydrolysis of carbohydrates, extrusion cooking, processing of cookies and candies, and alterations in gums. (JN)

Hoseney, R. Carl

1984-01-01

53

Chemical Changes in Lipids Produced by Thermal Processing.  

ERIC Educational Resources Information Center

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

Nawar, Wassef W.

1984-01-01

54

Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product  

NASA Technical Reports Server (NTRS)

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.

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

1997-01-01

55

Acceleration of chemical reaction by chaotic mixing  

E-print Network

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

M. Chertkov; V. Lebedev

2003-01-27

56

Coupled thermal/chemical/mechanical modeling of insensitive explosives in thermal environments  

SciTech Connect

The ability to predict the response of a weapon system that contains insensitive explosives to elevated temperatures is important in understanding its safety characteristics. To model such a system at elevated temperatures in a finite element computer code requires a variety of capabilities. These modeling capabilities include thermal diffusion and convection to transport the heat to the explosives in the weapon system, temperature based chemical reaction modeling of the decomposition of the explosive materials, and mechanical modeling of both the metal casing and the unreacted and decomposed explosive. The Chemical TOPAZ code has been developed to model coupled thermal/chemical problems where we do not need to model the mass motion. We have also developed the LYNX2D code, based on PALM2D and Chemical TOPAZ, which is an implicit, two-dimensional coupled thermal/chemical/mechanical finite element model computer code. Some representative examples are shown. {copyright} {ital 1996 American Institute of Physics.}

Nichols, A.L. III [Lawrence Livermore National Laboratory, Livermore, California, 94550 (United States)

1996-05-01

57

Cores from the Salton Sea scientific drilling program: Metamorphic reaction progress as a function of chemical and thermal environment: Final report  

SciTech Connect

The study investigated the downhole progressive metamorphism at the Salton Sea site by monitoring and evaluating discontinuous and continuous metamorphic reactions. The main emphasis was placed on: (1) the addition of petrographic, geochemical, and mineralogical data to the Salton Sea data base; (2) determination of downhole reactions; (3) evaluation of the progress of individual continuous reaction (epsilon) and the overall reaction progress (epsilon/sub T/) during the transition from one metamorphic zone to the next; and (4) evaluation and correlation of mineral reactions and reaction progress with mineral phase and organic material geothermometry. To these ends, thirty-three samples from the Salton Sea core were analyzed for: (1) quantitative modal mineralogy using the x-ray diffraction reference intensity method (RIM), (2) 30 major and trace elements in the whole rock and (3) mineral chemistry and structural state. In addition, a subset of these samples were used for temperature determinations using vitrinite reflectivity.

Papike, J.J.; Shearer, C.K.

1987-05-13

58

Classification of Chemical Reactions: Stages of Expertise  

ERIC Educational Resources Information Center

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…

Stains, Marilyne; Talanquer, Vicente

2008-01-01

59

Visualization of chemical reaction dynamics: Toward understanding complex polyatomic reactions  

PubMed Central

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

SUZUKI, Toshinori

2013-01-01

60

Combustion chemical vapor deposited coatings for thermal barrier coating systems  

SciTech Connect

The new deposition process, combustion chemical vapor deposition, shows a great deal of promise in the area of thermal barrier coating systems. This technique produces dense, adherent coatings, and does not require a reaction chamber. Coatings can therefore be applied in the open atmosphere. The process is potentially suitable for producing high quality CVD coatings for use as interlayers between the bond coat and thermal barrier coating, and/or as overlayers, on top of thermal barrier coatings. In this report, the evaluation of alumina and ceria coatings on a nickel-chromium alloy is described.

Hampikian, J.M.; Carter, W.B. [Georgia Institute of Technology, Atlanta, GA (United States). School of Materials Science and Engineering

1995-12-31

61

Thermal, chemical, and mechanical cookoff modeling  

Microsoft Academic Search

A Thermally Reactive, Elastic-plastic eXplosive code, TREX, has been developed to analyze coupled thermal, chemical and mechanical effects associated with cookoff simulation of confined or unconfined energetic materials. In confined systems, pressure buildup precedes thermal runaway, and unconfined energetic material expands to relieve high stress. The model was developed based on nucleation, decomposition chemistry, and elastic\\/plastic mechanical behavior of a

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

1994-01-01

62

Chemical reactions in reverse micelle systems  

DOEpatents

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.

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

1993-08-24

63

Critical phenomena in a system with two competing exothermic and endothermic reactions. Part I, Thermal explosion  

SciTech Connect

This article examines the laws of thermal explosion for chemical reactions in which heat is absorbed and liberated simultaneously. The thermal equilibration time is much less than the characteristic times of the chemical reactions if the heats of reaction and activation energies are large. It is determined that the reaction rates vary during the establishment of thermal equilibrium, which alters the temperature conditions, but in that case the temperature change is quasistationary (e.g., at each instant the rate of heat production in the exothermic reaction is equal to the overall rate of heat absorption). A simple model case is considered which demonstrates the major states and transformation regions in the case of autocatalytic reactions, in which a wide range of relationships exist for the kinetics of the exothermic and endothermic reactions.

Borovikov, M.B.; Burovoi, I.A.; Gol'dshleger, U.I.

1984-07-01

64

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

NASA Technical Reports Server (NTRS)

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

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

2014-01-01

65

Excited state quenching via "unsuccessful" chemical reactions.  

PubMed

We discuss the results of recent photochemical reaction path computations on 1n,pi* azoalkanes interacting with a single quencher molecule. We provide computational and experimental evidence that there are two basic mechanisms for the true quenching of 1n,pi* states both based on unsuccessful chemical reactions. The first mechanism is based upon an unsuccessful hydrogen atom transfer and may occur through two different (direct and stepwise) routes. The second mechanism is based on an unsuccessful charge transfer reaction that occurs exclusively in a direct fashion. We show that the efficiency of the two quenching mechanisms is substantially due to the existence of two different types of conical intersections between the excited and ground state potential energy surfaces of the reacting bimolecular system. PMID:12659494

Sinicropi, Adalgisa; Nau, Werner M; Olivucci, Massimo

2002-08-01

66

Molecular Dynamics Simulations of Chemical Reactions for Use in Education  

ERIC Educational Resources Information Center

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…

Qian Xie; Tinker, Robert

2006-01-01

67

Chemical Reaction due to Stronger Ramachandran Interaction  

E-print Network

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

Andrew Das Arulsamy

2011-10-15

68

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

E-print Network

reaction network that performs a function: it uses autocatalysis in a time- controlled microfluidic device the reactions in space and time.1-5 An example of a chemical network is an array of 16 coupled reactionsA Synthetic Reaction Network: Chemical Amplification Using Nonequilibrium Autocatalytic Reactions

Ismagilov, Rustem F.

69

Continuous Time Markov Chain Models for Chemical Reaction  

E-print Network

Chapter 7 Continuous Time Markov Chain Models for Chemical Reaction Networks 7.1 Chemical reaction of the reactants and to the length of the time interval. In other words, since for the reaction to occur a molecule that is available at time t and is a positive constant, the reaction rate constant. Mathematically, Ft

Anderson, David F.

70

Reflections on the design of solar thermal chemical reactors: thoughts in transformation  

Microsoft Academic Search

We illustrate a process for designing solar thermal chemical reactors for industrial applications. The process is iterative and involves developing a numerical model of the reactor that links the radiation heat transfer to the other modes of heat transfer and the kinetics of the chemical reaction. Reactors that effectively convert solar energy to chemical energy match well the solar flux

R. Palumbo; M. Keunecke; S. Möller; A. Steinfeld

2004-01-01

71

Thermal maps of gases in heterogeneous reactions  

NASA Astrophysics Data System (ADS)

More than 85 per cent of all chemical industry products are made using catalysts, the overwhelming majority of which are heterogeneous catalysts that function at the gas-solid interface. Consequently, much effort is invested in optimizing the design of catalytic reactors, usually by modelling the coupling between heat transfer, fluid dynamics and surface reaction kinetics. The complexity involved requires a calibration of model approximations against experimental observations, with temperature maps being particularly valuable because temperature control is often essential for optimal operation and because temperature gradients contain information about the energetics of a reaction. However, it is challenging to probe the behaviour of a gas inside a reactor without disturbing its flow, particularly when trying also to map the physical parameters and gradients that dictate heat and mass flow and catalytic efficiency. Although optical techniques and sensors have been used for that purpose, the former perform poorly in opaque media and the latter perturb the flow. NMR thermometry can measure temperature non-invasively, but traditional approaches applied to gases produce signals that depend only weakly on temperature are rapidly attenuated by diffusion or require contrast agents that may interfere with reactions. Here we present a new NMR thermometry technique that circumvents these problems by exploiting the inverse relationship between NMR linewidths and temperature caused by motional averaging in a weak magnetic field gradient. We demonstrate the concept by non-invasively mapping gas temperatures during the hydrogenation of propylene in reactors packed with metal nanoparticles and metal-organic framework catalysts, with measurement errors of less than four per cent of the absolute temperature. These results establish our technique as a non-invasive tool for locating hot and cold spots in catalyst-packed gas-solid reactors, with unprecedented capabilities for testing the approximations used in reactor modelling.

Jarenwattananon, Nanette N.; Glöggler, Stefan; Otto, Trenton; Melkonian, Arek; Morris, William; Burt, Scott R.; Yaghi, Omar M.; Bouchard, Louis-S.

2013-10-01

72

Chemical Reaction Dynamics accompanying Electron-Transfer Osamu SUGINO  

E-print Network

transfer as does in the redox, while the latter appears in the photochemical reactions. Simulating bothChemical Reaction Dynamics accompanying Electron-Transfer Osamu SUGINO Institute for Solid State Physics, the University of Tokyo 5-1-5 Kashiwanoha, Chiba 277-8581 1. Introduction Many chemical reactions

Katsumoto, Shingo

73

Plasmon-driven sequential chemical reactions in an aqueous environment  

PubMed Central

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

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

2014-01-01

74

Continuous time Markov chain models for chemical reaction networks  

E-print Network

Continuous time Markov chain models for chemical reaction networks David F. Anderson Departments for the model for the reaction is that the probability of the reaction occurring in a small time interval (t and to the length of the time interval. In other words, since for the reaction to occur a molecule

Kurtz, Tom

75

CONTINUOUS TIME MARKOV CHAIN MODELS FOR CHEMICAL REACTION NETWORKS  

E-print Network

Chapter 1 CONTINUOUS TIME MARKOV CHAIN MODELS FOR CHEMICAL REACTION NETWORKS David F. Anderson of identifying the different time scales and deriving the reduced models. Keywords: Reaction network, Markov for the reaction is that the probability of the reaction occurring in a small time inter- val (t, t + t] should

Anderson, David F.

76

Spectroscopy and reactions of molecules important in chemical evolution  

NASA Technical Reports Server (NTRS)

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.

Becker, R. S.

1974-01-01

77

Coupled Thermal-Chemical-Mechanical Modeling of Validation Cookoff Experiments  

SciTech Connect

The cookoff of energetic materials involves the combined effects of several physical and chemical processes. These processes include heat transfer, chemical decomposition, and mechanical response. The interaction and coupling between these processes influence both the time-to-event and the violence of reaction. The prediction of the behavior of explosives during cookoff, particularly with respect to reaction violence, is a challenging task. To this end, a joint DoD/DOE program has been initiated to develop models for cookoff, and to perform experiments to validate those models. In this paper, a series of cookoff analyses are presented and compared with data from a number of experiments for the aluminized, RDX-based, Navy explosive PBXN-109. The traditional thermal-chemical analysis is used to calculate time-to-event and characterize the heat transfer and boundary conditions. A reaction mechanism based on Tarver and McGuire's work on RDX{sup 2} was adjusted to match the spherical one-dimensional time-to-explosion data. The predicted time-to-event using this reaction mechanism compares favorably with the validation tests. Coupled thermal-chemical-mechanical analysis is used to calculate the mechanical response of the confinement and the energetic material state prior to ignition. The predicted state of the material includes the temperature, stress-field, porosity, and extent of reaction. There is little experimental data for comparison to these calculations. The hoop strain in the confining steel tube gives an estimation of the radial stress in the explosive. The inferred pressure from the measured hoop strain and calculated radial stress agree qualitatively. However, validation of the mechanical response model and the chemical reaction mechanism requires more data. A post-ignition burn dynamics model was applied to calculate the confinement dynamics. The burn dynamics calculations suffer from a lack of characterization of the confinement for the flaw-dominated failure mode experienced in the tests. High-pressure burning rates are needed for more detailed post-ignition studies. Sub-models for chemistry, mechanical response and burn dynamics need to be validated against data from less complex experiments. The sub-models can then be used in integrated analysis for comparison with experimental data taken during integrated tests.

ERIKSON,WILLIAM W.; SCHMITT,ROBERT G.; ATWOOD,A.I.; CURRAN,P.D.

2000-11-27

78

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

ERIC Educational Resources Information Center

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)

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

2001-01-01

79

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...

80

Shock initiated thermal and chemical responses of HMX crystal from ReaxFF molecular dynamics simulation.  

PubMed

To gain an atomistic-level understanding of the thermal and chemical responses of condensed energetic materials under thermal shock, we developed a thermal shock reactive dynamics (TS-RD) computational protocol using molecular dynamics simulation coupled with ReaxFF force field. ?-Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) was selected as a a target explosive due to its wide usage in the military and industry. The results show that a thermal shock initiated by a large temperature gradient between the "hot" region and the "cold" region results in thermal expansion of the particles and induces a thermal-mechanical wave propagating back and forth in the system with an averaged velocity of 3.32 km s(-1). Heat propagating along the direction of thermal shock leads to a temperature increment of the system and thus chemical reaction initiation. Applying a continuum reactive heat conduction model combined with the temperature distribution obtained from the RD simulation, a heat conduction coefficient is derived as 0.80 W m(-1) K(-1). The chemical reaction mechanisms during thermal shock were analyzed, showing that the reaction is triggered by N-NO2 bond breaking followed by HONO elimination and ring fission. The propagation rates of the reaction front and reaction center are obtained to be 0.069 and 0.038 km s(-1), based on the time and spatial distribution of NO2. The pressure effect on the thermal shock was also investigated by employing uniaxial compression before the thermal shock. We find that compression significantly accelerates thermal-mechanical wave propagation and heat conduction, resulting in higher temperature and more excited molecules and thus earlier initiation and faster propagation of chemical reactions. PMID:24899535

Zhou, Tingting; Song, Huajie; Liu, Yi; Huang, Fenglei

2014-07-21

81

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

E-print Network

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

Anderson, James B.

82

Chemical Changes in Proteins Produced by Thermal Processing.  

ERIC Educational Resources Information Center

Discusses effects of thermal processing on proteins, focusing on (1) the Maillard reaction; (2) heat denaturation of proteins; (3) aggregation, precipitation, gelation, and degradation; and (4) other thermally induced protein reactions. Also discusses effects of thermal processing on muscle foods, egg proteins, fruits and vegetables, and cereal…

Dutson, T. R.; Orcutt, M. W.

1984-01-01

83

Chemical kinetics computer program for static and flow reactions  

NASA Technical Reports Server (NTRS)

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.

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

1972-01-01

84

Students’ Microscopic, Macroscopic, and Symbolic Representations of Chemical Reactions  

Microsoft Academic Search

This study examined the mental representations of chemical reactions used by six students (three male, three female) who achieved above-average grades in a college freshman chemistry class at a large midwestern university. The representations expressed by the students in structured interviews were categorized as microscopic, macroscopic, or symbolic representations of chemical reactions. The study revealed that the participants did make

Michael E. Hinton; Mary B. Nakhleh

1999-01-01

85

Solar-Thermal Fluid-Wall Reaction Processing  

DOEpatents

The present invention provides a method for carrying out high temperature thermal dissociation reactions requiring rapid-heating and short residence times using solar energy. In particular, the present invention provides a method for carrying out high temperature thermal reactions such as dissociation of hydrocarbon containing gases and hydrogen sulfide to produce hydrogen and dry reforming of hydrocarbon containing gases with carbon dioxide. In the methods of the invention where hydrocarbon containing gases are dissociated, fine carbon black particles are also produced. The present invention also provides solar-thermal reactors and solar-thermal reactor systems.

Weimer, A. W.; Dahl, J. K.; Lewandowski, A. A.; Bingham, C.; Raska Buechler, K. J.; Grothe, W.

2006-04-25

86

Advanced Chemical Heat Pumps Using Liquid-Vapor Reactions  

E-print Network

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

Kirol, L.

87

Deterministic Function Computation with Chemical Reaction Networks*  

PubMed Central

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

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

2013-01-01

88

An Analysis of the Algebraic Method for Balancing Chemical Reactions.  

ERIC Educational Resources Information Center

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…

Olson, John A.

1997-01-01

89

Chemical Looping Combustion Reactions and Systems  

SciTech Connect

Chemical Looping Combustion (CLC) is one promising fuel-combustion technology, which can facilitate economic CO{sub 2} 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 topical report discusses the results of four complementary efforts: (5.1) the development of process and economic models to optimize important design considerations, such as oxygen carrier circulation rate, temperature, residence time; (5.2) the development of high-performance simulation capabilities for fluidized beds and the collection, parameter identification, and preliminary verification/uncertainty quantification; (5.3) the exploration of operating characteristics in the laboratoryscale bubbling bed reactor, with a focus on the oxygen carrier performance, including reactivity, oxygen carrying capacity, attrition resistance, resistance to deactivation, cost and availability; and (5.4) the identification of kinetic data for copper-based oxygen carriers as well as the development and analysis of supported copper oxygen carrier material. Subtask 5.1 focused on the development of kinetic expressions for the Chemical Looping with Oxygen Uncoupling (CLOU) process and validating them with reported literature data. The kinetic expressions were incorporated into a process model for determination of reactor size and oxygen carrier circulation for the CLOU process using ASPEN PLUS. An ASPEN PLUS process model was also developed using literature data for the CLC process employing an iron-based oxygen carrier, and the results of the process model have been utilized to perform a relative economic comparison. In Subtask 5.2, the investigators studied the trade-off between modeling approaches and available simulations tools. They quantified uncertainty in the high-performance computing (HPC) simulation tools for CLC bed applications. Furthermore, 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.

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

90

Multidimensional thermal-chemical cookoff modeling  

SciTech Connect

Multidimensional thermal/chemical modeling is an essential step in the development of a predictive capability for cookoff of energetic materials in systems subjected to abnormal thermal environments. COYOTE II is a state-of-the-art two- and three-dimensional finite element code for the solution of heat conduction problems including surface-to-surface thermal radiation heat transfer and decomposition chemistry. Multistep finite rate chemistry is incorporated into COYOTE II using an operator-splitting methodology; rate equations are solved element-by-element with a modified matrix-free stiff solver, CHEMEQ. COYOTE II is purposely designed with a user-oriented input structure compatible with the database, the pre-processing mesh generation, and the post-processing tools for data visualization shared with other engineering analysis codes available at Sandia National Laboratories. As demonstrated in a companion paper, decomposition during cookoff in a confined or semi-confined system leads to significant mechanical behavior. Although mechanical effect are not presently considered in COYOTE II, the formalism for including mechanics in multidimensions is under development.

Baer, M.R.; Gross, R.J.; Gartling, D.K.; Hobbs, M.L.

1994-08-01

91

Thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates of BTATz-CMDB propellant.  

PubMed

The composite modified double base (CMDB) propellants (nos. RB0601 and RB0602) containing 3,6-bis (1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine (BTATz) without and with the ballistic modifier were prepared and their thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates were investigated. The results show that there are three mass-loss stages in TG curve and two exothermic peaks in DSC curve for the BTATz-CMDB propellant. The first two mass-loss stages occur in succession and the temperature ranges are near apart, and the decomposition peaks of the two stages overlap each other, inducing only one visible exothermic peak appear in DSC curve during 350-550 K. The reaction mechanisms of the main exothermal decomposition processes of RB0601 and RB0602 are all classified as chemical reaction, the mechanism functions are f(alpha)=(1-alpha)(2), and the kinetic equations are dalpha/dt = 10(19.24)(1-alpha)(2)e(-2.32x10(4)/T) and dalpha/dt = 10(20.32)(1-alpha)(2)e(-2.32x10(4)/T). The thermal safety evaluation on the BTATz-CMDB propellants was obtained. With the substitution of 26% RDX by BTATz and with the help of the ballistic modifier in the CMDB propellant formulation, the burning rate can be improved by 89.0% at 8 MPa and 47.1% at 22 MPa, the pressure exponent can be reduced to 0.353 at 14-20 MPa. PMID:20542638

Yi, Jian-Hua; Zhao, Feng-Qi; Wang, Bo-Zhou; Liu, Qian; Zhou, Cheng; Hu, Rong-Zu; Ren, Ying-Hui; Xu, Si-Yu; Xu, Kang-Zhen; Ren, Xiao-Ning

2010-09-15

92

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

ERIC Educational Resources Information Center

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)

Wright, Stephen W.

2002-01-01

93

Thermal conductivity characteristics of dewatered sewage sludge by thermal hydrolysis reaction.  

PubMed

The purpose of this study is to quantify the thermal conductivity of sewage sludge related to reaction temperature for the optimal design of a thermal hydrolysis reactor. We continuously quantified the thermal conductivity of dewatered sludge related to the reaction temperature. As the reaction temperature increased, the dewatered sludge is thermally liquefied under high temperature and pressure by the thermal hydrolysis reaction. Therefore, the bound water in the sludge cells comes out as free water, which changes the dewatered sludge from a solid phase to slurry in a liquid phase. As a result, the thermal conductivity of the sludge was more than 2.64 times lower than that of the water at 20. However, above 200, it became 0.704 W/m* degrees C, which is about 4% higher than that of water. As a result, the change in physical properties due to thermal hydrolysis appears to be an important factor for heat transfer efficiency. Implications: The thermal conductivity of dewatered sludge is an important factor the optimal design of a thermal hydrolysis reactor. The dewatered sludge is thermally liquefied under high temperature and pressure by the thermal hydrolysis reaction. The liquid phase slurry has a higher thermal conductivity than pure water. PMID:25562934

Song, Hyoung Woon; Park, Keum Joo; Han, Seong Kuk; Jung, Hee Suk

2014-12-01

94

Nonstatistical Dynamics in Thermal Reactions of Polyatomic Molecules  

NASA Astrophysics Data System (ADS)

A brief review is presented of post-RRKM models for unimolecular reaction kinetics. The dynamics of the gas-phase SN2 reaction are discussed, and the important role of phase-space bottlenecks is highlighted. The remainder of the review is devoted to experimental and trajectory simulation results on thermal reactions of organic molecules that exhibit nonstatistical dynamics quite unlike that seen in the SN2 reaction. Specifically, the intermediates generated in these reactions decay much faster than RRKM theory would predict, and often with bimodal or multimodal lifetime distributions. A qualitative model for this behavior based on overlaps of transitional regions in the molecular phase space is discussed.

Carpenter, Barry K.

2005-05-01

95

Chemical potential and thermodynamic functions of thermal radiation  

NASA Astrophysics Data System (ADS)

Thermodynamic functions of the photon number of thermal radiation are described. The temperature dependence ? = 3.602 kT of the chemical potential of thermal radiation is found by differentiation of these functions.

Laptev, V. I.

2010-02-01

96

Heterogeneous reactions in non-thermal plasma flue gas desulfurization  

Microsoft Academic Search

This paper demonstrates that the main reaction mechanism of flue gas desulfurization (FGD) by pulsed corona discharge or electron beam, which generates non-thermal plasmas (NTP), is heterogeneous. The experimental results in this paper suggest that the main reactions in FGD by NTP are activated reactions in liquid phase. According to Huie’s mechanism, it is considered that the ionic radical SO-3

Ruinian Li; Keping Yan; Jinsong Miao; Xiaoli Wu

1998-01-01

97

Morphological changes of amphiphilic molecular assemblies induced by chemical reactions.  

PubMed

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

Nakagawa, Koh M; Noguchi, Hiroshi

2015-02-01

98

Non-equilibrium effects in high temperature chemical reactions  

NASA Technical Reports Server (NTRS)

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.

Johnson, Richard E.

1987-01-01

99

Morphological changes of amphiphilic molecular assemblies induced by chemical reaction  

E-print Network

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

Koh M. Nakagawa; Hiroshi Noguchi

2014-11-21

100

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...

101

Chemical Master versus Chemical Langevin for First-Order Reaction Networks  

E-print Network

Chemical Master versus Chemical Langevin for First-Order Reaction Networks Desmond J. Higham Raya in computational cell biology, and in this case, the interactions are typically first-order. The Chemical Langevin effectively. In this work, we obtain expressions for the first and second moments of the Chemical Langevin

Mottram, Nigel

102

Photo, thermal and chemical degradation of riboflavin  

PubMed Central

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

Kazi, Sadia Hafeez; Ahmed, Sofia; Anwar, Zubair; Ahmad, Iqbal

2014-01-01

103

Kinetics of Chemical Reactions in Flames  

NASA Technical Reports Server (NTRS)

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.

Zeldovich, Y.; Semenov, N.

1946-01-01

104

Effect of curvature of the reaction path on dynamic effects in endothermic chemical reactions and product energies in exothermic reactions  

Microsoft Academic Search

Collinear quasiclassical trajectories are examined for two realistic potential energy surfaces for atom?diatomic molecule reactions for two reaction attributes: (1) vibrational energy of the products of a thermal?energy exothermic reaction; (2) threshold energy for endothermic reaction of ground?state reagents. Eight different mass combinations are studied. The potential energy surfaces differ primarily in the amount of potential energy released in an

James W. Duff; Donald G. Truhlar

1975-01-01

105

Quantum Chemical Approach to Estimating the Thermodynamics of Metabolic Reactions  

NASA Astrophysics Data System (ADS)

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.

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

2014-11-01

106

Quantum chemical approach to estimating the thermodynamics of metabolic reactions.  

PubMed

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. PMID:25387603

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

2014-01-01

107

Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks  

ERIC Educational Resources Information Center

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…

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

2011-01-01

108

Is the simplest chemical reaction really so simple?  

PubMed Central

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

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

2014-01-01

109

Elementary reaction modeling of solid oxide electrolysis cells: Main zones for heterogeneous chemical/electrochemical reactions  

NASA Astrophysics Data System (ADS)

A theoretical model of solid oxide electrolysis cells considering the heterogeneous elementary reactions, electrochemical reactions and the transport process of mass and charge is applied to study the relative performance of H2O electrolysis, CO2 electrolysis and CO2/H2O co-electrolysis and the competitive behavior of heterogeneous chemical and electrochemical reactions. In cathode, heterogeneous chemical reactions exist near the outside surface and the electrochemical reactions occur near the electrolyte. According to the mathematical analysis, the mass transfer flux D ?c determines the main zone size of heterogeneous chemical reactions, while the charge transfer flux ? ?V determines the other one. When the zone size of heterogeneous chemistry is enlarged, more CO2 could react through heterogeneous chemical pathway, and polarization curves of CO2/H2O co-electrolysis could be prone to H2O electrolysis. Meanwhile, when the zone size of electrochemistry is enlarged, more CO2 could react through electrochemical pathway, and polarization curves of CO2/H2O co-electrolysis could be prone to CO2 electrolysis. The relative polarization curves, the ratio of CO2 participating in electrolysis and heterogeneous chemical reactions, the mass and charge transfer flux and heterogeneous chemical/electrochemical reaction main zones are simulated to study the effects of cathode material characteristics (porosity, particle diameter and ionic conductivity) and operating conditions (gas composition and temperature).

Li, Wenying; Shi, Yixiang; Luo, Yu; Cai, Ningsheng

2015-01-01

110

Mineralization of hazardous chemicals by heme reaction  

SciTech Connect

The catalytic degradation of pentachlorophenol contaminated soil by heme and hydrogen peroxide has been reported. Here we studied evidence for the mechanism and mineralization by the heme catalyzed reaction for hazardous organopollutants. Ferryl heme radical and non-radical ferryl heme were generated rapidly by the interaction of heme and hydrogen peroxide (H{sub 2}O{sub 2}). The activated heme radical could initiate the oxidation of 5-aminosalicylic acid (5-ASA). The reactions by heme with H{sub 2}O{sub 2} could support the redox cycling between the ferryl species of heme and 5-ASA as the mechanistic routes of the heme catalyzed reaction. Hazardous compounds such as pentachlorophenol, phenanthrene and benzota[a]pyrene were mineralized 20, 6, and 7%, respectively, with 30 mM heme and 1500 mM H{sub 2}O{sub 2} after 24 hr reaction. This catalyzed degradation of organopollutants could be used as a novel technology for hazardous waste remediation.

Kang, G.; Jung, J.; Park, K. [Hankuk Univ. of Foreign Studies, Seoul (Korea, Democratic People`s Republic of); Stevens, D.K. [Utah State Univ., Logan, UT (United States)

1995-12-31

111

PERSPECTIVE Is the simplest chemical reaction really  

E-print Network

Aoizd a Department of Chemistry, Stanford University, Stanford, CA 94305-5080; b Max Born Institute The reaction in which a hydrogen atom collides with a hydrogen molecule to form a new hydrogen molecule plus (Fig. 2) in which the angle between the forming Ha­Hb bond and the breaking Hb­Hc bond is held fixed

Zare, Richard N.

112

Results of the 2010 Survey on Teaching Chemical Reaction Engineering  

ERIC Educational Resources Information Center

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…

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

2012-01-01

113

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

NASA Astrophysics Data System (ADS)

The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman-Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal-diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode.

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

2011-03-01

114

Probing Isotope Effects in Chemical Reactions Using Single Ions  

SciTech Connect

Isotope effects in reactions between Mg{sup +} in the 3p {sup 2}P{sub 3/2} excited state and molecular hydrogen at thermal energies are studied through single reaction events. From only {approx}250 reactions with HD, the branching ratio between formation of MgD{sup +} and MgH{sup +} is found to be larger than 5. From an additional 65 reactions with H{sub 2} and D{sub 2} we find that the overall fragmentation probability of the intermediate MgH{sub 2}{sup +}, MgHD{sup +}, or MgD{sub 2}{sup +} complexes is the same. Our study shows that few single ion reactions can provide quantitative information on ion-neutral reactions. Hence, the method is well suited for reaction studies involving rare species, e.g., rare isotopes or short-lived unstable elements.

Staanum, Peter F.; Hoejbjerre, Klaus; Drewsen, Michael [QUANTOP - Danish National Research Foundation Centre for Quantum Optics, University of Aarhus, 8000 Aarhus (Denmark); Department of Physics and Astronomy, University of Aarhus, 8000 Aarhus (Denmark); Wester, Roland [Physikalisches Institut, Universitaet Freiburg, Hermann-Herder-Strasse 3, 79104 Freiburg (Germany)

2008-06-20

115

Thermochemistry of silicon carbide growth by chemical transport reactions  

Microsoft Academic Search

Chemical Vapour Transport is a well known process widely used for the growth of monocrystals. This paper is a thermodynamic overview of different heterogeneous chemical systems, promising for the growth of silicon carbide by means of chemical transport reactions. The systems are Si-C-Y where Y is oxygen or a chalcogen (S, Se) and Si-C-H-X where X is an halogen (Cl,

D. Chaussende; G. Ferro; Y. Monteil; C. Brylinski; J. Bouix

2001-01-01

116

LIGAND: Database of Chemical Compounds and Reactions in Biological Pathways  

NSDL National Science Digital Library

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

117

Chemical memory reactions induced bursting dynamics in gene expression.  

PubMed

Memory is a ubiquitous phenomenon in biological systems in which the present system state is not entirely determined by the current conditions but also depends on the time evolutionary path of the system. Specifically, many memorial phenomena are characterized by chemical memory reactions that may fire under particular system conditions. These conditional chemical reactions contradict to the extant stochastic approaches for modeling chemical kinetics and have increasingly posed significant challenges to mathematical modeling and computer simulation. To tackle the challenge, I proposed a novel theory consisting of the memory chemical master equations and memory stochastic simulation algorithm. A stochastic model for single-gene expression was proposed to illustrate the key function of memory reactions in inducing bursting dynamics of gene expression that has been observed in experiments recently. The importance of memory reactions has been further validated by the stochastic model of the p53-MDM2 core module. Simulations showed that memory reactions is a major mechanism for realizing both sustained oscillations of p53 protein numbers in single cells and damped oscillations over a population of cells. These successful applications of the memory modeling framework suggested that this innovative theory is an effective and powerful tool to study memory process and conditional chemical reactions in a wide range of complex biological systems. PMID:23349679

Tian, Tianhai

2013-01-01

118

Coupled Thermal-Chemical-Mechanical Modeling of Validation Cookoff Experiments  

Microsoft Academic Search

The cookoff of energetic materials involves the combined effects of several physical and chemical processes. These processes include heat transfer, chemical decomposition, and mechanical response. The interaction and coupling between these processes influence both the time-to-event and the violence of reaction. The prediction of the behavior of explosives during cookoff, particularly with respect to reaction violence, is a challenging task.

WILLIAM W. ERIKSON; ROBERT G. SCHMITT; A. I. ATWOOD; P. D. CURRAN

2000-01-01

119

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

PubMed

Understanding the microscopic elementary process of chemical reactions, especially in condensed phase, is highly desirable for improvement of efficiencies in industrial chemical processes. Here we show an approach to gaining new insights into elementary reactions in condensed phase by combining quantum chemical calculations with a single-molecule analysis. Elementary chemical reactions in liquid-phase, revealed from quantum chemical calculations, are studied by tracking the fluorescence of single dye molecules undergoing a reversible redox process. Statistical analyses of single-molecule trajectories reveal molecular reaction kinetics and dynamics of elementary reactions. The reactivity dynamic fluctuations of single molecules are evidenced and probably arise from either or both of the low-frequency approach of the molecule to the internal surface of the SiO2 nanosphere or the molecule diffusion-induced memory effect. This new approach could be applied to other chemical reactions in liquid phase to gain more insight into their molecular reaction kinetics and the dynamics of elementary steps. PMID:24963600

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

2014-01-01

120

[Research on chemical reactions during ginseng processing].  

PubMed

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

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

2014-10-01

121

Earth's interdependent thermal, structural, and chemical evolution  

NASA Astrophysics Data System (ADS)

The popular view that 30-55% of Earth's global power is primordial, with deep layers emanating significant power, rests on misunderstandings and models that omit magmatism and outgassing. These processes link Earth's chemical and thermal evolution, while creating layers, mainly because magmas transport latent heat and radioactive isotopes rapidly upwards. We link chemistry to heat flow, measured and theoretical, to understand the interior layering and workings. Quasi-steady state conditions describe most of Earth's history: (1) Accretion was cold and was not a source of deep heat. (2) Friction during core formation cannot have greatly heated the interior (thermodynamics plus buoyancy). (3) Conduction is the governing microscopic mechanism in the deep Earth. (4) Using well-constrained values of thermal conductivity (k), we find that homogeneously distributed radionuclides provide extremely high internal temperature (T) under radial symmetry. Moreover, for any given global power, sequestering heat producing elements into the upper mantle reduces Earth's central temperature by a factor of 10 from a homogeneous distribution. Hence, (5) core formation was a major cooling event. From modern determinations of k(T) we provide a reference conductive geotherm. Present-day global power of 30 TW from heat flux measurements and sequestering of heat producing elements in the upper mantle and transition zone, produces nearly isothermal T = 5300 K below 670 km, which equals experimentally determined freezing of pure Fe0 at the inner core boundary. Core freezing buffers the interior temperatures, while the Sun constrains the surface temperature, providing steady state conditions: Earth's deep interior is isothermal due to these constraints, low flux and high k. Our geotherms point to a stagnant lower mantle and convection above 670 km. Rotational flattening cracks the brittle lithosphere, providing paths for buoyant magmas to ascend. Release of latent heat augments the conductive gradient, making these oriented cracks equivalent to vertical hot plates, thereby imparting a large lateral component and preferred direction to upper mantle circulation. The latent heat release limits lower mantle flux to 1 TW and its temperature change to 500 K High lower mantle temperatures require a bulk composition more like the Moon than chondrites, which is consistent with proposals that calcuim-aluminum inclusions constitute a presolar reservoir near the nebula center. From oxygen isotopes and chemical composition of meteorites, we provide a new class of meteoritic model, based on mixing and not volatile element depletion, for the types and amounts of Earth's heat producing elements. Our model permits crust preservation at ~ 4 Ga, whereas hypothetical primordial heat would delay this significantly. The lower mantle is chemically distinct from the peridotite (chondritic) upper mantle, being comprised of refractory phases with much higher Ca, Al and Ti contents than previously considered. Huge changes in chemistry and temperature are required across the transition zone and profoundly affect the workings of the Earth. The lower mantle formed during gravitational sorting very early on, as did the core, in the drive towards energy minimization.

Hofmeister, A.; Criss, R. E.

2012-12-01

122

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

PubMed

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

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

2014-01-01

123

Laser cutting with chemical reaction assist  

DOEpatents

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.

Gettemy, D.J.

1992-11-17

124

Chemical vapor detection with a multispectral thermal imager  

E-print Network

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

Chang, Chein-I

125

An Efficient Chemical Reaction Optimization Algorithm for Multiobjective Optimization.  

PubMed

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

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

2014-10-30

126

Process for the preparation of hydrogen. [series of chemical reactions based on cadmium with water reaction  

Microsoft Academic Search

Hydrogen is produced from water by the addition of heat to a series of chemical reactions which comprise the reaction of cadmium with water, and the subsequent recovery of the cadmium for re-use. The equipment used to produce the hydrogen requires only the input of water and heat to produce an output of hydrogen and oxygen gas.

duPont

1977-01-01

127

Nonstatistical dynamics in thermal reactions of polyatomic molecules.  

PubMed

A brief review is presented of post-RRKM models for unimolecular reaction kinetics. The dynamics of the gas-phase S(N)2 reaction are discussed, and the important role of phase-space bottlenecks is highlighted. The remainder of the review is devoted to experimental and trajectory simulation results on thermal reactions of organic molecules that exhibit nonstatistical dynamics quite unlike that seen in the S(N)2 reaction. Specifically, the intermediates generated in these reactions decay much faster than RRKM theory would predict, and often with bimodal or multimodal lifetime distributions. A qualitative model for this behavior based on overlaps of transitional regions in the molecular phase space is discussed. PMID:15796696

Carpenter, Barry K

2005-01-01

128

Primary Chemical Reactions Induced by Radioactive Nuclear Transformations  

SciTech Connect

A series of chemical reactions is suggested to describe primary chemical transformations induced by Auger electrons from radioactive nuclear decay in glassy and crystalline frozen aqueous media. The mechanism is based on Moessbauer emission spectroscopy data supplemented by data on reactions in the tracks of fast positrons and electrons in an aqueous medium. It is shown that variation of temperature, the degree of crystallinity, the concentration of electron acceptors, etc., results in correlated changes in the yields of the final reaction products--Fe{sup 2+}, Fe{sup 3+} or Sn{sup 2+}, Sn{sup 4+} ions, positronium atoms, and molecular radiolytic hydrogen. These correlations indicate the similarity of chemical processes in the nanometer vicinity of decayed {sup 57}Co and {sup 119m}Sn nuclei and in the tracks of fast positrons and electrons. This similarity is caused by the same behavior of secondary intratrack electrons produced due to ionization losses of fast positrons, electrons, and Auger electrons.

Byakov, V.M.; Stepanov, S.V. [Institute of Theoretical and Experimental Physics, Bol'shaya Cheremushkinskaya ul. 25, Moscow, 117259 (Russian Federation); Kulikov, L.A.; Perfil'ev, Yu.D. [Moscow State University, Vorob'evy gory, Moscow, 119899 (Russian Federation)

2005-06-01

129

Hierarchy of reaction dynamics in a thermally fluctuating environment.  

PubMed

Nonlinear dynamics in the passage over a rank-one saddle is investigated as a function of temperature in the presence of stochastic, thermal fluctuation. The analyses are based on a framework we developed recently adopting a multidimensional underdamped Langevin equation (without any assumption for the form of the potential of mean force). The framework can in principle provide a single coordinate to enable us to predict the final destination of the reaction in a thermally fluctuating media. At each temperature, the preciseness or the error of the reaction coordinate is evaluated in capturing the true reaction dynamics at different levels of approximations. By using the Müller-Brown potential as an illustrative example, it is found that a hierarchy of dynamical structure exists in the region of a rank-one saddle, in which the crossing dynamics qualitatively changes as the temperature increases. We discuss the mechanism of how the reaction coordinate persists, which provides a boundary of the reaction to divide the phase space into the reactive and the nonreactive regions, even in the presence of thermal fluctuation. PMID:20544103

Kawai, Shinnosuke; Komatsuzaki, Tamiki

2010-07-21

130

Kramers problem for nonequilibrium current-induced chemical reactions  

NASA Astrophysics Data System (ADS)

We discuss the use of tunneling electron current to control and catalyze chemical reactions. Assuming the separation of time scales for electronic and nuclear dynamics we employ Langevin equation for a reaction coordinate. The Langevin equation contains nonconservative current-induced forces and gives nonequilibrium, effective potential energy surface for current-carrying molecular systems. The current-induced forces are computed via Keldysh nonequilibrium Green's functions. Once a nonequilibrium, current-depended potential energy surface is defined, the chemical reaction is modeled as an escape of a Brownian particle from the potential well. We demonstrate that the barrier between the reactant and the product states can be controlled by the bias voltage. When the molecule is asymmetrically coupled to the electrodes, the reaction can be catalyzed or stopped depending on the polarity of the tunneling current.

Dzhioev, Alan A.; Kosov, D. S.

2011-08-01

131

Theoretical studies of the dynamics of chemical reactions  

SciTech Connect

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

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

1993-12-01

132

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

NASA Technical Reports Server (NTRS)

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

Gokoglu, Suleyman A.

1988-01-01

133

On the role of chemical reactions in initiating ultraviolet laser ablation in poly(methyl methacrylate)  

SciTech Connect

The role of chemical reactions is investigated versus the thermal and mechanical processes occurring in a polymer substrate during irradiation by a laser pulse and subsequent ablation. Molecular dynamics simulations with an embedded Monte Carlo based reaction scheme were used to study ultraviolet ablation of poly(methyl methacrylate) at 157 nm. We discuss the onset of ablation, the mechanisms leading to ablation, and the role of stress relaxation of the polymer matrix during ablation. Laser induced heating and chemical decomposition of the polymer substrate are considered as ablation pathways. It is shown that heating the substrate can set off ablation via mechanical failure of the material only for very short laser pulses. For longer pulses, the mechanism of ejection is thermally driven limited by the critical number of bonds broken in the substrate. Alternatively, if the photon energy goes towards direct bond breaking, it initiates chemical reactions, polymer unzipping, and formation of gaseous products, leading to a nearly complete decomposition of the top layers of substrates. The ejection of small molecules has a hollowing out effect on the weakly connected substrates which can lead to lift-off of larger chunks. Excessive pressure buildup upon the creation of gaseous molecules does not lead to enhanced yield. The larger clusters are thermally ejected, and an entrainment of larger polymer fragments in gaseous molecules is not observed.

Prasad, Manish; Conforti, Patrick F.; Garrison, Barbara J. [Department of Chemistry, 104 Chemistry Building, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States)

2007-05-15

134

Asymmetric chemical reactions by polarized quantum beams  

NASA Astrophysics Data System (ADS)

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 (2009). 4) V.I.Burkov, L.A.Goncharova, G.A.Gusev, H.Hashimoto, F.Kaneko, T.Kaneko, K. Kobayashi, H.Mita, E.V.Moiseenko, T.Ogawa, N.G.Poluhina, T.Saito, S.Shima, J.Takahashi, M.Tanaka, Y.Tao, V.A.Tsarev, J.Xu, H.Yabuta, K.Yagi-Watanabe, H.Yan, G.Zhang, Origins Life Evol. Biosphere, 39 295 (2009).

Takahashi, Jun-Ichi; Kobayashi, Kensei

135

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...

136

Chemical generation of atomic iodine for chemical oxygen iodine laser. I. Modelling of reaction systems  

NASA Astrophysics Data System (ADS)

The mathematical modelling of reaction systems for chemical generation of atomic iodine is presented. This process is aimed to be applied in the chemical oxygen-iodine laser (COIL), where it can save a substantial part of energy of singlet oxygen and so increase the laser output power. In the suggested method, gaseous reactants for I atoms generation are admixed into the COIL primary gas flow containing singlet oxygen. Two reaction systems were proposed, based on the reaction of hydrogen iodide with chemically generated atomic fluorine or chlorine. It was found that the reaction path via Cl atoms better matches the experimental conditions of COIL with a yield of atomic iodine of up to 67%. As a result of modelling, a suitable reaction system and design of experimental arrangement for the effective production of atomic iodine in laser conditions were found.

Jirásek, Vít.; Špalek, Otomar; Kodymová, Jarmila; ?enský, Miroslav

2001-07-01

137

Modeling pore collapse and chemical reactions in shock-loaded HMX crystals  

NASA Astrophysics Data System (ADS)

The localization of deformation in shock-loaded crystals of high explosive material leads to the formation of hot spots, which, if hot enough, initiate chemical reactions. The collapse of microscopic pores contained within a crystal is one such process that localizes energy and generates hot spots. Given the difficulty of resolving the details of pore collapse in shock compression experiments, it is useful to study the problem using direct numerical simulation. In this work, we focus on simulating the shock-induced closure of a single pore in crystalline ?-HMX using a multiphysics finite element code. To address coupled thermal-mechanical-chemical responses, the model incorporates a crystal-mechanics-based description of thermoelasto-viscoplasticity, the crystal melting behavior, and transformation kinetics for a single-step decomposition reaction. The model is applied to stress wave amplitudes of up to 11 GPa to study the details of pore collapse, energy localization, and the early stages of reaction initiation.

Austin, R. A.; Barton, N. R.; Howard, W. M.; Fried, L. E.

2014-05-01

138

Determining Interconnections in Chemical Reaction Networks Antonis Papachristodoulou and Ben Recht  

E-print Network

functionality in the neighborhood of the nominal reaction rates. But most importantly, networks are rarelyDetermining Interconnections in Chemical Reaction Networks Antonis Papachristodoulou and Ben Recht Abstract-- We present a methodology for robust determina- tion of chemical reaction network

Nowak, Robert

139

Chemical pathways in ultracold reactions of SrF molecules  

SciTech Connect

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.

Meyer, Edmund R.; Bohn, John L. [JILA, NIST, and Department of Physics, University of Colorado, Boulder, Colorado 80309-0440 (United States)

2011-03-15

140

Researches on Preliminary Chemical Reactions in Spark-Ignition Engines  

NASA Technical Reports Server (NTRS)

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.

Muehlner, E.

1943-01-01

141

Favorite Demonstration: Demonstrating Indigo Carmine Oxidation-Reduction Reactions--A Choreography for Chemical Reactions  

NSDL National Science Digital Library

The indigo carmine demonstration (Ferguson et al. 1973), also referred to as a traffic-light demonstration (Flinn Scientific 2007a), is an example of a set of oxidation-reduction reactions that occurs within one solution. This type of demonstration can be used to introduce the concept of chemical reaction to undergraduate nonscience majors. Through their observations guided by the instructor, students begin to develop and construct the following concepts: color changes, reaction rates, reversible reactions, energy requirements (endothermic/exothermic), and equilibrium.

Majerich, David M.; Schmuckler, Joseph S.

2008-03-01

142

Program Helps To Determine Chemical-Reaction Mechanisms  

NASA Technical Reports Server (NTRS)

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.

Bittker, D. A.; Radhakrishnan, K.

1995-01-01

143

2011 Chemical Reactions at Surfaces Gordon Research Conference  

SciTech Connect

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.

Peter Stair

2011-02-11

144

Molecular Codes in Biological and Chemical Reaction Networks  

PubMed Central

Shannon’s theory of communication has been very successfully applied for the analysis of biological information. However, the theory neglects semantic and pragmatic aspects and thus cannot directly be applied to distinguish between (bio-) chemical systems able to process “meaningful” information from those that do not. Here, we present a formal method to assess a system’s semantic capacity by analyzing a reaction network’s capability to implement molecular codes. We analyzed models of chemical systems (martian atmosphere chemistry and various combustion chemistries), biochemical systems (gene expression, gene translation, and phosphorylation signaling cascades), an artificial chemistry, and random reaction networks. Our study suggests that different chemical systems posses different semantic capacities. No semantic capacity was found in the model of the martian atmosphere chemistry, the studied combustion chemistries, and highly connected random networks, i.e. with these chemistries molecular codes cannot be implemented. High semantic capacity was found in the studied biochemical systems and in random reaction networks where the number of second order reactions is twice the number of species. We conclude that our approach can be applied to evaluate the information processing capabilities of a chemical system and may thus be a useful tool to understand the origin and evolution of meaningful information, e.g. in the context of the origin of life. PMID:23372756

Görlich, Dennis; Dittrich, Peter

2013-01-01

145

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...

146

Jet quenching and holographic thermalization with a chemical potential  

NASA Astrophysics Data System (ADS)

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

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

2014-03-01

147

Dissipation Scale Fluctuations and Chemical Reaction Rates in Turbulent Flows  

E-print Network

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

Victor Yakhot

2007-06-29

148

Chemical generation of atomic iodine for chemical oxygen–iodine laser. I. Modelling of reaction systems  

Microsoft Academic Search

The mathematical modelling of reaction systems for chemical generation of atomic iodine is presented. This process is aimed to be applied in the chemical oxygen–iodine laser (COIL), where it can save a substantial part of energy of singlet oxygen and so increase the laser output power. In the suggested method, gaseous reactants for I atoms generation are admixed into the

V??t Jirásek; Otomar Špalek; Jarmila Kodymová; Miroslav ?enský

2001-01-01

149

The role of chemical reactions in the Chernobyl accident  

SciTech Connect

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.

Grishanin, E. I., E-mail: egrishanin@orexovo.net [Russian Research Center Kurchatov Institute (Russian Federation)

2010-12-15

150

Multiscale stochastic simulations of chemical reactions with regulated scale separation  

SciTech Connect

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

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

2013-07-01

151

Theoretical Chemical Dynamics Studies of Elementary Combustion Reactions  

SciTech Connect

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.

Donald L. Thompson

2006-04-27

152

Shock-induced chemical reactions in organic materials and explosives  

NASA Astrophysics Data System (ADS)

Interrogating chemical reactions behind a shock front is immensely difficult and, as a result, the details of shock-induced chemistry remain poorly understood. Previous research has shown that dimerizations, polymerizations, ring-opening and decomposition reactions can occur under shock compression, depending on molecular structure. Questions regarding the thresholds for incipient reaction, the nature of first and subsequent reaction steps, and the influence of shock input conditions on reaction kinetics remain to be answered. Here, we have applied in-situ electromagnetic gauging at multiple Lagrangian positions to elucidate the evolution of multiple-wave structures associated with shock-induced reactions of several simple functional groups: carbon-carbon double (-C=C-) and triple bonds, and nitriles. The relative order of group reactivity under single shock conditions for these simple molecules is discussed. From measurements of the reactive flow, we have obtained detailed information about the temporal evolution of the waves, and global kinetic rates associated with transformation(s) between partially- and fully-reacted states. Near the reactive thresholds, evolution in particle velocities point to reaction timescales on the order of tens-to-hundreds of nanoseconds. We further compare evidence of reaction from gas gun-driven experiments to recent results using laser-driven shocks. Spectroscopic details will be presented from both types of experiments.

Dattelbaum, Dana; Sheffield, Stephen; McGrane, Shawn; Goodwin, Peter

2012-02-01

153

A Review of Study on Thermal Energy Transport System by Synthesis and Decomposition Reactions of Methanol  

NASA Astrophysics Data System (ADS)

The study on thermal energy transport system by synthesis and decomposition reactions of methanol was reviewed. To promote energy conservation and global environment protection, a two-step liquid-phase methanol synthesis process, which starts with carbonylation of methanol to methyl formate, then followed by the hydrogenolysis of the formate, was studied to recover wasted or unused discharged heat from industrial sources for the thermal energy demands of residential and commercial areas by chemical reactions. The research and development of the system were focused on the following three points. (1) Development of low-temperature decomposition and synthetic catalysts, (2) Development of liquid phase reactor (heat exchanger accompanying chemical reaction), (3) Simulation of the energy transport efficiency of entire system which contains heat recovery and supply sections. As the result of the development of catalyst, promising catalysts which agree with the development purposes for the methyl formate decomposition reaction and the synthetic reaction are being developed though some studies remain for the methanol decomposition and synthetic reactions. In the fundamental development of liquid phase reactor, the solubilities of CO and H2 gases in methanol and methyl formate were measured by the method of total pressure decrease due to absorption under pressures up to 1500kPa and temperatures up to 140°C. The diffusivity of CO gas in methanol was determined by measuring the diameter and solution time of single CO bubbles in methanol. The chemical reaction rate of methanol synthesis by hydrogenolysis of methyl formate was measured using a plate-type of Raney copper catalyst in a reactor with rectangular channel and in an autoclave reactor. The reaction characteristics were investigated by carrying out the experiments at various temperatures, flow rates and at various catalyst development conditions. We focused on the effect of Raney copper catalyst thickness on the liquid-phase chemical reaction by varying the development time of the catalyst. Investigation results of the catalyst such as surface area, pore radius, lattice size, and photographs of scanning electron microscope (SEM) were also given. In the simulation of energy transport efficiency of this system, by simulating the energy transfer system using two-step liquid phase methanol decomposition and synthetic reactions, and comparing with the technology so far, it can be expected that an innovative energy transfer system is possible to realize.

Liu, Qiusheng; Yabe, Akira; Kajiyama, Shiro; Fukuda, Katsuya

154

The Electrochemical Thermodynamics for Chemical Reactions in Dispersed Cells.  

PubMed

There is a large specific surface area in a dispersed cell, so much so that there are some notable differences in thermodynamic quantities for a chemical reaction in the cell because of the strong surface effect. The thermodynamic relations between the electromotive force (emf) and the dispersity of a cell and between each of thermodynamic properties and the dispersivity of the cell are derived, and the effects of degree of dispersion of substances in the cell on the emf and the thermodynamic properties are discussed. The results show that the emf, the equilibrium constant, the entropy for reaction, the heat of reaction, and the enthalpy of reaction vary with the dispersivities of the reactants or/and the products in the cell. And two new concepts, surface emf and dispersion cell, are put forward in this paper. Copyright 1999 Academic Press. PMID:10441416

Yong-Qiang; Chun-Hui; Jin-Chuan

1999-09-01

155

Thermal Reaction of Cinnamate Oligomers and Their Effect on the Orientational Stability of Liquid Crystals  

NASA Astrophysics Data System (ADS)

Cinnamate groups are well-known for a dimerization reaction upon exposure to ultraviolet irradiation and a thermal reaction after being heated. In this study, to verify the thermal reaction of the cinnamate group in detail, we investigated the thermal crosslinking of cinnamate oligomers. The thermal reaction of cinnamate oligomers of low molecular weight is induced more readily by thermal energy compared with that of cinnamate polymers. This reaction is attributed to a radical reaction involving the carbon-carbon double bond in the cinnamate group. The orientation of the liquid crystal depended on the length of the spacers in the cinnamate oligomers.

Hah, Hyundae; Sung, Shi?Joon; Park, Jung?Ki

2006-08-01

156

Shock-induced chemical reactions in simple organic molecules  

NASA Astrophysics Data System (ADS)

Interrogating chemical reactions behind a shock front is immensely difficult and, as a result, the details of shock-induced chemistry remain poorly understood. Previous research has shown that dimerizations, polymerizations, ring-opening and decomposition reactions can occur under shock compression, depending on molecular structure. Questions regarding the thresholds for incipient reaction, the nature of first and subsequent reaction steps, and the influence of shock input conditions on reaction kinetics remain to be answered. Here, we have applied in-situ electromagnetic gauging at multiple Lagrangian positions to elucidate the evolution of multiple-wave structures associated with shock-induced reactions of several simple functional groups: carbon-carbon double (-C=C-) and triple bonds, and nitriles. The relative order of group reactivity under single shock conditions for these simple molecules is discussed. From measurements of the reactive flow, we have obtained detailed information about the temporal evolution of the waves, and global kinetic rates associated with transformation(s) between partially- and fully-reacted states. Near the reactive thresholds, evolution in particle velocities point to reaction timescales on the order of tens-to-hundreds of nanoseconds.

Dattelbaum, Dana M.; Sheffield, S. A.

2012-03-01

157

Photo-induced chemical reaction of trans-resveratrol.  

PubMed

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 ?W 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

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

2015-03-15

158

Electrochemical Reactions During Ru Chemical Mechanical Planarization and Safety Considerations  

NASA Astrophysics Data System (ADS)

We analyzed electrochemical reactions during ruthenium (Ru) chemical mechanical planarization (CMP) using a potentiostat and a quartz crystal microbalance, and considered the potential safety issues. We evaluated the valence number derived from Faraday's law using the dissolution mass change of Ru and total coulomb consumption in the electrochemical reactions for Ru in acidic solution and slurry. The valence numbers of dissolved Ru ions were distributed in the range of 2 to 3.5. As toxic ruthenium tetroxide (RuO4) has a valence number of 8, we were able to conclude that no toxic RuO4 was produced in the actual Ru CMP.

Shima, Shohei; Wada, Yutaka; Tokushige, Katsuhiko; Fukunaga, Akira; Tsujimura, Manabu

2011-05-01

159

Laser studies of chemical reaction and collision processes  

SciTech Connect

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.

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

1993-12-01

160

A fully coupled thermal, chemical, mechanical cookoff model  

SciTech Connect

Cookoff modeling of confined energetic materials involves the coupling of thermal, chemical and mechanical effects. In the past, modeling has focussed on the prediction of thermal runaway with little regard to the effects of mechanical behavior of the energetic material. To address the mechanical response of the energetic material, a constitutive submodel has been developed which can be incorporated into thermal-chemical-mechanical analysis. This work presents development of this submodel and its incorporation into a fully coupled one-dimensional, thermal-chemical-mechanical computer code to simulate thermal initiation of energetic materials. Model predictions include temperature, chemical species, stress, strain, solid/gas pressure, solid/gas density, yield function, and gas volume fraction. Sample results from a scaled aluminum tube filled with RDX exposed to a constant temperature bath at 500 K will be displayed. The micromechanical submodel is based on bubble mechanics which describes nucleation, decomposition, and elastic/plastic mechanical behavior. This constitutive material description requires input of temperatures and reacted fraction of the energetic material as provided by the reactive heat flow code, XCHEM, and the mechanical response is predicted using a quasistatic mechanics code, SANTOS. A parametric sensitivity analysis indicates that a small degree of decomposition causes significant pressurization of the energetic material, which implies that cookoff modeling must consider the strong interaction between thermal-chemistry and mechanics. This document consists of view graphs from the poster session.

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

1994-05-01

161

Chemical reaction fouling model for single-phase heat transfer  

SciTech Connect

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.

Panchal, C.B. [Argonne National Lab., IL (United States); Watkinson, A.P. [British Columbia Univ., Vancouver, BC (Canada)

1993-08-01

162

Crossed molecular beam studies of atmospheric chemical reaction dynamics  

SciTech Connect

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.

Zhang, Jingsong

1993-04-01

163

Implementation of a vibrationally linked chemical reaction model for DSMC  

NASA Technical Reports Server (NTRS)

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.

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

1994-01-01

164

Separation of the isotopes of boron by chemical exchange reactions  

DOEpatents

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.

McCandless, Frank P. (Bozeman, MT); Herbst, Ronald S. (Idaho Falls, ID)

1995-01-01

165

Separation of the isotopes of boron by chemical exchange reactions  

DOEpatents

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.

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

1995-05-30

166

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

SciTech Connect

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

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

1993-12-01

167

The nature of chemical reaction-driven tip-streaming  

NASA Astrophysics Data System (ADS)

The discovery of chemical reaction-driven tip-streaming (also known as "an amazing drop") was made about a decade ago during measurements of the dynamic interfacial tension of a water-alkali pendant droplet immersed in oil-linoleic acid. A plausible explanation for this self-sustained ejection of micron sized droplets from the tip of the macroscopic pendant drop was offered at that time and attributed to Marangoni stresses driving the reaction-produced surfactant along the interface. Later, asymptotic theory based on the analysis of a complete fluid dynamical formulation supported this hypothesis. As this discovery promised a way of microdroplet generation without the need for complex microchannel geometries or externally imposed flow or electric fields, we were recently motivated to study the influence of the reagent concentrations and reaction rate on the droplet generation. However, in an attempt to recreate the original experiments, we revealed that the cause for tip-streaming is not what it originally seemed to be. This led to a series of experiments clarifying the role of the Marangoni stresses and the crucial differences from similar phenomena. As the mechanism by which the phenomenon was originally thought to operate was supported by recent theoretical studies, the present work leads to new intriguing questions of existence and conditions under which a chemical reaction alone can drive Marangoni stresses capable of self-sustaining the process of tip-streaming.

Mayer, H. C.; Krechetnikov, R.

2013-05-01

168

Thermal and chemical stability of Romanian bentonite  

Microsoft Academic Search

Ca–bentonite originating from a Romanian deposit was leached in 0.5–8.0 M HCl solution at 90 °C for 4 h. This material was\\u000a fully characterized through BET, thermogravimetry, X-rays diffraction, and elemental analysis. The acid treatment at high\\u000a temperature altered the crystallinity, but produced an increase in the surface area and thermal stability. The resulting acid-treated\\u000a bentonite turned out to be an efficient adsorbent

A. V. Ursu; G. Jinescu; F. Gros; I. D. Nistor; N. D. Miron; G. Lisa; M. Silion; G. Djelveh; A. Azzouz

169

Physio-chemical reactions in recycle aggregate concrete.  

PubMed

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

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

2009-04-30

170

An infrared radiation based thermal biosensor for enzymatic biochemical reactions.  

PubMed

In this paper, a thermal biosensor based on the infrared radiation energy is proposed for calorimetric measurement of biochemical reactions. Having a good structure design combined with MEMS technology as well as employing the Si /SiGe quantum well sensing material with a high TCR and low 1/f noise, the sensor shows potentials to be high sensitive and real-time. The urea enzymatic reaction was tested to verify the performance of sensor, which demonstrates a linear detection range from 0.5mM to 150mM and a relative standard deviation less than 1%. For the sensor fabrication, wafer-level transfer bonding is a key process, which makes the integration of quantum well material and a free standing structure possible. It reduces the heat loss from the sensor to the surrounding environment. PMID:23365944

Zhang, Lei; Dong, Tao; Zhao, Xinyan; Yang, Zhaochu; Pires, Nuno M M

2012-01-01

171

A Thermal Field Theory with Non-uniform Chemical Potential  

E-print Network

We investigate thermal one-loop effective potentials in multi-flavor models with chemical potentials. We study four-dimensional models in which each flavor have different global U(1) charges. Accordingly they have different chemical potentials. We call these "non-uniform chemical potentials," which are organized into a diagonal matrix \\mu. The mass matrix at a vacuum does not commute with \\mu. We find that the effective potential is divided into three parts. The first part is the Coleman-Weinberg potential. The UV divergence resides only in this part. The second is the correction to the Coleman-Weinberg potential that is independent of temperature, and the third depends on both temperature and \\mu. Our result is a generalization of the thermal potentials in previous studies for models with single and multi-flavors with (uniform) chemical potentials and reproduces all the known results correctly.

Arai, Masato; Sasaki, Shin

2013-01-01

172

Bioconjugate functionalization of thermally carbonized porous silicon using a radical coupling reaction  

PubMed Central

The high stability of Salonen’s thermally carbonized porous silicon (TCPSi) has attracted attention for environmental and biochemical sensing applications, where corrosion-induced zero point drift of porous silicon-based sensor elements has historically been a significant problem. Prepared by the high temperature reaction of porous silicon with acetylene gas, the stability of this silicon carbide-like material also poses a challenge—many sensor applications require a functionalized surface, and the low reactivity of TCPSi has limited the ability to chemically modify its surface. This work presents a simple reaction to modify the surface of TCPSi with an alkyl carboxylate. The method involves radical coupling of a dicarboxylic acid (sebacic acid) to the TCPSi surface using a benzoyl peroxide initiator. The grafted carboxylic acid species provides a route for bioconjugate chemical modification, demonstrated in this work by coupling propylamine to the surface carboxylic acid group through the intermediacy of pentafluorophenol and 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride (EDC). The stability of the carbonized porous Si surface, both before and after chemical modification, is tested in phosphate buffered saline solution and found to be superior to either hydrosilylated (with undecylenic acid) or thermally oxidized porous Si surfaces. PMID:20967329

Sciacca, Beniamino; Alvarez, Sara D.; Geobaldo, Francesco; Sailor, Michael J.

2011-01-01

173

Propagation of Reactions in Thermally-damaged PBX-9501  

SciTech Connect

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

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

2010-03-05

174

Automated microreactor system for reaction development and online optimization of chemical processes  

E-print Network

Developing the optimal conditions for chemical reactions that are common in fine chemical and pharmaceutics is a difficult and expensive task. Because syntheses in these fields have multiple reaction pathways, a significant ...

McMullen, Jonathan Patrick

2010-01-01

175

Chemical and mechanical feedback during reaction rim growth  

NASA Astrophysics Data System (ADS)

The system MgO-SiO2, including the mineral reaction quadruple periclase-forsterite-enstatite-quartz, has for several years become a favored target for laboratory and thought experiments on reaction rim growth, on the possible grain-scale pressure variability evolving during metamorphic reactions, and on the role of the local reaction volume in guiding kinetic pathways. Both isotope tracer and microstructure analyses indicate that the relative opposite fluxes of MgO and SiO2 components obey the limitations in space dictated by the stoichiometry of the local partial reactions. However, if the component's mobility is high, this implies local competition between mineral growth and the yield strength of the surrounding matrix, thus local pressure variation. Experimentally this is validated by the significant differences in Opx rim thickness, either forming around Ol in Qtz matrix, or around Qtz in Ol matrix, in one and the same experiment. Tantamount observations have been experimentally made in the CaO-SiO2 and CaO-MgO-SiO2 systems. In all these laboratory experiments, the presence of traces of water has been identified as a leading variable controlling the mobility of chemical species. Trace amounts of water follow local pressure gradients and speed up reaction rates where local volume change is negative. New results indicate that at least in coarse grained rocks, total water contents in the 10 ppm range might increase chemical fluxes along grain boundaries by orders of magnitude. The majority of metamorphic rocks in the Earth's crust is dominated by aluminuous silicates and quartz. Reaction rims in aluminosilicate lithologies have been studied in samples of high-pressure felsic granulites from the Bohemian Massif (Variscan belt of Central Europe). They show well developed plagioclase reaction rims around kyanite grains in two microstructural settings. Plagioclase rims around kyanite inclusions within large perthites have a radial thickness of up to 50 ?m, whereas the radial thickness of plagioclase rims around kyanites in the polycrystalline matrix is significantly larger, up to 200 ?m. The difference in the rim thickness for the two microstructural settings is ascribed to the complex interplay of the efficiency of chemical mass transfer and the mechanical response of the surrounding matrix next to the reaction site. Our data based on numerical modelling show that the microstructure may be generated and maintained on the geological time scale as a result of the mechanical feedback induced by the local reactions taking place in restricted space. In general, the observations from experimental and natural systems indicate that assumed equilibria in metamorphic rocks must be generally considered as local equilibria. This includes not only the chemical composition of metamorphic minerals, but also the strength of the surrounding matrix in which they form.

Milke, R.; Tajcmanova, L.

2012-12-01

176

Thermal reaction studies of organic model compound-mineral matter interactions in solids  

SciTech Connect

The solid-state chemistry of silica-immobilized phenethyl phenyl ethers is being investigated in the presence of interdispersed aluininosilicates at temperatures relevant to coal processing to gain a better understanding of the impact of mineral matter on pyrolysis and liquefaction mechanisms. Results demonstrate the dramatic effect that aluminosilicates can have in altering the normal thermal reaction pathways for these models of ether linkages in lignin and low rank coals. An investigation of the chemistry of these model compounds at low temperatures (ca. 150-200{degrees}C) in the presence of aluminosilicates, including montmorillonite, is currently being investigated to delineate the chemical transformations that can occur during lignin maturation.

Buchanan, A.C. III; Britt, P.F.; Thomas, K.B.

1995-07-01

177

EFFECTS OF THERMAL TREATMENTS ON THE CHEMICAL REACTIVITY OF TRICHLOROETHYLENE  

EPA Science Inventory

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

178

Anaphylactic reactions to low-molecular weight chemicals.  

PubMed

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

Nowak, Daria; Panaszek, Bernard

2015-01-01

179

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

PubMed

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

Vaiano, V; Sannino, D; Ciambelli, P

2014-10-31

180

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

E-print Network

, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan The chemical reactions of transition metalMass Spectroscopy of Chemical Reaction of 3d Metal Clusters Involved in Chemical Vapor Deposition clusters in the gas phase have aroused considerable scientific interest and are also of critical scientific

Maruyama, Shigeo

181

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

NASA Astrophysics Data System (ADS)

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

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

2012-04-01

182

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

ERIC Educational Resources Information Center

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

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

2013-01-01

183

Tungsten-dependent formaldehyde ferredoxin oxidoreductase: Reaction mechanism from quantum chemical calculations  

E-print Network

redox reactions, while the latter catalyzes a non-redox hydration of acetylene. In Pyrococcus furiosusTungsten-dependent formaldehyde ferredoxin oxidoreductase: Reaction mechanism from quantum chemical April 2011 Keywords: Tungstoenzyme Formaldehyde oxidoreductase Reaction mechanism Density functional

Liao, Rongzhen

184

Fuels and chemicals from biomass using solar thermal energy  

NASA Technical Reports Server (NTRS)

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

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

1981-01-01

185

Nature of the chemical reaction for furfural modified asphalt  

SciTech Connect

Three of the most serious problems of asphalt pavements today are rutting, cracking, and susceptibility to moisture damage (stripping). Asphalt manufacturers have been mixing asphalts with polymers to produce polymer-modified asphalts with improved rheological properties. However, the costs for these improved polymer-modified asphalts are almost double that of regular asphalts. FHWA researchers have found that asphalt modified by the chemical, furfural (which is prepared by simple elimination reaction of aldopentoses obtained from oat hulls), exhibited better stripping properties and was less temperature susceptible than the virgin asphalt while costing less than polymer-modified asphalts. This paper discusses the possible structure of the furfural-modified asphalt, data for the virgin and furfural-modified asphalts and their Corbett fractions, data from a model reaction between phenol and furfural, and a possible explanation of this structure based on these data.

Memon, G.M.; Chollar, B.H. [FHWA Engineering, Inc., McLean, VA (United States)

1994-12-31

186

Predicting Formation Damage in Aquifer Thermal Energy Storage Systems Utilizing a Coupled Hydraulic-Thermal-Chemical Reservoir Model  

NASA Astrophysics Data System (ADS)

In aquifer thermal energy storage (ATES) systems, large amounts of energy can be stored by injecting hot water into deep or intermediate aquifers. In a seasonal production-injection cycle, water is circulated through a system comprising the porous aquifer, a production well, a heat exchanger and an injection well. This process involves large temperature and pressure differences, which shift chemical equilibria and introduce or amplify mechanical processes. Rock-fluid interaction such as dissolution and precipitation or migration and deposition of fine particles will affect the hydraulic properties of the porous medium and may lead to irreversible formation damage. In consequence, these processes determine the long-term performance of the ATES system and need to be predicted to ensure the reliability of the system. However, high temperature and pressure gradients and dynamic feedback cycles pose challenges on predicting the influence of the relevant processes. Within this study, a reservoir model comprising a coupled hydraulic-thermal-chemical simulation was developed based on an ATES demonstration project located in the city of Berlin, Germany. The structural model was created with Petrel, based on data available from seismic cross-sections and wellbores. The reservoir simulation was realized by combining the capabilities of multiple simulation tools. For the reactive transport model, COMSOL Multiphysics (hydraulic-thermal) and PHREEQC (chemical) were combined using the novel interface COMSOL_PHREEQC, developed by Wissmeier & Barry (2011). It provides a MATLAB-based coupling interface between both programs. Compared to using COMSOL's built-in reactive transport simulator, PHREEQC additionally calculates adsorption and reaction kinetics and allows the selection of different activity coefficient models in the database. The presented simulation tool will be able to predict the most important aspects of hydraulic, thermal and chemical transport processes relevant to formation damage in ATES systems. We would like to present preliminary results of the structural reservoir model and the hydraulic-thermal-chemical coupling for the demonstration site. Literature: Wissmeier, L. and Barry, D.A., 2011. Simulation tool for variably saturated flow with comprehensive geochemical reactions in two- and three-dimensional domains. Environmental Modelling & Software 26, 210-218.

Müller, Daniel; Regenspurg, Simona; Milsch, Harald; Blöcher, Guido; Kranz, Stefan; Saadat, Ali

2014-05-01

187

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

Microsoft Academic Search

Irradiation of chemically reactive particulate suspensions by high power, pulsed laser radiation initiates reactions at the sites of the particles so that besides the absorbed optical energy, chemical energy is liberated. In addition to the release of chemical energy, chemical reaction can result in gas production both of which result in enhancement in the amplitude of the photoacoustic effect. Here

Han Jung Park; Binbin Wu; Gerald J. Diebold

2011-01-01

188

Resonant radiofrequency magnetic field effects on a chemical reaction  

NASA Astrophysics Data System (ADS)

Observations of the effect of a radiofrequency magnetic field on the progress of a chemical reaction are reported. It is shown that the fluorescence of an exciplex formed in the photoreaction of anthracene-d 10 and 1,3-dicyanobenzene (DCB) is attenuated when a 30-40 MHz oscillating field is applied. The effect is interpreted in the framework of the radical pair mechanism, in terms of a change in the extent of singlet?triplet interconversion in the {anthracene cation-DCB anion} radical pair when the oscillating field is in resonance with hyperfine splittings in the DCB anion radical.

Woodward, J. R.; Jackson, R. J.; Timmel, C. R.; Hore, P. J.; McLauchlan, K. A.

1997-07-01

189

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

NASA Technical Reports Server (NTRS)

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

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

1976-01-01

190

Thermalization with chemical potentials, and higher spin black holes  

E-print Network

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

Mandal, Gautam; Sorokhaibam, Nilakash

2015-01-01

191

Influence of seasonal timing on thermal ecology and thermal reaction norm evolution in Wyeomyia smithii.  

PubMed

Evolutionary changes in the seasonal timing of life-history events can alter a population's exposure to seasonally variable environmental factors. We illustrate this principle in Wyeomyia smithii by showing that: (1) geographic divergence in diapause timing reduces differences among populations in the thermal habitat experienced by nondiapause stages; and (2) the thermal habitat of the growing season is more divergent at high compared with low temperatures with respect to daily mean temperatures. Geographic variation in thermal reaction norms for development time was greater in a warm compared with a cool rearing treatment, mirroring the geographic trend in daily mean temperature. Geographic variation in body size was unrelated to geographic temperature variation, but was also unrelated to development time or fecundity. Our results suggest that proper interpretation of geographic trends may often require detailed knowledge of life-history timing. PMID:17903189

Ragland, G J; Kingsolver, J G

2007-11-01

192

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

PubMed

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

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

2014-05-01

193

Thermal photon v2 with slow quark chemical equilibration  

NASA Astrophysics Data System (ADS)

Elliptic flow of direct photons in high-energy heavy-ion collisions has been a topic of great interest since it was experimentally found to be larger than most hydrodynamic expectations. I discuss the implication of possible late formation of the quark component in a hot QCD medium on the photon elliptic flow, because quarks are the source of thermal photons in the deconfined phase. Hydrodynamic equations are numerically solved with the evolution equations for quark and gluon number densities. The numerical results suggest that thermal photon v2 is visibly enhanced by the slow chemical equilibration of quarks and gluons, reducing the aforementioned problem.

Monnai, Akihiko

2014-08-01

194

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

ERIC Educational Resources Information Center

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

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

2014-01-01

195

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

Microsoft Academic Search

The chemical reactions of transition metal clusters in the gas phase have aroused considerable scientific interest and are also of critical scientific importance. For example, these reactions are involved in the synthesis of single-walled carbon nanotubes, which are considered ideal materials because of their outstanding properties. Alcohol catalytic chemical vapor deposition (ACCVD) is one of the best synthetic processes for

Shuhei Inoue; Shigeo Maruyama

2008-01-01

196

MODEL OF CHEMICAL REACTION EQUILIBRIUM OF SULFURIC ACID SALTS OF TRIOCTYLAMINE  

Microsoft Academic Search

The chemical reaction of trioctylamine (TOA) and sulfuric acid in organic solvent\\/aqueous solution was carried out. TOA salt products of various kinds were obtained based on different conditions of operation and organic solvents. An equilibrium model, based on the chemical reaction of sulfuric acid and trioctylamine, is proposed. The equilibrium constants of various reactions of trioctylamine and sulfuric acid were

MAW-LING WANG; KWAN-HUA HU

1993-01-01

197

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

E-print Network

On persistence of chemical reaction networks with time-dependent kinetics and no global work. The new results allow the consideration of reaction rates which are time-varying, thus for persistence of chemical reaction networks are proposed, which extend those obtained by the authors in previous

Sontag, Eduardo

198

Thermalization with chemical potentials, and higher spin black holes  

E-print Network

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

Gautam Mandal; Ritam Sinha; Nilakash Sorokhaibam

2015-01-19

199

Thermalization with a chemical potential from AdS spaces  

E-print Network

The time-scale of thermalization in holographic dual models with a chemical potential in diverse number of dimensions is systematically investigated using the gauge/gravity duality. We consider a model with a thin-shell of charged dust collapsing from the boundary toward the bulk interior of asymptotically anti-de Sitter (AdS) spaces. In the outer region there is a Reissner-Nordstr\\"om-AdS black hole (RNAdS-BH), while in the inner region there is an anti-de Sitter space. We consider renormalized geodesic lengths and minimal area surfaces as probes of thermalization, which in the dual quantum field theory (QFT) correspond to two-point functions and expectation values of Wilson loops, respectively. We show how the behavior of these extensive probes changes for charged black holes in comparison with Schwarzschild-AdS black holes (AdS-BH), for different values of the black hole mass and charge. The full range of values of the chemical potential over temperature ratio in the dual QFT is investigated. In all cases, the structure of the thermalization curves shares similar features with those obtained from the AdS-BH. On the other hand, there is an important difference in comparison with the AdS-BH: the thermalization times obtained from the renormalized geodesic lengths and the minimal area surfaces are larger for the RNAdS-BH, and they increase as the black hole charge increases.

Damian Galante; Martin Schvellinger

2012-05-07

200

Possible application of solar-thermal energy in the chemical industry  

NASA Astrophysics Data System (ADS)

Eight chemicals are identified that require substantial amounts of nonrecoverable energy for their production. The chemicals are: ethylene, vinyl chloride, styrene, propylene, butadiene, isoprene, hydrogen, and phosphorus. These chemicals are used to produce a wealth of products such as plastics, rubbers and fertilizers. In most cases, these energy intensive materials are at the top of a pyramid of subsequent, exothermic reactions and products that do not require additional thermal energy except for separation processes. Their production at present is centralized and done on a large scale, and most of the organics are produced in refineries where hydrocarbon energy is abundant. This association with refineries means at present that direct substitution of solar energy for hydrocarbon fired heaters may not be convenient, even though scientifically feasible. Other solar energy applications are production of caustic soda from thermodynamic cycles, ethylene from ethanol, and butadiene from ethanol.

Martin, L. R.

1982-06-01

201

Mass Accommodation and Chemical Reaction at Gas-Liquid Interfaces  

NASA Astrophysics Data System (ADS)

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

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

2006-12-01

202

Development of porous solid reactant for thermal-energy storage and temperature upgrade using carbonation\\/decarbonation reaction  

Microsoft Academic Search

Cyclic reaction performances of solid reactants for a CaO–CO2 chemical heat-pump designed for upgrading and storing high-temperature thermal energy were studied. Solid reactants composed of CaO as the reactant and CaTiO3 as the inert framework were prepared using the conventional powder method or the metal alkoxide method. Upon experiments of cyclic operation between CaO carbonation and CaCO3 decarbonation at 1023K,

Masahiko Aihara; Toshiyuki Nagai; Junro Matsushita; Yoichi Negishi; Haruhiko Ohya

2001-01-01

203

Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks  

SciTech Connect

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

Ziaul Huque

2007-08-31

204

Thermal, chemical, and mechanical response of rigid polyurethane foam  

SciTech Connect

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

Hobbs, M.L.

1997-12-01

205

Reduction of Chemical Reactions in Nitrogen and Nitrogen–Hydrogen Plasma Jets Flowing into Atmospheric Air  

Microsoft Academic Search

The large number of possible chemical reactions represents a severe burdenfor modeling of even relatively simple plasma systems. Reduced sets ofchemical reactions have been obtained for numerical simulations of nitrogenand nitrogen-hydrogen plasma jets flowing into an atmospheric airenvironment. The important or active reactions are determined based on asimplified reduction method. A reaction is considered active if it leadsto higher sensitivities

J. H. Park; E. Pfender; C. H. Chang

2000-01-01

206

Enzyme catalysis Enzyme catalysis is the catalysis of chemical reactions by  

E-print Network

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

Cavanagh, John

207

Impact of fluid deformation on mixing-induced chemical reactions in heterogeneous flows  

NASA Astrophysics Data System (ADS)

Fast chemical reactions in geophysical flows are controlled by fluid mixing, which perturbs local chemical equilibria and thus triggers chemical reactions. Spatial fluctuations in the flow velocity lead to deformation of material fluid elements, which form the support volumes of transported chemical species. We develop an approach based on a lamellar representation of fluid mixing that provides a direct link between fluid deformation, the distribution of concentration gradients, and the upscaled reaction rates for fast reversible reactions. The temporal evolution of effective reaction rates is determined by the flow topology and the distribution of local velocity gradients. This leads to a significant increase of the reaction efficiency, which turns out to be orders of magnitude larger than in homogeneous flow. This approach allows for the systematic evaluation of the temporal evolution of equilibrium reaction rates and establishes a direct link between the reaction efficiency and the spatial characteristics of the underlying flow field as quantified by the deformation of material fluid elements.

Borgne, Tanguy Le; Ginn, Timothy R.; Dentz, Marco

2014-11-01

208

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

E-print Network

-1- SENSITIVITY OF CHEMICAL REACTION NETWORKS: A STRUCTURALAPPROACH. 1. EXAMPLES AND THE CARBON for sensitivity Corresponding Author: Atsushi Mochizuki Address: Theoretical Biology Laboratory, RIKEN, Wako 351 examines their "sensitivity": each enzyme mediating a reaction in the system is increased

Fiedler, Bernold

209

A procedure for the assessment of the toxicity of intermediates and products formed during the accidental thermal decomposition of a chemical species  

Microsoft Academic Search

The knowledge of the substances which form when a molecule undergoes chemical reactions under unusual conditions is required by European legislation to evaluate the risks associated with an industrial chemical process. A thermal decomposition is often the result of a loss of control of the process which leads to the formation of many substances in some cases not easily predictable.

Ilaria Di Somma; Antonino Pollio; Gabriele Pinto; Maria De Falco; Elio Pizzo; Roberto Andreozzi

2010-01-01

210

Experimental results of exothermic reaction with concentration gradient catalyst in a solar chemical heat pump  

Microsoft Academic Search

A solar chemical heat pump can upgrade low-temperature solar heat of about 80°C to about 150-200°C by using the reversible chemical reactions of 2-propanol\\/acetone\\/hydrogen, which are composed of endothermic and exothermic reactions. In the exothermic process of the above reaction, a temperature peak occurs near the inlet of the reaction zone in the case of uniform catalyst arrangement. Such a

T. Takashima; T. Doi; Y. Ando; T. Tanaka; R. Miyahara; J. Kamoshida

1997-01-01

211

Millimeter-wave imaging of thermal and chemical signatures.  

SciTech Connect

Development of a passive millimeter-wave (mm-wave) system is described for remotely mapping thermal and chemical signatures of process effluents with application to arms control and nonproliferation. Because a large amount of heat is usually dissipated in the air or waterway as a by-product of most weapons of mass destruction facilities, remote thermal mapping may be used to detect concealed or open facilities of weapons of mass destruction. We have developed a focal-plane mm-wave imaging system to investigate the potential of thermal mapping. Results of mm-wave images obtained with a 160-GHz radiometer system are presented for different target scenes simulated in the laboratory. Chemical and nuclear facilities may be identified by remotely measuring molecular signatures of airborne molecules emitted from these facilities. We have developed a filterbank radiometer to investigate the potential of passive spectral measurements. Proof of principle is presented by measuring the HDO spectral line at 80.6 GHz with a 4-channel 77-83 GHz radiometer.

Gopalsami, N.

1999-03-30

212

Surface Cracking and Interface Reaction Associated Delamination Failure of Thermal and Environmental Barrier Coatings  

NASA Technical Reports Server (NTRS)

In this paper, surface cracking and interface reactions of a BSAS coating and a multi-layer ZTO2-8wt%Y2O3 and mullite/BSAS/Si thermal and environmental barrier coating system on SiC/SiC ceramic matrix composites were characterized after long-term combined laser thermal gradient and furnace cyclic tests in a water vapor containing environment. The surface cracking was analyzed based on the coating thermal gradient sintering behavior and thermal expansion mismatch stress characteristics under the thermal cyclic conditions. The interface reactions, which were largely enhanced by the coating surface cracking in the water vapor environment, were investigated in detail, and the reaction phases were identified for the coating system after the long- term exposure. The accelerated coating delamination failure was attributed to the increased delamination driving force under the thermal gradient cyclic loading and the reduced interface adhesion due to the detrimental interface reactions.

Zhu, Dongming; Choi, Sung R.; Eldridge, Jeffrey I.; Lee, Kang N.; Miller, Robert A.

2003-01-01

213

Variation in thermal performance and reaction norms among populations of Drosophila melanogaster.  

PubMed

The major goal of evolutionary thermal biology is to understand how variation in temperature shapes phenotypic evolution. Comparing thermal reaction norms among populations from different thermal environments allows us to gain insights into the evolutionary mechanisms underlying thermal adaptation. Here, we have examined thermal adaptation in six wild populations of the fruit fly (Drosophila melanogaster) from markedly different natural environments by analyzing thermal reaction norms for fecundity, thorax length, wing area, and ovariole number under ecologically realistic fluctuating temperature regimes in the laboratory. Contrary to expectation, we found only minor differences in the thermal optima for fecundity among populations. Differentiation among populations was mainly due to differences in absolute (and partly also relative) thermal fecundity performance. Despite significant variation among populations in the absolute values of morphological traits, we observed only minor differentiation in their reaction norms. Overall, the thermal reaction norms for all traits examined were remarkably similar among different populations. Our results therefore suggest that thermal adaptation in D. melanogaster predominantly involves evolutionary changes in absolute trait values rather than in aspects of thermal reaction norms. PMID:24299409

Klepsatel, Peter; Gáliková, Martina; De Maio, Nicola; Huber, Christian D; Schlötterer, Christian; Flatt, Thomas

2013-12-01

214

Free-Electron Lasers, Thermal Diffusion, Chemical Kinetics, and Surgery  

NASA Astrophysics Data System (ADS)

Experiments demonstrate that the Mark-III FEL is a particularly effective tool for etching soft matter with remarkably little damage surrounding the site when tuned to wavelengths near 6.45 microns. Based on these observatons, human neuorsurgical and ophthalmic procedures were developed and have been performed successfully. A thermodynamic model was proposed to account for the wavelength dependence; however, the dynamics have not been well understood. We have theoretically investigated thermal diffusion and chemical kinetics in a system of alternating layers of protein and water as heated by a Mark-III FEL. The model is representative of cornea and the exposure conditions are comparable to previous experimental FEL investigations. A substantial temperature enhancement develops in the surface layer on the ten-nanosecond time scale. We consider the onset of both the helix-coil transition and chemical bond breaking of collagen in terms of the thermal, chemical, and structural properties of the system as well as laser wavelength and pulse structure.

Edwards, Glenn; Hutson, M. Shane

2001-11-01

215

Thermal/chemical degradation of ceramic cross-flow filter materials  

SciTech Connect

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

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

1989-11-01

216

Non-isothermal thermal decomposition reaction kinetics of 2-nitroimino-5-nitro-hexahydro-1,3,5-triazine (NNHT).  

PubMed

The thermal behavior and decomposition reaction kinetics of 2-nitroimino-5-nitro-hexahydro-1,3,5-triazine (NNHT) were investigated by TG-DTG and DSC under atmospheric pressure and flowing nitrogen gas conditions. The results show that the thermal decomposition process of NNHT has two mass loss stages. The exothermic decomposition reaction mechanism obeys chemical reaction rule. The kinetic parameters of the reaction are E(a)=131.77 kJ mol(-1), lg(A/s(-1))=12.56, respectively. The kinetic equation can be expressed as: dalpha/dt = 10(12.86)(1-alpha)(3/2)3(-1.5849 x 10(4)/T)). The critical temperature of thermal explosion of NNHT obtained from the peak temperature (T(p)) is T(bp)=467.22K. The entropy of activation (DeltaS( not equal)), enthalpy of activation (DeltaH( not equal)), and free energy of activation (DeltaG( not equal)) of the reaction are -7.978 J mol(-1)K(-1), 127.99 kJ mol(-1) and 131.62 kJ mol(-1), respectively. PMID:19185997

Zhang, Jiao-qiang; Gao, Hong-xu; Su, Li-hong; Hu, Rong-zu; Zhao, Feng-qi; Wang, Bo-zhou

2009-08-15

217

Thermal and ion beam induced thin film reactions in Cu-Al bilayers  

Microsoft Academic Search

Thermal and ion beam induced thin film reactions in Cu-Al bilayers were investigated by Rutherford backscattering and X-ray diffraction. A marker experiment was performed to study the moving species during the reaction using W embedded in the interface. At the initial stage of the thermally induced reaction, CuAl2, which is the most Al rich phase in the Cu-Al system, was

Tamou Yoshitaka; Li Jian; Stephen W. Russell; James W. Mayer

1992-01-01

218

Thermal and Microcanonical Rates of Unimolecular Reactions from an Energy Diffusion Theory Approach  

E-print Network

Thermal and Microcanonical Rates of Unimolecular Reactions from an Energy Diffusion Theory Approach; In Final Form: September 13, 1999 We present an energy diffusion theory approach for computing thermal compared to the thermal energy. The weak-collision limit has been extensively studied.1-9 However

Miller, William H.

219

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

E-print Network

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

Anderson, James B.

220

Chemical composition and thermal property of cuttlefish ( Sepia pharaonis) muscle  

Microsoft Academic Search

The chemical composition and thermal property of cuttlefish (Sepia pharaonis) muscle were studied. The head and mantle contained 11.9–14.9% protein, 0.5% fat, 1.2–1.3% ash, and 0.6–1.8% collagen. Lipids from the head and mantle contained phospholipid as the major component (78.6–87.8% of total lipid), with 10.6–19.5% diglyceride. Polyunsaturated fatty acids constituted 50.3–54.9% of fatty acids with a high content of DHA

Amonrat Thanonkaew; Soottawat Benjakul; Wonnop Visessanguan

2006-01-01

221

Thermal, chemical and spectral equilibration in heavy-ion collisions  

E-print Network

We have considered the equilibration in a relativistic heavy ion collision using our transport model. We applied periodic boundary conditions to close the system in a box. We found that the thermal equilibration takes place in the first 20-40 fm/c which time is comparable to the duration of a heavy ion collision. The chemical equilibration is a much slower process and the system does not equilibrate in a heavy ion collision. We have also shown that the mass spectra of broad resonances immediately follows their in-medium spectral functions.

Gábor András Almási; György Wolf

2014-07-08

222

Application of magnetic microfluidic chip to chemical and electrochemical reactions  

NASA Astrophysics Data System (ADS)

A new type of the microfluidic chip is proposed, which is composed of a network of magnetic channels instead of solid channels. The magnetic channels are formed by the heterogeneous magnetic field distribution (called magnetic walls or magnetic barriers) around a ferromagnetic track imbedded on a chip surface. The channel is surrounded not by solid walls, but by a liquid-liquid interface with a diamagnetic or a paramagnetic solution (called an environmental solution) supported by the magnetic wall. After injecting a solution (called a test solution) with magnetism different from the environmental solution into the channel, the test solution smoothly proceeds into the channel in a frictionless mode. In the static state, the test solution takes a tube-like shape owing to the conventional interfacial tension and the magnetic pressure. The liquid-liquid interface also behaves like a self-repairable, elastic membrane, so that the test solutions, even if mixed with bubbles and solid particles, can smoothly flow without choking. Mass and heat easily transfer through the magnetic wall, so that this system can be applied to effective reactors for various chemical and electrochemical reactions. Figs 10, Refs 27.

Aogaki, R.; Ito, E.; Ogata, M.

2006-12-01

223

Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks  

SciTech Connect

This is an annual technical report for the work done over the last year (period ending 9/30/2004) on the project titled ''Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks''. The aim of the project is to develop an efficient chemistry model for combustion simulations. The reduced chemistry model will be developed mathematically without the need of having extensive knowledge of the chemistry involved. To aid in the development of the model, Neural Networks (NN) will be used via a new network topology know as Non-linear Principal Components Analysis (NPCA). We report on the development of a procedure to speed up the training of NPCA. The developed procedure is based on the non-parametric statistical technique of kernel smoothing. When this smoothing technique is implemented as a Neural Network, It is know as Generalized Regression Neural Network (GRNN). We present results of implementing GRNN on a test problem. In addition, we present results of an in house developed 2-D CFD code that will be used through out the project period.

Nelson Butuk

2004-12-01

224

Chemical reactions between Venus' surface and atmosphere - An update. (Invited)  

NASA Astrophysics Data System (ADS)

The surface of Venus, at ~740K, is hot enough to allow relatively rapid chemical reactions between it and the atmosphere, i.e. weathering. Venus chemical weathering has been explored in detail [1], to the limits of available data. New data from Venus Express (VEx) and new ideas from exoplanets have sparked a modest renewal of interest in Venus weathering. Venus' surface cannot be observed in visible light, but there are several NIR ';windows' through its atmosphere that allow surface imaging. The VIRTIS spectrometer on VEx viewed the surface through one window [2]; emissivity variations among lava flows on Imdr and Themis Regios have been explained as varying degrees of weathering, and thus age [3]. The VMC camera on VEx also provides images through a NIR window, which suggest variable degrees of weathering on some basaltic plains [4]. Indirect evidence for weathering may come from varying SO2 abundance at Venus' cloud tops; repeated rapid increases and gradual declines may represent volcanic eruptions followed by weathering to form sulfate minerals [5]. Continued geochemical modeling relevant to Venus weathering is motivated by expolanet studies [6]. Models have been extended to hypothetical exo-Venuses of different temperatures and surface compositions [7]. The idea that Venus' atmosphere composition can be buffered by reaction with its surface was explored in detail, and the derived constraint extended to other types of planets [8]. Several laboratories are investigating Venus weathering, motivated in part by the hope that they can provide real constraints on timescales of Venus volcanism [3]. Aveline et al. [9] are extending early studies [10] by reacting rocks and minerals with concentrated SO2 (to accelerate reaction rates to allow detectability of products). Kohler et al. [11] are investigating the stability of metals and chalcogenides as possible causes of the low-emissivity surfaces at high elevations. Berger and Aigouy [12] studied rock alteration on a hypothetical early Venus with a water-rich atmosphere. Martin et al. [13] investigated the fate of weathered rock when heated (by igneous or impact events). Our understanding of Venus' geological history is stymied by a lack of data - spacecraft observations of and/or at its surface. VMC on VEx may continue to provide new data on surface emissivity, but their interpretation is inherently ambiguous. Laboratory experiments seem the most promising approach - attempting to quantify rates of weathering and thus volcanism [3], and (with luck) framing significant problems that can be directly answered by spacecraft observations. [1] Fegley B.Jr. et al. (1997) In Venus II. U. Ariz. Press. p. 591. [2] Helbert J. et al. (2008) GRL 35, L11201. [3] Smrekar S.E et al. (2010) Science 328, 605-608. [4] Basilevsky A.T. et al. (2012) Icarus 217, 434-450. [5] Marcq E. et al. (2013) Nature Geoscience 6, 25-28. [6] Kane S.R. et al. (2013) Astrophysical J. 770, L20. [7] Schaefer L. & Fegley B.Jr. (2011) Astrophysical J. 729, 6. [8] Treiman A.H. & Bullock M.A. (2012) Icarus 217, 534-541. [9] Aveline D.C. et al. (2011) Lunar Planet. Sci. Conf. 42, Abstr. #2165. [10] Fegley B.Jr. & Prinn R.G. (1989) Nature 337, 55-58. [11] Kohler E. et al. (2012) Lunar Planet. Sci. Conf. 43, Abstr. #2749. [12] Berger G. & Aigouy T. (2011) Lunar Planet. Sci. Conf. 42, Abstr. #1660. [13] Martin A.M. et al. (2012) Earth Planet. Sci. Lett. 331-332, 291-304.

Treiman, A. H.

2013-12-01

225

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

NASA Technical Reports Server (NTRS)

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

Schredder, J. M.; Fujita, T.

1984-01-01

226

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

NASA Astrophysics Data System (ADS)

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

Schredder, J. M.; Fujita, T.

1984-10-01

227

Chemical TOPAZ: Modifications to the heat transfer code TOPAZ: The addition of chemical reaction kinetics and chemical mixtures  

SciTech Connect

This is a report describing the modifications which have been made to the heat flow code TOPAZ to allow the inclusion of thermally controlled chemical kinetics. This report is broken into parts. The first part is an introduction to the general assumptions and theoretical underpinning that were used to develop the model. The second section describes the changes that have been implemented into the code. The third section is the users manual for the input for the code. The fourth section is a compilation of hints, common errors, and things to be aware of while you are getting started. The fifth section gives a sample problem using the new code. This manual addenda is written with the presumption that most readers are not fluent with chemical concepts. Therefore, we shall in this section endeavor to describe the requirements that must be met before chemistry can occur and how we have modeled the chemistry in the code.

Nichols, A.L. III.

1990-06-07

228

Investigations of the thermal reactions of chlorine on the GaAs(100) surface  

Microsoft Academic Search

The thermal reactions of Cl2 with the GaAs(100) surface were studied using XPS, LEED and thermal desorption spectroscopy. Chlorine uptake at 175 K is initially very rapid, but an extensive corrosion phase is not formed. Five thermal desorption features are seen, with cracking patterns corresponding to GaCl, As2, GaCl3, Cl2 and AsCl3. The implications for the thermal etching of gallium

C. L. French; W. S. Balch; J. S. Foord

1991-01-01

229

Thermal and chemical degradation of inorganic membrane materials. Topical report  

SciTech Connect

This report describes the results of a literature review to evaluate the long-term thermal and chemical degradation of inorganic membranes that are being developed to separate gaseous products produced by the gasification or combustion of coal in fixed-, fluidized-, and entrained-bed gasifiers, direct coal-fired turbines, and pressurized-fluidized-bed combustors. Several impurities, such as H{sub 2}S, NH{sub 3}, SO{sub 2}, NO{sub x}, and trace metal compounds are generated during coal conversion, and they must be removed from the coal gas or the combustor flue gas to meet environmental standards. The use of membranes to separate these noxious gases is an attractive alternative to their removal by sorbents such as zinc titanate or calcium oxide. Inorganic membranes that have a high separation efficiency and exhibit both thermal and chemical stability would improve the economics of power generation from coal. The U.S. Department of Energy is supporting investigations to develop inorganic membranes for separating hydrogen from coal gas streams and noxious impurities from hot coal- and flue-gas streams. Membrane materials that have been investigated in the past include glass (silica), alumina, zirconia, carbon, and metals (Pd and Pt).

Krishnan, G.N.; Sanjurjo, A.; Wood, B.J.; Lau, K.H.

1994-04-01

230

Impact of organic-mineral matter interactions on thermal reaction pathways for coal model compounds  

SciTech Connect

Coal is a complex, heterogeneous solid that includes interdispersed mineral matter. However, knowledge of organic-mineral matter interactions is embryonic, and the impact of these interactions on coal pyrolysis and liquefaction is incomplete. Clay minerals, for example, are known to be effective catalysts for organic reactions. Furthermore, clays such as montmorillonite have been proposed to be key catalysts in the thermal alteration of lignin into vitrinite during the coalification process. Recent studies by Hatcher and coworkers on the evolution of coalified woods using microscopy and NMR have led them to propose selective, acid-catalyzed, solid state reaction chemistry to account for retained structural integrity in the wood. However, the chemical feasibility of such reactions in relevant solids is difficult to demonstrate. The authors have begun a model compound study to gain a better molecular level understanding of the effects in the solid state of organic-mineral matter interactions relevant to both coal formation and processing. To satisfy the need for model compounds that remain nonvolatile solids at temperatures ranging to 450 C, model compounds are employed that are chemically bound to the surface of a fumed silica (Si-O-C{sub aryl}linkage). The organic structures currently under investigation are phenethyl phenyl ether (C{sub 6}H{sub 5}CH{sub 2}CH{sub 2}OC{sub 6}H{sub 5}) derivatives, which serve as models for {beta}-alkyl aryl ether units that are present in lignin and lignitic coals. The solid-state chemistry of these materials at 200--450 C in the presence of interdispersed acid catalysts such as small particle size silica-aluminas and montmorillonite clay will be reported. Initial focus will be on defining the potential impact of these interactions on coal pyrolysis and liquefaction.

Buchanan, A.C. III; Britt, P.F.; Struss, J.A. [Oak Ridge National Lab., TN (United States). Chemical and Analytical Sciences Div.

1995-07-01

231

Effect of chemical vapor infiltration on erosion and thermal properties of porous carbon\\/carbon composite thermal insulation  

Microsoft Academic Search

A highly porous carbon\\/carbon composite, known as carbon bonded carbon fiber (CBCF) and used as thermal insulation, was densified by chemical vapor infiltration (CVI). The erosion resistance, thermal conductivity and thermal expansion coefficient were measured with interest to utilization of the CVI densified composite as erosion protection in furnaces that employ inert gas quenching. It was found that the erosion

R. I Baxter; R. D Rawlings; N Iwashita; Y Sawada

2000-01-01

232

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

ERIC Educational Resources Information Center

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

Tellinghuisen, Joel

2006-01-01

233

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

ERIC Educational Resources Information Center

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

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

2008-01-01

234

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

ERIC Educational Resources Information Center

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

Kadioglu, Cansel; Uzuntiryaki, Esen

2008-01-01

235

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

ERIC Educational Resources Information Center

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

Goodney, David E.

2006-01-01

236

Fluctuation Spectroscopy: The Determination of Chemical Reaction Rates Based on the Optical Density Fluctuation  

Microsoft Academic Search

The analysis of the half-width of the frequency spectrum due to the concentration fluctuation around the equilibrium value should give the rate constant of a chemical reaction under the appropriate condition. Specially, in a chemical reaction among the molecular species which have respectively different light absorption coefficients, the concentration fluctuations of each component molecule induce the corresponding fluctuation of the

Akiyoshi Watanabe; Yoshi-ichi Sato; Yoshito Amako

1978-01-01

237

Study on solar chemical heat pump system -- Basic experiment on falling film reaction of 2-propanol dehydrogenation  

SciTech Connect

It is not easy to use solar energy because it has low energy density and is interrupted by passing clouds. Furthermore it is difficult to continuously get high-temperature thermal energy from the sun under a poor solar condition such as in Japan. However, it is easy to get low-temperature thermal energy. Therefore, the authors use a chemical heat pump, which uses endothermic and exothermic reactions, in order to upgrade low-temperature thermal energy obtained from the sun. They adopted 2-propanol/acetone/hydrogen system as the chemical reaction. In the endothermic process of this system, improvement of the heat utilization factor was one of the serious subjects to realize this system. In order to solve this problem, they made a new type reactor called a falling-liquid film reactor (FFR) and experimented the dehydrogenation reaction of 2-propanol. The major result was that the FFR provides four times as high heat utilization factor as a conventional liquid-phase suspension reactor (LSR) does. In this paper, the authors describe the detailed results obtained from above experiments.

Doi, Takuya; Ando, Yuji; Takashima, Takumi; Tanaka, Tadayoshi [Electrotechnical Lab., Tsukuba Ibaraki (Japan). Energy Technology Div.

1997-12-31

238

Computational Analyses of Complex Flows with Chemical Reactions  

NASA Astrophysics Data System (ADS)

The heat and mass transfer phenomena in micro-scale for the mass transfer phenomena on drug in cylindrical matrix system, the simulation of oxygen/drug diffusion in a three dimensional capillary network, and a reduced chemical kinetic modeling of gas turbine combustion for Jet propellant-10 have been studied numerically. For the numerical analysis of the mass transfer phenomena on drug in cylindrical matrix system, the governing equations are derived from the cylindrical matrix systems, Krogh cylinder model, which modeling system is comprised of a capillary to a surrounding cylinder tissue along with the arterial distance to veins. ADI (Alternative Direction Implicit) scheme and Thomas algorithm are applied to solve the nonlinear partial differential equations (PDEs). This study shows that the important factors which have an effect on the drug penetration depth to the tissue are the mass diffusivity and the consumption of relevant species during the time allowed for diffusion to the brain tissue. Also, a computational fluid dynamics (CFD) model has been developed to simulate the blood flow and oxygen/drug diffusion in a three dimensional capillary network, which are satisfied in the physiological range of a typical capillary. A three dimensional geometry has been constructed to replicate the one studied by Secomb et al. (2000), and the computational framework features a non-Newtonian viscosity model for blood, the oxygen transport model including in oxygen-hemoglobin dissociation and wall flux due to tissue absorption, as well as an ability to study the diffusion of drugs and other materials in the capillary streams. Finally, a chemical kinetic mechanism of JP-10 has been compiled and validated for a wide range of combustion regimes, covering pressures of 1atm to 40atm with temperature ranges of 1,200 K--1,700 K, which is being studied as a possible Jet propellant for the Pulse Detonation Engine (PDE) and other high-speed flight applications such as hypersonic missiles. The comprehensive skeletal mechanism consists of 58 species and 315 reactions including in CPD, Benzene formation process by the theory for polycyclic aromatic hydrocarbons (PAH) and soot formation process on the constant volume combustor, premixed flame characteristics.

Bae, Kang-Sik

239

Phase and chemical equilibria in the transesterification reaction of vegetable oils with supercritical lower alcohols  

NASA Astrophysics Data System (ADS)

Calculations of thermodynamic data are performed for fatty acid triglycerides, free fatty acids, and fatty acid methyl esters, participants of the transesterification reaction of vegetable oils that occurs in methanol. Using the obtained thermodynamic parameters, the phase diagrams for the reaction mixture are constructed, and the chemical equilibria of the esterification reaction of free fatty acids and the transesterification reaction of fatty acid triglycerides attained upon treatment with supercritical methanol are determined. Relying on our analysis of the obtained equilibria for the esterification reaction of fatty acids and the transesterification reaction of triglycerides attained upon treatment with lower alcohols, we select the optimum conditions for performing the reaction in practice.

Anikeev, V. I.; Stepanov, D. A.; Ermakova, A.

2011-08-01

240

Kinetic models with chemical reactions and nonequilibrium entropy in open systems  

NASA Astrophysics Data System (ADS)

Nonuniform relaxation problems are applied to simulate complex non-equilibrium processes with chemical reactions in open systems. The present paper is a continuation of our studies at a new level, in particular, 2D flows are considered. Besides the slow chemical reactions, the so-called fast reactions are studied. A special attention is paid to studying the behavior of non-equilibrium entropy and entropy flux in such complex open systems.

Aristov, Vladimir; Frolova, Anna; Zabelok, Sergey

2014-12-01

241

Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks  

SciTech Connect

This is an annual technical report for the work done over the last year (period ending 9/30/2005) on the project titled ''Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks''. The aim of the project is to develop an efficient chemistry model for combustion simulations. The reduced chemistry model will be developed mathematically without the need of having extensive knowledge of the chemistry involved. To aid in the development of the model, Neural Networks (NN) will be used via a new network topology know as Non-linear Principal Components Analysis (NPCA). We report on the significant development made in developing a truly meshfree computational fluid dynamics (CFD) flow solver to be coupled to NPCA. First, the procedure of obtaining nearly analytic accurate first order derivatives using the complex step method (CSM) is extended to include computation of accurate meshfree second order derivatives via a theorem described in this report. Next, boosted generalized regression neural network (BGRNN), described in our previous report is combined with CSM and used to obtain complete solution of a hard to solve wave dominated sample second order partial differential equation (PDE): the cubic Schrodinger equation. The resulting algorithm is a significant improvement of the meshfree technique of smooth particle hydrodynamics method (SPH). It is suggested that the demonstrated meshfree technique be termed boosted smooth particle hydrodynamics method (BSPH). Some of the advantages of BSPH over other meshfree methods include; it is of higher order accuracy than SPH; compared to other meshfree methods, it is completely meshfree and does not require any background meshes; It does not involve any construction of shape function with their associated solution of possibly ill conditioned matrix equations; compared to some SPH techniques, no equation for the smoothing parameter is required; finally it is easy to program.

Nelson Butuk

2006-09-21

242

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

E-print Network

DNS of a Mach 4 Boundary Layer with Chemical Reactions M. Pino Mart´in Graham V. Candler Aerospace simulation (DNS) database is used to develop a greater understanding of the turbulence-chemistry interaction by endothermic reactions and destabilized by exother- mic reactions. In our previous work,2,3 we used DNS

Martín, Pino

243

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

E-print Network

A modified next reaction method for simulating chemical systems with time dependent propensities method. In this paper we make explicit use of the fact that the initiation times of the reactions can introduce our representation of the reaction times as the fir- ing times of independent,

Anderson, David F.

244

A Unified Approach to the Study of Chemical Reactions in Freshman Chemistry.  

ERIC Educational Resources Information Center

Provides rationale and objectives for presenting chemical reactions in a unified, logical six-stage approach rather than a piecemeal approach. Stages discussed include: introduction, stable electronic configurations and stable oxidation states, reactions between two free elements, ion transfer/proton transfer reactions, double displacement…

Cassen, T.; DuBois, Thomas D.

1982-01-01

245

Thermal decomposition of sodium bicarbonate and its effect on the reaction of sodium bicarbonate and sulfur dioxide in a simulated flue gas  

SciTech Connect

The effect of thermally decomposing sodium bicarbonate while simultaneously reacting with SO/sub 2/, was studied. The study was performed by quantitatively determining the rate of thermal decomposition as a function of particle size in an SO/sub 2/ free gas stream. The rate of reaction of sodium carbonate (product of the thermal decomposition) with SO/sub 2/ was then studied, and the data applied to a pore-plugging model which accounts for the loss in reactivity with increased reaction time. The reaction of sodium bicarbonate with SO/sub 2/ was then studied and the results compared to that for sodium carbonate. From the analysis of the data, the activation energy for the thermal decomposition reaction, the SO/sub 2/ sodium carbonate and SO/sub 2/ sodium bicarbonate reaction were derived. The thermal decomposition reaction of sodium biocarbonate was found to be similar to that of calcium carbonate below the point where heat transfer is rate limiting. The degree of conversion of sodium bicarbonate was found to be 12-17 times greater (depending on particle size) than that of sodium carbonate in the temperature range 250/sup 0/-350/sup 0/F (120/sup 0/-177/sup 0/C). This greater conversion was qualitatively explained by hypothesizing the formation of an activated species during thermal decomposition which would be more chemically reactive.

Keener, T.C.

1982-01-01

246

CHEMICAL SYNTHESIS USING 'GREENER' ALTERNATIVE REACTION CONDITIONS AND MEDIA  

EPA Science Inventory

The chemical research during the last decade has 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 ...

247

SUBSTITUTION REACTIONS FOR THE DETOXIFICATION OF HAZARDOUS CHEMICALS  

EPA Science Inventory

Chemical Treatment is one of several treatment techniques used for the remediation of toxic and hazardous chemicals. Chemical treatment in this report is defined as substitution of halogens by hydrogens for the conversion of halogenated organic toxicant into its native hydrocarb...

248

Real-time quantitative investigation of photochemical reaction using thermal lens measurements: Theory and experiment  

SciTech Connect

In this work the time-resolved mode-mismatched thermal lens method is applied to investigate Cr(VI) species in water. An abnormal behavior of the thermal lens transient induced by a photochemical reaction was observed during optical excitation. With the purpose of better understanding this phenomenon, the existing theoretical model of thermal lens effect was generalized in order to take the time dependence of the absorbance of the sample into account due to the changes in concentration resulting from photochemical reaction and diffusion of absorbing species. Consequently, the photochemical reaction rate can be quantitatively evaluated by this technique with the generalized model. The adopted procedure demonstrates the usefulness of the time-resolved thermal lens method for the study of photochemical reactions under the presence of absorbing species diffusion with the advantage of monitoring the processes in a quantitative way and with a temporal resolution of a few milliseconds.

Pedreira, P. R. B.; Hirsch, L. R.; Pereira, J. R. D.; Medina, A. N.; Bento, A. C.; Baesso, M. L.; Rollemberg, Maria C.; Franko, Mladen; Shen Jun [Departamento de Fisica, Universidade Estadual de Maringa, Avenida Colombo 5790, 87020-900, Maringa, Parana (Brazil); Departamento de Quimica, Universidade Estadual de Maringa, 87020-900, Maringa, Parana (Brazil); Laboratory for Environmental Research, University of Nova Gorica, Vipavska 13, SI-5000 Nova Gorica (Slovenia); National Research Council of Canada, Institute for Fuel Cell Innovation, 3250 East Mall, Vancouver, British Columbia V6T 1W5 (Canada)

2006-08-15

249

Dynamics and evolution of the deep mantle resulting from thermal, chemical, phase and melting effects  

E-print Network

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.3. Thermal conductivityDynamics and evolution of the deep mantle resulting from thermal, chemical, phase and melting the silicate mantle and liquid iron alloy outer core ­ is the most important boundary inside our planet

Tackley, Paul J.

250

Mixing and chemical reaction in sheared and nonsheared homogeneous turbulence  

NASA Technical Reports Server (NTRS)

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

Leonard, Andy D.; Hill, James C.

1992-01-01

251

Thermally Stable Nanocatalyst for High Temperature Reactions: Pt-Mesoporous Silica Core-Shell Nanoparticles  

SciTech Connect

Recent advances in colloidal synthesis enabled the precise control of size, shape and composition of catalytic metal nanoparticles, allowing their use as model catalysts for systematic investigations of the atomic-scale properties affecting catalytic activity and selectivity. The organic capping agents stabilizing colloidal nanoparticles, however, often limit their application in high-temperature catalytic reactions. Here we report the design of a high-temperature stable model catalytic system that consists of Pt metal core coated with a mesoporous silica shell (Pt{at}mSiO{sub 2}). While inorganic silica shells encaged the Pt cores up to 750 C in air, the mesopores directly accessible to Pt cores made the Pt{at}mSiO{sub 2} nanoparticles as catalytically active as bare Pt metal for ethylene hydrogenation and CO oxidation. The high thermal stability of Pt{at}mSiO{sub 2} nanoparticles permitted high-temperature CO oxidation studies, including ignition behavior, which was not possible for bare Pt nanoparticles because of their deformation or aggregation. The results suggest that the Pt{at}mSiO{sub 2} nanoparticles are excellent nanocatalytic systems for high-temperature catalytic reactions or surface chemical processes, and the design concept employed in the Pt{at}mSiO{sub 2} core-shell catalyst can be extended to other metal-metal oxide compositions.

Joo, Sang Hoon; Park, J.Y.; Tsung, C.-K.; Yamada, Y.; Yang, P.; Somorjai, G.A.

2008-10-25

252

Light hydrocarbons in hydrothermal and magmatic fumaroles: hints of catalytic and thermal reactions  

NASA Astrophysics Data System (ADS)

Volcanic gaseous mixtures emitted from active volcanoes frequently show variable amounts of saturated (alkanes), unsaturated (alkenes) and aromatic volatile hydrocarbons. Three major patterns of distributions can be recognized, apparently related to the chemical-physical environment of formation of the gas exhalations: alkane-rich, low-temperature gas emissions from recently active volcanic areas; aromatic-rich hydrothermal manifestations; and alkene-rich, ‘magmatic’ fumaroles on active volcanoes. Thermodynamic data, together with theoretical and practical findings from the petroleum industry, point to two main types of reactions occurring in these volcanic environments: cracking and reforming. Cracking processes, mainly caused by thermal effects, occur when hydrocarbon-bearing hydrothermal fluids enter and mix with a hot and dry, rapidly rising magmatic gas phase. The most probable products are light alkenes with carbon numbers decreasing with increasing reaction temperatures. The presence of aromatic species in hydrothermal fluids can be linked to reforming processes, catalysed by several possible agents, such as smectites and zeolites, generally present in the hydrothermally altered volcanic terranes, and facilitated by long residence times in a hydrothermal envelope.

Capaccioni, Bruno; Martini, Marino; Mangani, Filippo

1995-02-01

253

Photothermal-reaction-assisted two-photon lithography of silver nanocrystals capped with thermally cleavable ligands  

Microsoft Academic Search

We report an alternative approach to produce micropatterns of metallic nanoparticles using photothermal-reaction-assisted two-photon direct laser writing. The patterns are achieved using a facile surface treatment of silver nanoparticles (Ag NPs) functionalized with thermally cleavable ligands; N-(tert-butoxycarbonyl)-L-cysteine methyl ester. The ligand cleavage initiated by pulsed laser-induced thermal reaction results in a significant change in dispersiblility of the nanocrystals, thereby enabling

Won Jin Kim; Xavier Vidal; Alexander Baev; Hong Sub Jee; Mark T. Swihart; Paras N. Prasad

2011-01-01

254

A lattice gas automata model for heterogeneous chemical reactions at mineral surfaces and in pore networks  

SciTech Connect

A lattice gas automata (LGA) model is described, which couples solute transport with chemical reactions at mineral surfaces and in pore networks. Chemical reactions and transport are integrated into a FHP-I LGA code as a module so that the approach is readily transportable to other codes. Diffusion in a box calculations are compared to finite element Fickian diffusion results and provide an approach to quantifying space-time ratios of the models. Chemical reactions at solid surfaces, including precipitation/dissolution, sorption, and catalytic reaction, can be examined with the model because solute diffusion and mineral surface processes are all treated explicitly. The simplicity and flexibility of the LGA approach provides the ability to study the interrelationship between fluid flow and chemical reactions in porous materials, at a level of complexity that has not previously been computationally possible. 20 refs., 8 figs.

Wells, J.T. (Washington Univ., Seattle, WA (USA). Dept. of Geological Sciences); Janecky, D.R.; Travis, B.J. (Los Alamos National Lab., NM (USA))

1990-01-15

255

Application of Reversible Chemical Reactions for Temperature Amplification  

E-print Network

In a recent survey of 108 industries in the U.S., it was found that large amounts of thermal energy at relatively low temperatures was discharged to the atmosphere through industrial effluents. For the purpose of thermally upgrading such low...

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

256

Chemical characteristics of the major thermal springs of Montana  

USGS Publications Warehouse

Twenty-one thermal springs in western Montana were sampled for chemical, isotope, and gas compositions. Most of the springs issue dilute to slightly saline sodium-bicarbonate waters of neutral to slightly alkaline pH. A few of the springs issue sodium-mixed anion waters of near neutral pH. Fluoride concentrations are high in most of the thermal waters, up to 18 milligramsper litre, while F/Cl ratios range from 3/1 in the dilute waters to 1/10 in the slightly saline waters. Most of the springs are theoretically in thermodynamic equilibrium with respect to calcite and fluorite. Nitrogen is the major gas escaping from most of the hot springs; however, Hunters Hot Springs issue principally methane. The deuterium content of the hot spring waters is typical of meteoric water in western Montana. Geothermal calculations based on silica concentrations and Na-K-Ca ratios indicate that most of the springs are associated with low temperature aquifers (less than 100?C). Chalcedony may be controlling the silica concentrations in these low temperature aquifers even in 'granitic' terranes.

Mariner, R.H.; Presser, T.S.; Evans, W.C.

1976-01-01

257

CHEMICAL REACTIONS OF AQUATIC HUMIC MATERIALS WITH SELECTED OXIDANTS  

EPA Science Inventory

A study was conducted to identify the specific organic reaction products of natural aquatic humic materials with selected oxidants (KMnO4, HOCl, Cl02, O3 and monochloramine). Reaction products were identified by GC/MS after solvent extraction and derivatization. The two most reac...

258

Heat-Of-Reaction Chemical Heat Pumps--Possible Configurations  

E-print Network

ABSTRACT Chemical heat pumps utilize working fluids which undergo reversible chemical changes. Mechanically driven reactive heat pump cycles or, alternatively, hl~a: driven heat pumps in which either heat engine or heat pump working fluid... is reactive, are consid ~red. As such, chemical heat pumps can be classified by (a) drive (electric drive, waste heat drive, or prime energy drive), (b) operating mode (periodic or continuous), (c) type of coupling between the heat ,'ngine .1nd heat pump...

Kirol, L. D.

259

Soret and chemical reaction effects on unsteady two-dimensional natural convection along a vertical plate  

NASA Astrophysics Data System (ADS)

In this paper, a numerical solution of the unsteady two-dimensional natural convection along a vertical plate in the presence of Soret and chemical reaction effects is presented. The governing non-dimensional coupled non-linear partial differential equations have been evaluated by using an implicit finite-difference technique of Crank-Nicolson scheme. Numerical predictions for the velocity, concentration, local and average skin-friction and Sherwood number for distinct values of chemical reaction parameter and Soret number are plotted graphically. It is found that the fluid velocity and concentration decreases while increasing chemical reaction parameter whereas an increase in the Soret number increases the fluid velocity and concentration.

Raju, S. Suresh Kumar; Narahari, M.; Pendyala, Rajashekhar

2014-10-01

260

Characterization of chemically modified enzymes for bioremediation-reactions. 1997 annual progress report  

SciTech Connect

'Many, if not most, biological transformation reactions of interest to US Department of Energy (DOE) site remediation involve substrates that are only sparingly soluble in aqueous environments. Hence, destruction of these recalcitrant and toxic materials would benefit tremendously if their degradation could be performed in nonaqueous environments. Organic biocatalysis may be motivated by the nature of the substrate itself, augmented mass transport, ease of product recovery, or novel reaction pathways afforded by the organic solvent. For instance, polychlorinated biphenyls (PCBs) are sparingly soluble in water, but may be more effectively processed when solubilized by organic liquids. However, naturally-occurring enzymes are not soluble in organic solvents. Indeed, most spontaneously denature and, depending on the solvent used, typically form inactive and insoluble precipitates. The objective of the current work is to gain a fundamental understanding of the molecular and catalytic properties of enzymes that have been chemically-modified so that they are catalytically-active and chemically-thermally-stable in organic solvents. The premise for this study is that highly stable enzymes which are catalytically active in both water and in a range of organic solvents are optimally suited for bioremediation where substrates of interest are more soluble and may be processed with greater specificity in nonaqueous solvents. The proposed research program will enable the development of nonaqueous bioremediation technologies for the treatment of DOE sites contaminated with aqueous-insoluble organic compounds. Such compounds may include dense nonaqueous phase liquids, trichloroethylene (TCE), trichloroacetic acid, trans-dichloroethylene, diesel fuel, and PCBs. These compounds have been identified as targets for technology development in the ``EM Technology Needs Database,'''' and are contaminants at the following DOE sites: K-25 Site plumes; ORNL WAGS 1, 4, and 5; Paducah plumes; Portsmouth plumes; the X-701B Holding Pond; and the Y-12 Poplar Creek and Bear Creek Watersheds.'

Kaufman, E.N. [Oak Ridge National Lab., TN (US); Adams, M.W.W. [Univ. of Georgia, Athens, GA (US)

1997-09-01

261

The colorants, antioxidants, and toxicants from nonenzymatic browning reactions and the impacts of dietary polyphenols on their thermal formation.  

PubMed

Nonenzymatic browning reactions proceed with the starting reactants of sugar and/or protein during thermal processing and storage of food. In addition to food color formation, the process also contributes to the loss of essential nutrients, generation of beneficial antioxidants, and production of toxicants, including 5-hydroxymethylfurfural (5-HMF), reactive carbonyl species, advanced glycation end products (AGEs), and heterocyclic amines (HAs). Recent research has demonstrated that dietary polyphenols can actively participate in nonenzymatic browning reactions, contributing to the generation of new colorants and antioxidants. More importantly, polyphenol addition has been found to be an effective approach to mitigate heat-induced formation of toxicants, mainly through inhibiting oxidative pathways and trapping reactive intermediates. In the matrix of polyphenol-fortified foods, a complex array of chemical interactions happen among polyphenols, traditional nutritional components, and neo-formed compounds they are thermally converted to. These reactions play a significant role in the colorants, antioxidants as well as toxicants production. Our findings support the potential of dietary polyphenols for increasing the antioxidant content and for reducing the level of toxicants when they participate in nonenzymatic browning reactions in fortified food products. PMID:25468403

Zhang, Xinchen; Tao, Ningping; Wang, Xichang; Chen, Feng; Wang, Mingfu

2015-02-11

262

Digital isothermal quantification of nucleic acids via simultaneous chemical initiation of recombinase polymerase amplification reactions on SlipChip.  

PubMed

In this paper, digital quantitative detection of nucleic acids was achieved at the single-molecule level by chemical initiation of over one thousand sequence-specific, nanoliter isothermal amplification reactions in parallel. Digital polymerase chain reaction (digital PCR), a method used for quantification of nucleic acids, counts the presence or absence of amplification of individual molecules. However, it still requires temperature cycling, which is undesirable under resource-limited conditions. This makes isothermal methods for nucleic acid amplification, such as recombinase polymerase amplification (RPA), more attractive. A microfluidic digital RPA SlipChip is described here for simultaneous initiation of over one thousand nL-scale RPA reactions by adding a chemical initiator to each reaction compartment with a simple slipping step after instrument-free pipet loading. Two designs of the SlipChip, two-step slipping and one-step slipping, were validated using digital RPA. By using the digital RPA SlipChip, false-positive results from preinitiation of the RPA amplification reaction before incubation were eliminated. End point fluorescence readout was used for "yes or no" digital quantification. The performance of digital RPA in a SlipChip was validated by amplifying and counting single molecules of the target nucleic acid, methicillin-resistant Staphylococcus aureus (MRSA) genomic DNA. The digital RPA on SlipChip was also tolerant to fluctuations of the incubation temperature (37-42 °C), and its performance was comparable to digital PCR on the same SlipChip design. The digital RPA SlipChip provides a simple method to quantify nucleic acids without requiring thermal cycling or kinetic measurements, with potential applications in diagnostics and environmental monitoring under resource-limited settings. The ability to initiate thousands of chemical reactions in parallel on the nanoliter scale using solvent-resistant glass devices is likely to be useful for a broader range of applications. PMID:21476587

Shen, Feng; Davydova, Elena K; Du, Wenbin; Kreutz, Jason E; Piepenburg, Olaf; Ismagilov, Rustem F

2011-05-01

263

Polymerase chain reaction with phase change as intrinsic thermal control  

NASA Astrophysics Data System (ADS)

This research demonstrated that without any external temperature controller, the capillary convective polymerase chain reaction (ccPCR) powered by a candle can operate with the help of phase change. The candle ccPCR system productively amplified hepatitis B virus 122 base-pairs DNA fragment. The detection sensitivity can achieve at an initial DNA concentration to 5 copies per reaction. The results also show that the candle ccPCR system can operate functionally even the ambient temperature varies from 7 °C to 45 °C. These features imply that the candle ccPCR system can provide robust medical detection services.

Hsieh, Yi-Fan; Yonezawa, Eri; Kuo, Long-Sheng; Yeh, Shiou-Hwei; Chen, Pei-Jer; Chen, Ping-Hei

2013-04-01

264

Will water act as a photocatalyst for cluster phase chemical reactions? Vibrational overtone-induced dehydration reaction of methanediol  

SciTech Connect

The possibility of water catalysis in the vibrational overtone-induced dehydration reaction of methanediol is investigated using ab initio dynamical simulations of small methanediol-water clusters. Quantum chemistry calculations employing clusters with one or two water molecules reveal that the barrier to dehydration is lowered by over 20 kcal/mol because of hydrogen-bonding at the transition state. Nevertheless, the simulations of the reaction dynamics following OH-stretch excitation show little catalytic effect of water and, in some cases, even show an anticatalytic effect. The quantum yield for the dehydration reaction exhibits a delayed threshold effect where reaction does not occur until the photon energy is far above the barrier energy. Unlike thermally induced reactions, it is argued that competition between reaction and the irreversible dissipation of photon energy may be expected to raise the dynamical threshold for the reaction above the transition state energy. It is concluded that quantum chemistry calculations showing barrier lowering are not sufficient to infer water catalysis in photochemical reactions, which instead require dynamical modeling.

Kramer, Zeb C.; Takahashi, Kaito; Skodje, Rex T. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215 (United States); Vaida, Veronica [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215 (United States); CIRES, University of Colorado, Boulder, Colorado 80309 (United States)

2012-04-28

265

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

E-print Network

WATER RESOURCES RESEARCH, VOL. ???, XXXX, DOI:10.1029/, Simulation of chemical reaction via/$9.00 within any single Eulerian "block" of material, the concen- trations of reactants are everywhere equal

266

EVALUATION OF CHEMICAL REACTION MECHANISMS FOR PHOTOCHEMICAL SMOG. PART 2. QUANTITATIVE EVALUATION OF THE MECHANISMS (REVISED)  

EPA Science Inventory

Six chemical reaction mechanisms for photochemical smog were analyzed to determine why, under identical conditions, they predict different maximum ozone concentrations. To perform the analysis, a counter species technique was used to determine the contributions of individual reac...

267

Chemical and isotopic composition of water from thermal springs and mineral springs of Washington  

USGS Publications Warehouse

Water from thermal springs of Washington range in chemical composition from dilute NaHC03, to moderately saline C02-charged NaHC03-Cl waters. St. Martin 's Hot Spring which discharges a slightly saline NaCl water, is the notable exception. Mineral springs generally discharge a moderately saline C02-charged NaHC03-Cl water. The dilute Na-HC03 waters are generally associated with granite. The warm to hot waters charged with C02 issue on or near the large stratovolcanoes and many of the mineral springs also occur near the large volcanoes. The dilute waters have oxygen isotopic compositions which indicate relatively little water-rock exchange. The C02-charged waters are usually more enriched in oxygen-18 due to more extensive water-rock reaction. Carbon-13 in the C02-charged thermal waters is more depleted (-10 to -12 permil) than in the cold C02-charged soda springs (-2 to -8 permil) which are also scattered throughout the Cascades. The hot and cold C02-charged waters are supersaturated with respect to CaC03, but only the hot springs are actively depositing CaC03. Baker, Gamma, Sulphur , and Ohanapecosh seem to be associated with thermal aquifers of more than 100C. (USGS)

Mariner, R.H.; Presser, T.S.; Evans, W.C.

1982-01-01

268

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

NASA Technical Reports Server (NTRS)

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

Radhakrishnan, Krishnan; Bittker, David A.

1993-01-01

269

Selective Growth of Straight Carbon Nanotubes by Low-Pressure Thermal Chemical Vapor Deposition  

E-print Network

Selective Growth of Straight Carbon Nanotubes by Low-Pressure Thermal Chemical Vapor Deposition) were grown by low-pressure thermal chemical vapor deposition using pure ethylene. It was found preferentially bridged between Fe nanoparticles under a low pressure of 100 Pa. Moreover, utilizing this method

Hasegawa, Shuji

270

Relict olivine grains, chondrule recycling, and implications for the chemical, thermal, and mechanical processing  

E-print Network

Relict olivine grains, chondrule recycling, and implications for the chemical, thermal other incompatible ele- ments in olivine. Terrestrial weathering in a hot desert environment may have repeated thermal, chemical, and mechanical process- ing during a ``recycling" process over an extended time

271

Theoretical approach to modelling the low-barrier chemical reactions initiated by pulsed electron beam  

NASA Astrophysics Data System (ADS)

A possibility to analyze low-barrier chemical reactions induced by electron beam is proposed within the framework of generalization of classical Kramers approach. A relationship for calculation of chemical reaction rate is received for potential barriers comparable with energy of system. It has been shown that results of our approach agree with results of dynamical modeling within 2% not only in the area of applicability of classical (Kramers) approach but also more widely.

Aktaev, N. E.

2014-11-01

272

Exothermic and endothermic chemical reactions involving very many particles modeled with molecular dynamics  

Microsoft Academic Search

The traditional continuum approach of modeling chemical reactions with specified kinetic rates suffers from numerical difficulties in reactive flows and other highly non-equilibrium situations due to the stiffness of the differential equations in both space and time. These drawbacks can be eliminated within the framework of the discrete-particle approach in which the chemical reactions are modeled by means of two-body

W. Alda; D. A. Yuen; H.-P. Lüthi; J. R. Rustad

2000-01-01

273

Thermal, chemical, and mechanical response of rigid polyurethane foam  

Microsoft Academic Search

Rigid polyurethane foams are frequently used as encapsulants to isolate and support thermally sensitive components within weapon systems. When exposed to abnormal thermal environments, such as fire, the polyurethane foam decomposes to form products having a wide distribution of molecular weights and can dominate the overall thermal response of the system. Mechanical response of the decomposing foam, such as thermal

1997-01-01

274

Dephosphorylation reactions with deferoxamine, a potential chemical nuclease.  

PubMed

We report a detailed kinetic and mechanistic study of the reaction of a widely used therapeutic agent, deferoxamine (DFO), which contains three nucleophilic hydroxamate groups, with the model phosphate diester bis-2,4-dinitrophenylphosphate BDNPP. We clarify the mechanism by detecting important phosphorylated intermediates in the model reaction and show that the mechanism can be extended to the reaction with DNA. The effectiveness of DFO in cleaving DNA was examined over a range of pH in the absence and presence of a biologically available metal (Zn(2+)). The results inform and complement ongoing studies involving DFO, which can act as a powerful nucleophile toward DNA and other targets susceptible to nucleophilic attack. PMID:22049907

Orth, Elisa S; Medeiros, Michelle; Bortolotto, Tiago; Terenzi, Hernán; Kirby, Anthony J; Nome, Faruk

2011-12-16

275

Femtosecond electron diffraction and spectroscopic studies of a solid state organic chemical reaction  

NASA Astrophysics Data System (ADS)

Photochromic diarylethene molecules are excellent model systems for studying electrocyclic reactions, in addition to having important technological applications in optoelectronics. The photoinduced ring-closing reaction in a crystalline photochromic diarylethene derivative was fully resolved using the complementary techniques of transient absorption spectroscopy and femtosecond electron crystallography. These studies are detailed in this thesis, together with the associated technical developments which enabled them. Importantly, the time-resolved crystallographic investigation reported here represents a highly significant proof-of-principle experiment. It constitutes the first study directly probing the molecular structural changes associated with an organic chemical reaction with sub-picosecond temporal and atomic spatial resolution---to follow the primary motions directing chemistry. In terms of technological development, the most important advance reported is the implementation of a radio frequency rebunching system capable of producing femtosecond electron pulses of exceptional brightness. The temporal resolution of this newly developed electron source was fully characterized using laser ponderomotive scattering, confirming a 435 +/- 75 fs instrument response time with 0.20 pC bunches. The ultrafast spectroscopic and crystallographic measurements were both achieved by exploiting the photoreversibility of diarylethene. The transient absorption study was first performed, after developing a novel robust acquisition scheme for thermally irreversible reactions in the solid state. It revealed the formation of an open-ring excited state intermediate, following photoexcitation of the open-ring isomer with an ultraviolet laser pulse, with a time constant of approximately 200 fs. The actual ring closing was found to occur from this intermediate with a time constant of 5.3 +/- 0.3 ps. The femtosecond diffraction measurements were then performed using multiple crystal orientations and a large number of different samples. To analyse the results, an innovative method was developed in which the apparently complex ring-closing reaction is distilled down to a small number of basic rotations. Immediately following photoexcitation, sub-picosecond structural changes associated with the formation of the intermediate are observed. The rotation of the thiophene rings is identified as the key motion. Subsequently, on the few picosecond time scale, the time-resolved diffraction patterns are observed to converge towards those associated with the closed-ring photoproduct. The formation of the closed-ring molecule is thus unambiguously witnessed.

Jean-Ruel, Hubert

276

Controllable redox reaction of chemically purified DNA-single walled carbon nanotube hybrids with hydrogen peroxide.  

PubMed

We report for the first time the controllable redox reaction of chemically purified ssDNA-HiPco SWNT hybrids with hydrogen peroxide. Compared with the suspensions before separation, the purified SWNT suspensions become inert with hydrogen peroxide which may serve as a platform for further chemical manipulation. In the presence of thiocyanate ions, the reaction of SWNTs with hydrogen peroxide is initiated and accelerated at the earlier reaction stage, accompanied with the near-infrared spectral suppression. At the later stage, the suppressed spectral intensity is recovered overtime. The thiocyanate ions may work as a mediator being able to control the reaction rate as well as the tunable properties of the reaction. The tunable redox reaction of SWNTs and H2O2 mediated by thiocyanate ions may offer a new sensing scheme for continuously monitoring H2O2 concentrations. PMID:18611008

Xu, Yang; Pehrsson, Pehr E; Chen, Liwei; Zhao, Wei

2008-08-01

277

Production of a Gas- Controlling a Chemical Reaction  

NSDL National Science Digital Library

In this activity, students have seen a few reactions that produce a gas.They will adjust the amount of baking soda and vinegar to control the amount of gas produced in the reaction. The materials needed are basic and easily available anywhere. There is a downloadable activity sheet that will be very helpful to educators, and will help students stay on track. An assessment sheet is also available on the activity page to keep track of students progress. There is also a step by step guide as to how to perform the experiment, and how to introduce it t the students.

Kessler, James; Galvan, Patti

2010-01-01

278

Direct Monte Carlo simulation of chemical reaction systems: Dissociation and recombination  

E-print Network

Direct Monte Carlo simulation of chemical reaction systems: Dissociation and recombination Shannon of Physics. I. INTRODUCTION In earlier studies1­5 we have found the direct Monte Carlo simulation method6 Monte Carlo simulation of dissociation-recombination reac- tions of the type M AB M A B. These reactions

Anderson, James B.

279

Unraveling the chemical dynamics of bimolecular reactions of ground state boron atoms, B(2  

E-print Network

Unraveling the chemical dynamics of bimolecular reactions of ground state boron atoms, B(2 PjArticle on the web 8th March 2004 The reaction dynamics of atomic boron, B(2 P), with acetylene, C2H2(X 1 Sg þ molecular beams technique. Only the atomic boron versus hydrogen atom exchange pathway was observed. Forward

Kaiser, Ralf I.

280

Glow Discharge Enhanced Chemical Reaction: Application in Ammonia Synthesis and Hydrocarbon Gas Cleanup  

E-print Network

reforming ........................................................................................ 12 2.1.5 Water gas shift reaction .............................................................................. 13 2.2 Plasma physics... and thus lower the required reaction temperatures and avoid unwanted by-product formation.[9] 2.2 Plasma physics Plasma is described as the fourth state of matter. Unlike solid, liquid and gas, plasma usually character with high energy, chemical...

Ming, Pingjia

2014-06-05

281

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

E-print Network

rna;b a;br2na;b ÿ Rnanb; (1) where R is the reaction rate coefficient, v is the velocity of the flow chemical reaction, A B ! C, in a statistically stationary bounded chaotic flow at large Peclet number Pe lamellar structure in the bulk part of the flow is terminated by an exponential decay, / expÿt (where

Lebedev, Vladimir

282

A coupled chemical burster: The chlorine dioxide-iodide reaction in two flow reactors  

E-print Network

A coupled chemical burster: The chlorine dioxide-iodide reaction in two flow reactors Miles Dolnika (Received 13 July 1992; accepted 1 October 1992) The dynamical behavior of the chlorine dioxide, bursting behavior has been observed in the chlorine dioxide -iodide reaction in a CSTR." When the excitable

Epstein, Irving R.

283

An approximate Riemann solver for thermal and chemical nonequilibrium flows  

NASA Technical Reports Server (NTRS)

Among the many methods available for the determination of inviscid fluxes across a surface of discontinuity, the flux-difference-splitting technique that employs Roe-averaged variables has been used extensively by the CFD community because of its simplicity and its ability to capture shocks exactly. This method, originally developed for perfect gas flows, has since been extended to equilibrium as well as nonequilibrium flows. Determination of the Roe-averaged variables for the case of a perfect gas flow is a simple task; however, for thermal and chemical nonequilibrium flows, some of the variables are not uniquely defined. Methods available in the literature to determine these variables seem to lack sound bases. The present paper describes a simple, yet accurate, method to determine all the variables for nonequilibrium flows in the Roe-average state. The basis for this method is the requirement that the Roe-averaged variables form a consistent set of thermodynamic variables. The present method satisfies the requirement that the square of the speed of sound be positive.

Prabhu, Ramadas K.

1994-01-01

284

Chemical Principles Revisited. Redox Reactions and the Electropotential Axis.  

ERIC Educational Resources Information Center

This paper suggests a nontraditional pedagogic approach to the subject of redox reactions and electrode potentials suitable for freshman chemistry. Presented is a method for the representation of galvanic cells without the introduction of the symbology and notation of conventional cell diagrams. (CW)

Vella, Alfred J.

1990-01-01

285

Characterization and Modeling of a Coupled Thermal-Hydrological-Mechanical-Chemical-Biological Experimental Facility at DUSEL  

NASA Astrophysics Data System (ADS)

A design is being formulated for a large-scale subsurface experimental facility at the 4850 foot level of the Homestake Mine in South Dakota. The purpose of the experiment is to investigate coupled Thermal-Hydrological-Mechanical-Chemical-Biological (THMCB) processes in fractured rock under stress and would be part of the proposed Deep Underground Science and Engineering Laboratory (DUSEL). Key questions we propose to answer are: 1) What are the effective reaction rates for mineral-fluid interaction in fractured rock under stress?; 2) How does mineral and fluid chemistry affect fracture mechanical behavior and permeability changes under stress at elevated temperatures?; and 3) How do microbial communities evolve in fractured rock under a thermal gradient and under changing stress conditions? In addition to the experiment as an in-situ laboratory for studying crustal processes, it has significant benefits for evaluating stimulation and production in Enhanced Geothermal Systems. Design and planning of the experiment included characterization of the geological, chemical, and isotopic characteristics of the rock and seeping fluids, thermal-hydrological and reactive transport modeling. During a reconnaissance study, strong heterogeneity in fracture fluxes and permeability were observed at the block site with some open boreholes continuously flowing at up to 1 liter/minute, and locally elevated fluid temperatures. A two-dimensional thermal-hydrological model was developed to evaluate fluid fluxes and temperatures as a function of heat input and borehole heater configuration. The dual permeability model considers fluid flow and heat transfer between an array of fractures and rock matrix, both having permeability anisotropy. A horizontal rock matrix permeability of 10-18 m2 was based on recent lab measurements, with a vertical matrix permeability estimated to be one order-of-magnitude higher to account for the strong nearly vertical foliation in the Homestake and Poorman formations. The fracture permeability was assumed to be anisotropic with a higher vertical permeability (kH=10-14 m2; kV=10-13 m2) to treat larger fracture apertures perpendicular to the least principal stress. Ten borehole heaters were emplaced at distances of 4 m with a heat input of 5 kW/m. Maximum convective fracture flow velocities of about 10 m/y were predicted after 5 years of heating with temperatures reaching close to 375°C. Reactive-transport models of the THMCB block will be a basis for the prediction of reaction-induced porosity/permeability changes as a function of the observed fracture fluxes and hydrological boundary conditions. The models use constraints from 87Sr/86Sr ratios measured in fluids, as well as other geochemical, mineralogical, and isotopic data.

Sonnenthal, E. L.; Elsworth, D.; Lowell, R. P.; Maher, K.; Mailloux, B. J.; Uzunlar, N.; Conrad, M. E.; Jones, T. L.; Olsen, N. J.

2010-12-01

286

Exploring the limits of ultrafast polymerase chain reaction using liquid for thermal heat exchange: A proof of principle  

NASA Astrophysics Data System (ADS)

Thermal ramp rate is a major limiting factor in using real-time polymerase chain reaction (PCR) for routine diagnostics. We explored the limits of speed by using liquid for thermal exchange rather than metal as in traditional devices, and by testing different polymerases. In a clinical setting, our system equaled or surpassed state-of-the-art devices for accuracy in amplifying DNA/RNA of avian influenza, cytomegalovirus, and human immunodeficiency virus. Using Thermococcus kodakaraensis polymerase and optimizing both electrical and chemical systems, we obtained an accurate, 35 cycle amplification of an 85-base pair fragment of E. coli O157:H7 Shiga toxin gene in as little as 94.1 s, a significant improvement over a typical 1 h PCR amplification.

Maltezos, George; Johnston, Matthew; Taganov, Konstantin; Srichantaratsamee, Chutatip; Gorman, John; Baltimore, David; Chantratita, Wasun; Scherer, Axel

2010-12-01

287

WORKSHOP ON STATUS OF TEST METHODS FOR ASSESSING POTENTIAL OF CHEMICALS TO INDUCE RESPIRATORY ALLERGIC REACTIONS  

EPA Science Inventory

Because of the association between allergy and asthma and the increasing incidence of morbidity and mortality due to asthma, there is growing concern over the potential of industrial chemicals to produce allergic reactions in the respiratory tract. Two classes of chemicals have b...

288

5.0 Application of Chemical Reaction Codes 5.1. Background  

E-print Network

Mineral precipitation/dissolution The distribution of aqueous species in a multi-component chemical system or more phases that includes an aqueous solution, such as the mass change resulting from the precipitation-dependent movement of one or more solutes during fluid flow. 5.2 5.1.1 Definition of Chemical Reaction Modeling

289

Shock wave and modeling study of the thermal decomposition reactions of pentafluoroethane and 2-H-heptafluoropropane.  

PubMed

The thermal decomposition reactions of CF3CF2H and CF3CFHCF3 have been studied in shock waves by monitoring the appearance of CF2 radicals. Temperatures in the range 1400-2000 K and Ar bath gas concentrations in the range (2-10) × 10(-5) mol cm(-3) were employed. It is shown that the reactions are initiated by C-C bond fission and not by HF elimination. Differing conclusions in the literature about the primary decomposition products, such as deduced from experiments at very low pressures, are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF2 formation was observed while the final CF2 yields remained close to two CF2 per C2F5H or three CF2 per C3F7H decomposed. This is explained by secondary bimolecular reactions which lead to comparably stable transient species like CF3H, releasing CF2 at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions in the decomposition mechanism. PMID:24352693

Cobos, C J; Sölter, L; Tellbach, E; Troe, J

2014-06-01

290

Control and detection of chemical reactions in microfluidic systems  

Microsoft Academic Search

Recent years have seen considerable progress in the development of microfabricated systems for use in the chemical and biological sciences. Much development has been driven by a need to perform rapid measurements on small sample volumes. However, at a more primary level, interest in miniaturized analytical systems has been stimulated by the fact that physical processes can be more easily

Andrew J. deMello

2006-01-01

291

X-ray Microspectroscopy and Chemical Reactions in Soil Microsites  

SciTech Connect

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

D Hesterberg; M Duff; J Dixon; M Vepraskas

2011-12-31

292

Chemical Reactions and Cloud Nucleation on Soot Aerosols  

NASA Astrophysics Data System (ADS)

Incomplete combustion causes enhanced levels of soot aerosols and polycyclic aromatic hydrocarbons in the urban atmosphere. In turn, the increased abundance of aerosols may facilitate increased cloudiness by acting as cloud condensation nuclei (CCN) and ice nuclei (IN). The goal of our study is to first identify and quantify chemical changes in atmospheric aerosols, such as the formation of surface hydrophilic functional groups upon exposed to ozone, and second, to assess the cloud nucleating ability of the oxidized aerosols. When first introduced into the atmosphere, soot is a hydrophobic substance and relatively poor CCN or IN. As soot encounters atmospheric oxidizing agents, such as ozone, its surface chemical properties may be altered. Thus, the soot particles become hydrophilic, and subsequently may be much more efficient cloud nuclei. In this study, soot samples are generated using various fuel sources including diesel and propane. Using a Fourier Transform Infrared Spectrometer equipped with a Horizontal Attenuated Total Reflectance cell, we observe the chemical changes at the soot surface as a function of ozone exposure. In addition, the ice nucleating ability of fresh and chemically aged soot is identified using a microscope cooling apparatus. Results will be presented and atmospheric implications discussed.

Brooks, S. D.; Mason, L.; Fornea, A.

2006-12-01

293

Development of a novel fingerprint for chemical reactions and its application to large-scale reaction classification and similarity.  

PubMed

Fingerprint methods applied to molecules have proven to be useful for similarity determination and as inputs to machine-learning models. Here, we present the development of a new fingerprint for chemical reactions and validate its usefulness in building machine-learning models and in similarity assessment. Our final fingerprint is constructed as the difference of the atom-pair fingerprints of products and reactants and includes agents via calculated physicochemical properties. We validated the fingerprints on a large data set of reactions text-mined from granted United States patents from the last 40 years that have been classified using a substructure-based expert system. We applied machine learning to build a 50-class predictive model for reaction-type classification that correctly predicts 97% of the reactions in an external test set. Impressive accuracies were also observed when applying the classifier to reactions from an in-house electronic laboratory notebook. The performance of the novel fingerprint for assessing reaction similarity was evaluated by a cluster analysis that recovered 48 out of 50 of the reaction classes with a median F-score of 0.63 for the clusters. The data sets used for training and primary validation as well as all python scripts required to reproduce the analysis are provided in the Supporting Information. PMID:25541888

Schneider, Nadine; Lowe, Daniel M; Sayle, Roger A; Landrum, Gregory A

2015-01-26

294

Reaction dynamics. Extremely short-lived reaction resonances in Cl + HD (v = 1) ? DCl + H due to chemical bond softening.  

PubMed

The Cl + H2 reaction is an important benchmark system in the study of chemical reaction dynamics that has always appeared to proceed via a direct abstraction mechanism, with no clear signature of reaction resonances. Here we report a high-resolution crossed-molecular beam study on the Cl + HD (v = 1, j = 0) ? DCl + H reaction (where v is the vibrational quantum number and j is the rotational quantum number). Very few forward scattered products were observed. However, two distinctive peaks at collision energies of 2.4 and 4.3 kilocalories per mole for the DCl (v' = 1) product were detected in the backward scattering direction. Detailed quantum dynamics calculations on a highly accurate potential energy surface suggested that these features originate from two very short-lived dynamical resonances trapped in the peculiar H-DCl (v' = 2) vibrational adiabatic potential wells that result from chemical bond softening. We anticipate that dynamical resonances trapped in such wells exist in many reactions involving vibrationally excited molecules. PMID:25554783

Yang, Tiangang; Chen, Jun; Huang, Long; Wang, Tao; Xiao, Chunlei; Sun, Zhigang; Dai, Dongxu; Yang, Xueming; Zhang, Dong H

2015-01-01

295

Thermal modelling of battery configuration and self-discharge reactions in vanadium redox flow battery  

NASA Astrophysics Data System (ADS)

During the operation of vanadium redox flow battery, the vanadium ions diffuse across the membrane as a result of concentration gradients between the two half-cells in the stack, leading to self-discharge reactions in both half-cells that will release heat to the electrolyte and subsequently increase the electrolyte temperature. In order to avoid possible thermal precipitation in the electrolyte solution and prevent possible overheating of the cell components, the electrolyte temperature needs to be known. In this study, the effect of the self-discharge reactions was incorporated into a thermal model based on energy and mass balances, developed for the purpose of electrolyte temperature control. Simulations results have shown that the proposed model can be used to investigate the thermal effect of the self-discharge reactions on both continuous charge-discharge cycling and during standby periods, and can help optimize battery designs and fabrication for different applications.

Tang, Ao; Bao, Jie; Skyllas-Kazacos, Maria

2012-10-01

296

Detailed Chemical Kinetic Reaction Mechanisms for Incineration of Organophosphorus and Fluoro-Organophosphorus Compounds  

SciTech Connect

A detailed chemical kinetic reaction mechanism is developed to describe incineration of the chemical warfare nerve agent sarin (GB), based on commonly used principles of bond additivity and hierarchical reaction mechanisms. The mechanism is based on previous kinetic models of organophosphorus compounds such as TMP, DMMP and DIMP that are often used as surrogates to predict incineration of GB. Kinetic models of the three surrogates and GB are then used to predict their consumption in a perfectly stirred reactor fueled by natural gas to simulate incineration of these chemicals. Computed results indicate that DIMP is the only one of these surrogates that adequately describes combustion of GB under comparable conditions. The kinetic pathways responsible for these differences in reactivity are identified and discussed. The most important reaction in GB and DIMP that makes them more reactive than TMP or DMMP is found to be a six-center molecular elimination reaction producing propene.

Glaude, P A; Melius, C; Pitz, W J; Westbrook, C K

2001-12-13

297

Diffusion reaction in a thermal gradient: Implications for the genesis of anorthitic plagioclase, high alumina basalt and igneous mineral layering  

NASA Astrophysics Data System (ADS)

Piston-cylinder experiments investigating the interaction between basaltic andesite melt and partially molten gabbro in a thermal gradient provide insight into melt-rock reaction processes occurring during magma differentiation in the crust. In two experiments juxtaposing basaltic andesite and gabbro at 0.5 GPa pressure for durations of either 13 or 26 days, diffusive chemical exchange between the two materials results in mineral layering and notable mineral compositions such as anorthitic plagioclase. Specifically, the basaltic andesite gains Al 2O 3, MgO and CaO from the gabbro and loses Na 2O, K 2O, SiO 2 and FeO to it with a plagioclase-rich layer developing at the interface between the two materials in a process termed diffusion-reaction. The percent crystallinity of the basaltic andesite increases during the process and the plagioclase crystals within the interface region develop anorthitic cores (up to An 90) that abruptly shift in composition to thin rims that are in Na-Ca exchange equilibrium with the co-existing melt. Both the mineralogical layering and bulk compositional change occurring at the interface are reproduced in model simulations of diffusion-reaction. Isotopic tracers ( 45Ca, 6Li, 84Sr and 136Ba) initially deposited at the basaltic andesite-gabbro interface in the 13-day experiment were detected in the cores of the anorthitic plagioclase after the experiment, demonstrating that the melt chemically communicates with the plagioclase cores over the duration of the diffusion-reaction experiment. The formation of anorthitic plagioclase during diffusion-reaction may explain its widespread occurrence in terrestrial volcanic rocks without requiring the presence of ultra-calcic melts. Textures and mineralogical changes in the gabbro indicate that chemical transport occurs throughout the experiments despite temperatures at the cold end of the experimental capsule approaching 500 °C. For instance, apatite, FeNiS, olivine and almost pure albite occur at distinct, specific horizons in the gabbro within the 26-day experiment. Because the bulk element profiles indicating chemical transport reflect analyses of almost completely solid gabbro, equilibration between minerals and fluids/melts must be rapid. The overall effect of the diffusion-reaction process is to make an ascending magma more primitive in composition (and in this case, produce anorthitic plagioclase) while making surrounding crustal wall rocks more evolved. Several observations within igneous rocks support the occurrence of this process, suggesting that the genesis of porphyritic high alumina basalt, ubiquitously observed at convergent margins, could reflect a diffusion-reaction process in the crust.

Lundstrom, Craig; Boudreau, Alan; Pertermann, Maik

2005-09-01

298

Dynamic simulation of impurity transport and chemical reactions in a Bridgman furnace for directional solidification of multi-crystalline silicon  

NASA Astrophysics Data System (ADS)

Numerical results from a dynamic simulation of impurity transport and reactions in a Bridgman furnace for directional solidification of multi-crystalline silicon are presented and compared to experimental results. The simulation includes the calculation of the thermal field, melt and gas flow velocity field, transport and chemical reactions of oxygen and carbon impurities for the entire process based on heating, melting and solidification phases. Carbon and oxygen distribution in the ingot is analyzed experimentally by means of FT-IR spectroscopy and LECO combustion method, the CO development by means of an ?-GC gas analyzer. The simulated impurity distribution in the ingot and the CO development above the free melt surface are in good agreement with the experimental results. Furthermore the results indicate that the carbon solubility limit is already reached at the stage of melting and SiC precipitates are likely to form at the early stage of growth.

Bellmann, M. P.; Panjwani, B.; Syvertsen, M.; Meese, E. A.

2013-04-01

299

Theory of reversible associative-dissociative diffusion-influenced chemical reaction. II. Bulk reaction  

NASA Astrophysics Data System (ADS)

A many-particle homogeneous reacting system of reactants, where bulk reversible reaction A + B ? C takes place, is considered in the framework of the kinetic theory approach. The various forms of kinetic equations in the thermodynamic limit are obtained, and important relations between kinetic coefficients characterizing the course of bulk and the corresponding geminate reactions are established. Based on the kinetic equations derived, different results available in the literature have been analyzed. Universal long-term kinetic laws of the reaction course are deduced.

Kipriyanov, Alexey A.; Doktorov, Alexander B.

2013-01-01

300

Theory of reversible associative-dissociative diffusion-influenced chemical reaction. I. Geminate reaction  

NASA Astrophysics Data System (ADS)

A many-particle, in the general case, inhomogeneous reacting system of independent pairs of reactants, where geminate reversible reaction A+Brightleftarrows C takes place, is considered in the framework of the kinetic theory approach. The kinetic equations in the thermodynamic limit are obtained, and important relations between kinetic coefficients characterizing the reaction course are established, as well as the relations between the kinetic dependencies under different initial conditions including the relations that extend the familiar literature results to the case of rather realistic model of the reacting system. Universal long-term kinetic laws of the reaction course are determined.

Doktorov, Alexander B.; Kipriyanov, Alexey A.

2011-09-01

301

X-ray imaging of chemically active valence electrons during a pericyclic reaction  

NASA Astrophysics Data System (ADS)

Time-resolved imaging of chemically active valence electron densities is a long-sought goal, as these electrons dictate the course of chemical reactions. However, X-ray scattering is always dominated by the core and inert valence electrons, making time-resolved X-ray imaging of chemically active valence electron densities extremely challenging. Here we demonstrate an effective and robust method, which emphasizes the information encoded in weakly scattered photons, to image chemically active valence electron densities. The degenerate Cope rearrangement of semibullvalene, a pericyclic reaction, is used as an example to visually illustrate our approach. Our work also provides experimental access to the long-standing problem of synchronous versus asynchronous bond formation and breaking during pericyclic reactions.

Bredtmann, Timm; Ivanov, Misha; Dixit, Gopal

2014-11-01

302

X-ray imaging of chemically active valence electrons during a pericyclic reaction.  

PubMed

Time-resolved imaging of chemically active valence electron densities is a long-sought goal, as these electrons dictate the course of chemical reactions. However, X-ray scattering is always dominated by the core and inert valence electrons, making time-resolved X-ray imaging of chemically active valence electron densities extremely challenging. Here we demonstrate an effective and robust method, which emphasizes the information encoded in weakly scattered photons, to image chemically active valence electron densities. The degenerate Cope rearrangement of semibullvalene, a pericyclic reaction, is used as an example to visually illustrate our approach. Our work also provides experimental access to the long-standing problem of synchronous versus asynchronous bond formation and breaking during pericyclic reactions. PMID:25424639

Bredtmann, Timm; Ivanov, Misha; Dixit, Gopal

2014-01-01

303

Indoor volatile organic compounds and chemical sensitivity reactions.  

PubMed

Studies of unexplained symptoms observed in chemically sensitive subjects have increased the awareness of the relationship between neurological and immunological diseases due to exposure to volatile organic compounds (VOCs). However, there is no direct evidence that links exposure to low doses of VOCs and neurological and immunological dysfunction. We review animal model data to clarify the role of VOCs in neuroimmune interactions and discuss our recent studies that show a relationship between chronic exposure of C3H mice to low levels of formaldehyde and the induction of neural and immune dysfunction. We also consider the possible mechanisms by which VOC exposure can induce the symptoms presenting in patients with a multiple chemical sensitivity. PMID:24228055

Win-Shwe, Tin-Tin; Fujimaki, Hidekazu; Arashidani, Keiichi; Kunugita, Naoki

2013-01-01

304

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

NASA Astrophysics Data System (ADS)

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

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

2013-04-01

305

Experimental results of exothermic reaction with concentration gradient catalyst in a solar chemical heat pump  

SciTech Connect

Solar chemical heat pump can upgrade the low temperature solar heat about 80 C to about 150--200 C by the reversible chemical reactions of 2-propanol/acetone/hydrogen, which are composed of endothermic and exothermic reactions. In the exothermic process of above reaction, a temperature peak occurs near the inlet of reaction zone in the case of arranging catalyst uniformly. Such a temperature distribution is not suitable for heat exchange. Therefore, the authors arrange the concentration of catalyst gradationally so as not to occur the temperature peak. In this paper, experimental results of exothermic reaction with concentration gradient catalyst in a double tubular exothermic reactor are presented. These results show that the arrangement of concentration gradient catalyst has the possibility about the temperature control in the catalytic reactor.

Takashima, Takumi; Doi, Takuya; Ando, Yuji; Tanaka, Tadayoshi [Electrotechnical Lab., Tsukuba, Ibaraki (Japan); Miyahara, Ryosuke; Kamoshida, Junji [Shibaura Inst. of Tech., Omiya, Saitama (Japan)

1997-12-31

306

Photothermal-reaction-assisted two-photon lithography of silver nanocrystals capped with thermally cleavable ligands  

SciTech Connect

We report an alternative approach to produce micropatterns of metallic nanoparticles using photothermal-reaction-assisted two-photon direct laser writing. The patterns are achieved using a facile surface treatment of silver nanoparticles (Ag NPs) functionalized with thermally cleavable ligands; N-(tert-butoxycarbonyl)-L-cysteine methyl ester. The ligand cleavage initiated by pulsed laser-induced thermal reaction results in a significant change in dispersiblility of the nanocrystals, thereby enabling a solvent-selective development process after photopatterning. We demonstrated that Ag NP patterns with submicron linewidths can be achieved using near infrared pulsed laser illumination.

Kim, Won Jin; Vidal, Xavier; Baev, Alexander; Jee, Hong Sub; Swihart, Mark T.; Prasad, Paras N. [Department of Chemistry, Institute for Lasers, Photonics, and Biophotonics, University at Buffalo, State University of New York, Buffalo, New York 14260 (United States)

2011-03-28

307

Thermal Behavior, Nonisothermal Decomposition Reaction Kinetics of Mixed Ester Double-base Gun Propellants  

Microsoft Academic Search

The thermal decomposition behavior and nonisothermal reaction kinetics of the double-base gun propellants containing the mixed ester of triethyleneglycol dinitrate(TEGDN) and nitroglycerin(NG) were investigated by thermogravimetry(TG) and differential thermogravimetry(DTG), and differential scanning calorimetry(DSC) under the high-pressure dynamic ambience. The results show that the thermal decomposition processes of the mixed nitric ester gun propellants have two mass-loss stages. Nitric ester evaporates

Jian-hua YI; Feng-qi ZHAO; Si-yu XU; Hong-xu GAO; Rong-zu HU

2008-01-01

308

Investigation of shock-induced and shock-assisted chemical reactions in molybdenum-silicon powder mixtures  

NASA Astrophysics Data System (ADS)

In this research, chemical reactions occurring in molybdenum and silicon powder mixtures under "shock-induced" (those occurring during the high-pressure shock state) and "shock-assisted" (those occurring subsequent to the shock event, but due to bulk temperature increases) conditions were investigated. Differences in the densities and yield strengths of the two constituents, in addition to the large heat of reaction associated with molybdenum disilicide (MoSi2) formation can lead to shock-induced as well as shock-assisted reactions, which make this an ideal system to delineate the kinetics and mechanisms of reactions occurring in shock-compressed powder mixtures. Shock recovery experiments performed on Mo + 2 Si powder mixtures employing cylindrical implosion geometry showed thermally initiated reactions. A mixed phase eutectic type microstructure of MoSi2 and Mo 5Si3, resulting from reaction occurring due to melting of both reactants, was observed in axial regions of the cylindrical compacts. In regions surrounding the mach stem, melting of only silicon and reaction occurring via dissolution and re-precipitation forming MoSi2 spherules surrounding molybdenum particles in a melted and solidified silicon matrix was observed. The planar pressure shock recovery geometry showed a single phase MoSi2, microstructure formed due to a solid-state pressure-induced reaction process. The time-resolved instrumented experiments were performed using a single stage gas gun in the velocity range of 500 m/s to 1 km/s, and employed poly-vinyl di-flouride (PVDF) stress gauges placed at the front and rear surfaces of the powder to determine the crush strength, densification history, and reaction initiation threshold conditions. Time-resolved experiments performed on ˜58% dense Mo + 2 Si powder mixtures at input stresses less than 4 GPa, showed characteristics of powder densification and dispersed propagated wave stress profiles with rise time >˜40 nanoseconds. At input stress between 4--6 GPa, the powder mixtures showed a sharp rise time (<˜10 ns) of propagated wave profile and an expanded state of products revealing conclusive evidence of shock-induced reaction. At input stresses greater than 6 GPa, the powder mixtures showed a lower rise time and transition to a low-compressibility (melt) state indicating lack of shock-induced reaction. The results of this work show that (a) premature formation of a melt phase restricts mixing between reactants and inhibits "shock-induced" reaction initiation, although "shock-assisted" reactions can still occur in time scales of thermal equilibrium, and (b) the crush strength of powder mixtures is the most important parameter that controls initiation of a "shock-induced" reaction. Reaction synthesis experiments conducted on 55--95% dense Mo + 2 Si powder mixture compacts under an applied electric field showed that SHS reactions that would have normally become extinguished without the application of electric field, were observed to be self-sustained. Under such conditions, the reaction kinetics were observed to be enhanced and the reaction products showed a highly refined microstructure.

Vandersall, Kevin Stewart

1999-10-01

309

RPMDRATE: Bimolecular chemical reaction rates from ring polymer molecular dynamics  

NASA Astrophysics Data System (ADS)

We present RPMDRATE, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH4, OH+CH4 and H+C2H6 reactions. Catalogue identifier: AENW_v1_0 Program summary URL: http://cpc.cs.qub.ac.uk/summaries/AENW_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: MIT license No. of lines in distributed program, including test data, etc.: 94512 No. of bytes in distributed program, including test data, etc.: 1395674 Distribution format: tar.gz Programming language: Fortran 90/95, Python (version 2.6.x or later, including any version of Python 3, is recommended). Computer: Not computer specific. Operating system: Any for which Python, Fortran 90/95 compiler and the required external routines are available. Has the code been vectorized or parallelized?: The program can efficiently utilize 4096+ processors, depending on problem and available computer. At low temperatures, 110 processors are reasonable for a typical umbrella integration run with an analytic potential energy function and gradients on the latest x86-64 machines.

Suleimanov, Yu. V.; Allen, J. W.; Green, W. H.

2013-03-01

310

Quantum chemical study of penicillin: Reactions after acylation  

NASA Astrophysics Data System (ADS)

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

Li, Rui; Feng, Dacheng; Zhu, Feng

311

Ca + HF - The anatomy of a chemical insertion reaction  

NASA Technical Reports Server (NTRS)

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

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

1987-01-01

312

Rate-Controlled Constrained-Equilibrium Theory of Chemical Reactions  

NASA Astrophysics Data System (ADS)

The Rate-Controlled Constrained-Equilibrium (RCCE) method for simplifying the treatment of reactions in complex systems is summarized and the selection of constraints for both close-to and far-from equilibrium systems is discussed. Illustrative examples of RCCE calculations of carbon monoxide concentrations in the exhaust products of an internal combustion engine and ignition delays for methane-oxygen mixtures in a constant volume adiabatic chamber are given and compared with "detailed" calculations. The advantages of RCCE calculations over "detailed" calculations are discussed.

Keck, James C.

2008-08-01

313

Theoretical Chemical Dynamics Studies of Elementary Combustion Reactions  

SciTech Connect

The objective of this research was to develop and apply methods for more accurate predictions of reaction rates based on high-level quantum chemistry. We have developed and applied efficient, robust methods for fitting global ab initio potential energy surfaces (PESs) for both spectroscopy and dynamics calculations and for performing direct dynamics simulations. Our approach addresses the problem that high-level quantum calculations are often too costly in computer time for practical applications resulting in the use of levels of theory that are often inadequate for reactions. A critical objective was to develop practical methods that require the minimum number of electronic structure calculations for acceptable fidelity to the ab initio PES. Our method does this by a procedure that determines the optimal configurations at which ab initio points are computed, and that ensures that the final fitted PES is uniformly accurate to a prescribed tolerance. Our fitting methods can be done automatically, with little or no human intervention, and with no prior knowledge of the topology of the PES. The methods are based on local fitting schemes using interpolating moving least-squares (IMLS). IMLS has advantages over the very effective modified-Shepard methods developed by Collins and others in that higher-order polynomials can be used and does not require derivatives but can benefit from them if available.

Donald L. Thompson

2009-09-30

314

Sensitivity of chemical reaction networks: A structural approach. 1. Examples and the carbon metabolic network.  

PubMed

In biological cells, chemical reaction pathways lead to complex network systems like metabolic networks. One experimental approach to the dynamics of such systems examines their "sensitivity": each enzyme mediating a reaction in the system is increased/decreased or knocked out separately, and the responses in the concentrations of chemicals or their fluxes are observed. In this study, we present a mathematical method, named structural sensitivity analysis, to determine the sensitivity of reaction systems from information on the network alone. We investigate how the sensitivity responses of chemicals in a reaction network depend on the structure of the network, and on the position of the perturbed reaction in the network. We establish and prove some general rules which relate the sensitivity response to the structure of the underlying network. We describe a hierarchical pattern in the flux response which is governed by branchings in the network. We apply our method to several hypothetical and real life chemical reaction networks, including the metabolic network of the Escherichia coli TCA cycle. PMID:25451520

Mochizuki, Atsushi; Fiedler, Bernold

2015-02-21

315

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

NASA Astrophysics Data System (ADS)

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

Tanaka, H.; Koizumi, S.; Hashimoto, T.; Kurosaki, K.; Ohmae, M.; Kobayashi, S.

2006-11-01

316

A study of the effects of solid phase reactions on the thermal degradation and ballistic properties of solid propellants  

NASA Technical Reports Server (NTRS)

The thermal stability of perchlorate composite propellants was studied at 135 and 170 C. The experimental efforts were concentrated on determining the importance of heterogeneous oxidizer-fuel reactions in the thermal degradation process. The experimental approach used to elucidate the mechanisms by which the oxidizer fuel composites thermally degrade was divided into two parts: (1) keeping the fuel constant and varying the nature of the oxidizers, and (2) holding the oxidizer constant and varying the fuel components. The fuel component primarily utilized in the first phase was polyethylene. Oxidizers included KClO4, KClO3, NH4ClO4 and NH4ClO4 doped with materials such as chlorate, phosphate and arsenate. In the second phase the oxidizer used was primarily NH4ClO4 while the fuels included saturated and unsaturated polybutadiene prepolymers and a series of bonding agents. Techniques employed in the current study include thermogravimetric measurements, differential thermal analysis, infrared, mass spectrometry, electron microscopy, and appropriate wet chemical analysis.

Schmidt, W. G.

1974-01-01

317

Chemical reactions of conformationally selected 3-aminophenol molecules in a beam with Coulomb-crystallized Ca{sup +} ions  

SciTech Connect

Many molecules exhibit multiple conformers that often easily interconvert under thermal conditions. Therefore, single conformations are difficult to isolate which renders the study of their distinct chemical reactivities challenging. We have recently reported a new experimental method for the characterization of conformer-specific effects in chemical reactions [Y.-P. Chang, K. D?ugo??cki, J. Küpper, D. Rösch, D. Wild, and S. Willitsch, “Specific chemical reactivities of spatially separated 3-aminophenol conformers with cold Ca{sup +} ions,” Science 342, 98–101 (2013)]. Different conformers are spatially separated using inhomogeneous electric fields and reacted with a Coulomb crystal of cold, spatially localized ions in a trap. As a first application, we studied reactions between the two conformers of 3-aminophenol and Ca{sup +}. We observed a twofold larger rate constant for the cis compared to the trans conformer which was rationalized in terms of the differences in the long-range ion-molecule interactions. The present article provides a detailed description of the new method and a full account of the experimental results as well as the accompanying theoretical calculations.

Rösch, Daniel; Willitsch, Stefan, E-mail: stefan.willitsch@unibas.ch [Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel (Switzerland)] [Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel (Switzerland); Chang, Yuan-Pin [Center for Free-Electron Laser Science, DESY, Notkestrasse 85, 22607 Hamburg (Germany)] [Center for Free-Electron Laser Science, DESY, Notkestrasse 85, 22607 Hamburg (Germany); Küpper, Jochen, E-mail: jochen.kuepper@cfel.de [Center for Free-Electron Laser Science, DESY, Notkestrasse 85, 22607 Hamburg (Germany) [Center for Free-Electron Laser Science, DESY, Notkestrasse 85, 22607 Hamburg (Germany); Department of Physics, University of Hamburg, Luruper Chaussee 149, 22761 Hamburg (Germany); The Hamburg Center for Ultrafast Imaging, University of Hamburg, Luruper Chaussee 149, 22761 Hamburg (Germany)

2014-03-28

318

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

SciTech Connect

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

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

2008-07-16

319

Nonisothermal Thermal Decomposition Reaction Kinetics of Double-base Propellant Catalyzed with Lanthanum Citrate  

Microsoft Academic Search

The decomposition reaction kinetics of the double-base (DB) rocket propellant composed of the mixed ester of triethyleneglycol dinitrate (TEGDN) and nitroglycerin (NG), and nitrocellulose (NC) with lanthanum citrate as a combustion catalyst was investigated by thermogravimetry and differential thermogravimetry (TG-DTG), and differential scanning calorimetry (DSC) under atmospheric pressure and flowing nitrogen gas conditions. The results showed that the thermal decomposition

Jianhua Yi; Fengqi Zhao; Siyu Xu; Hongxu Gao; Rongzu Hu; Haixia Hao; Qing Pei; Yin Gao

2007-01-01

320

Competition between charge exchange and chemical reaction - The D2/+/ + H system  

NASA Technical Reports Server (NTRS)

Study of the special features of molecular charge exchange and its competition with chemical reaction in the case of the D2(+) + H system. The trajectory surface hopping (TSH) model proposed by Tully and Preston (1971) is used to study this competition for a number of reactions involving the above system. The diatomics-in-molecules zero-overlap approximation is used to calculate the three adiabatic surfaces - one triplet and two singlet - which are needed to describe this system. One of the significant results of this study is that the chemical reaction and charge exchange are strongly coupled. It is also found that the number of trajectories passing into the chemical regions of the three surfaces depends very strongly on the surface crossings.-

Preston, R. K.; Cross, R. J., Jr.

1973-01-01

321

The prediction of thermal stability of self-reactive chemicals  

Microsoft Academic Search

Summary An advanced study on the thermal behaviour of double base (boost and sustain propellant) rocket motor used in a ground to air missile has been carried out by differential scanning calorimetry (DSC). The presence of two propellants as well as the different experimental conditions (open vs. closed crucibles) influence the relative thermal stability of the energetic materials. Several methods

B. Roduit; Ch. Borgeat; B. Berger; P. Folly; B. Alonso; J. N. Aebischer

2005-01-01

322

Mixing and chemical reaction in an idealized swirl chamber  

SciTech Connect

A vorticity-based, low-Mach-number model for simulating combustion in closed chambers is constructed. Numerical scheme is based on a mixed finite-difference pseudo-spectral discretization of the governing equations. Discrete evolution equations are integrated in time using a predictor-corrector scheme, while discrete elliptic systems are inverted with the help of fast-Poisson solver. Scheme is applied to analyze mixing and combustion in an idealized swirl cavity, which consists of the annular space between a spinning inner cylinder and a stationary reaction. To this end, we assume that the oxidizer and fuel are initially separated by a thin mixed region, and carefully control mixing levels by varying the duration of the swirl-driven mixing period. The mixture is then ignited along the boundary of the inner cylinder. When pre-mixing is complete, an axisymmetric flame front is established, and the reactants are consumed as the front propagates radially outwards. When the charge is partially mixed, combustion in the early stages predominantly occurs within a non-uniform premixed front. As this non-uniform front approaches the outer cylinder, a transition to a distributed combustion regime occurs. Following the transition, the remaining fuel burns at a slow rate within non-premixed flames which wrap around the inner cylinder. Results show that the mixing time has substantial effects on the pressure rise within the cavity and on the evolution of the burnt fraction, and that these effects become more pronounced as the Damkoehler number increases.

Knio, O.M.; Worlikar, A.S. [Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Mechanical Engineering; Najm, H.N. [Sandia National Labs., Livermore, CA (United States)

1996-01-01

323

Divergence and ontogenetic coupling of larval behaviour and thermal reaction norms in three closely related butterflies  

PubMed Central

Genetic trade-offs such as between generalist–specialist strategies can be masked by changes in compensatory processes involving energy allocation and acquisition which regulation depends on the state of the individual and its ecological surroundings. Failure to account for such state dependence may thus lead to misconceptions about the trade-off structure and nature of constraints governing reaction norm evolution. Using three closely related butterflies, we first show that foraging behaviours differ between species and change remarkably throughout ontogeny causing corresponding differences in the thermal niches experienced by the foraging larvae. We further predicted that thermal reaction norms for larval growth rate would show state-dependent variation throughout development as a result of selection for optimizing feeding strategies in the respective foraging niches of young and old larvae. We found substantial developmental plasticity in reaction norms that was species-specific and reflected the different ontogenetic niche shifts. Any conclusions regarding constraints on performance curves or species-differentiation in thermal physiology depend on when reaction norms were measured. This demonstrates that standardized estimates at single points in development, or in general, allow variation in only one ecological dimension, may sometimes provide incomplete information on reaction norm constraints. PMID:20719778

Berger, David; Friberg, Magne; Gotthard, Karl

2011-01-01

324

The reaction efficiency of thermal energy oxygen atoms with polymeric materials  

NASA Technical Reports Server (NTRS)

The reaction efficiency of several polymeric materials with thermal-energy (0.04 eV translational energy), ground-state (O3P) oxygen atoms was determined by exposing the materials to a room temperature gas containing a known concentration of atomic oxygen. The reaction efficiency measurements were conducted in two flowing afterglow systems of different configuration. Atomic oxygen concentration measurements, flow, transport and surface dose analysis is presented in this paper. The measured reaction efficiencies of Kapton, Mylar, polyethylene, D4-polyethylene and Tedlar are .001 to .0001 those determined with high-energy ground-state oxygen atoms in low earth orbit or in a high-velocity atom beam. D4-polyethylene exhibits a large kinetic isotope effect with atomic oxygen at thermal but not hyperthermal atom energies.

Koontz, S. L.; Nordine, Paul

1990-01-01

325

From graphite to porous carbon containing nanoparticles through chemical reactions  

SciTech Connect

Porous carbon containing large quantities of separated individual nanoparticles (2--100 nm) was produced. The chemical process includes fluorination or oxygenation of graphite, and then exposing the product (graphite fluoride or graphite oxide) to metal chlorides. The nanoparticles were metal halides or metal oxides, which could contain dopants if they were added during the synthesis process. The chlorides used in this research include those of Pd, Zn, Al and Li. Depending on the synthesis process, the carbon pores could be either filled with the nanoparticles, resulting in near-zero surface area and high metal concentration, or partially filled with nanoparticles, resulting in large surface areas. In this report, near zero surface areas were observed for a product of LiCl in carbon, and a surface area of 75 m{sup 2}/g was observed for the product of {gamma}-Al{sub 2}O{sub 3} in carbon. Heating these products in 1 atm air allowed the nanoparticles to become fused together in the form of metal oxide while the carbon was oxidized, producing metal oxides which have the same shape as the carbon precursors (fibers, fabrics, or powder) and large surface areas. These products are potentially useful in the area of batteries, high temperature gas sensors, and catalysts.

Hung, C.C. [NASA Lewis Research Center, Cleveland, OH (United States). Electro-Physics Branch; Corbin, J. [Cleveland State Univ., OH (United States). Dept. of Chemistry

1996-12-31

326

A coupled THC model of the FEBEX in situ test with bentonite swelling and chemical and thermal osmosis.  

PubMed

The performance assessment of a geological repository for radioactive waste requires quantifying the geochemical evolution of the bentonite engineered barrier. This barrier will be exposed to coupled thermal (T), hydrodynamic (H), mechanical (M) and chemical (C) processes. This paper presents a coupled THC model of the FEBEX (Full-scale Engineered Barrier EXperiment) in situ test which accounts for bentonite swelling and chemical and thermal osmosis. Model results attest the relevance of thermal osmosis and bentonite swelling for the geochemical evolution of the bentonite barrier while chemical osmosis is found to be almost irrelevant. The model has been tested with data collected after the dismantling of heater 1 of the in situ test. The model reproduces reasonably well the measured temperature, relative humidity, water content and inferred geochemical data. However, it fails to mimic the solute concentrations at the heater-bentonite and bentonite-granite interfaces because the model does not account for the volume change of bentonite, the CO(2)(g) degassing and the transport of vapor from the bentonite into the granite. The inferred HCO(3)(-) and pH data cannot be explained solely by solute transport, calcite dissolution and protonation/deprotonation by surface complexation, suggesting that such data may be affected also by other reactions. PMID:21783271

Zheng, Liange; Samper, Javier; Montenegro, Luis

2011-09-25

327

A coupled THC model of the FEBEX in situ test with bentonite swelling and chemical and thermal osmosis  

SciTech Connect

The performance assessment of a geological repository for radioactive waste requires quantifying the geochemical evolution of the bentonite engineered barrier. This barrier will be exposed to coupled thermal (T), hydrodynamic (H), mechanical (M) and chemical (C) processes. This paper presents a coupled THC model of the FEBEX (Full-scale Engineered Barrier EXperiment) in situ test which accounts for bentonite swelling and chemical and thermal osmosis. Model results attest the relevance of thermal osmosis and bentonite swelling for the geochemical evolution of the bentonite barrier while chemical osmosis is found to be almost irrelevant. The model has been tested with data collected after the dismantling of heater 1 of the in situ test. The model reproduces reasonably well the measured temperature, relative humidity, water content and inferred geochemical data. However, it fails to mimic the solute concentrations at the heater-bentonite and bentonite-granite interfaces because the model does not account for the volume change of bentonite, the CO{sub 2}(g) degassing and the transport of vapor from the bentonite into the granite. The inferred HCO{sub 3}{sup -} and pH data cannot be explained solely by solute transport, calcite dissolution and protonation/deprotonation by surface complexation, suggesting that such data may be affected also by other reactions.

Zheng, L.; Samper, J.; Montenegro, L.

2011-04-01

328

MFIX-DEM simulations of change of volumetric flow in fluidized beds due to chemical reactions  

Microsoft Academic Search

This study attempts to investigate the effect of gas volume change caused by chemical reactions on the flow hydrodynamics in a fluidized bed reactor. Various 2D simulations of ozone decomposition and the reverse reaction are conducted with a Eulerian–Lagrangian code-MFIX-DEM for a small-scale bubbling fluidized bed. The effect of particle size is studied by simulating two types of bed material

Tingwen Li; Chris Guenther

329

Dynamics of a vertically falling film in the presence of a first-order chemical reaction  

Microsoft Academic Search

The evolution of a vertically falling film in the presence of a simple first-order (exothermic or endothermic) chemical reaction is considered. The heat of reaction sets up surface tension gradients that induce thermocapillary stresses on the free-surface, thus affecting the evolution of the film. By using a long-wave expansion of the equations of motion and associated boundary conditions, we derive

Philip M. J. Trevelyan; Serafim Kalliadasis; John H. Merkin; Stephen K. Scott

2002-01-01

330

Characterization of plastic deformation and chemical reaction in titanium-polytetrafluoroethylene mixture  

NASA Astrophysics Data System (ADS)

The subject of this dissertation is the deformation process of a single metal - polymer system (titanium - polytetrafluoroethylene) and how this process leads to initiation of chemical reaction. Several different kinds of experiments were performed to characterize the behavior of this material to shock and impact. These mechanical conditions induce a rapid plastic deformation of the sample. All of the samples tested had an initial porosity which increased the plastic flow condition. It is currently believed that during the deformation process two important conditions occur: removal of the oxide layer from the metal and decomposition of the polymer. These conditions allow for rapid chemical reaction. The research from this dissertation has provided insight into the complex behavior of plastic deformation and chemical reactions in titanium - polytetrafluoroethylene (PTFE, Teflon). A hydrodynamic computational code was used to model the plastic flow for correlation with the results from the experiments. The results from this work are being used to develop an ignition and growth model for metal/polymer systems. Three sets of experiments were used to examine deformation of the 80% Ti and 20% Teflon materials: drop- weight, gas gun, and split-Hopkinson pressure bar. Recovery studies included post shot analysis of the samples using x-ray diffraction. Lagrangian hydrocode DYNA2D modeling of the drop-weight tests was performed for comparison with experiments. One of the reactions know to occur is Ti + C ? TiC (s) which results in an exothermic release. However, the believed initial reactions occur between Ti and fluorine which produces TixFy gases. The thermochemical code CHEETAH was used to investigate the detonation products and concentrations possible during Ti - Teflon reaction. CHEETAH shows that the Ti - fluorine reactions are thermodynamically favorable. This research represents the most comprehensive to date study of deformation induced chemical reaction in metal/polymers.

Davis, Jeffery Jon

1998-09-01

331

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

NASA Astrophysics Data System (ADS)

Irradiation of chemically reactive particulate suspensions by high power, pulsed laser radiation initiates reactions at the sites of the particles so that besides the absorbed optical energy, chemical energy is liberated. In addition to the release of chemical energy, chemical reaction can result in gas production both of which result in enhancement in the amplitude of the photoacoustic effect. Here we report photoacoustic and transient grating experiments with colloidal C in mixtures of H2O2 with H2O. The inclusion of H2O2 in an aqueous C suspension changes the normally endothermic reaction of C with H2O into the highly exothermic reaction of C with H2O2 leading to both an enhanced photoacoustic effect and an increase in light emission from the suspension. As well, laser-initiated exothermic reactions in suspensions of C with CH3NO2 and particulate Hg(CNO)2 in H2O are shown to result in greatly enhanced photoacoustic signal amplitudes.

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

2011-03-01

332

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

PubMed

Irradiation of chemically reactive particulate suspensions by high power, pulsed laser radiation initiates reactions at the sites of the particles so that besides the absorbed optical energy, chemical energy is liberated. In addition to the release of chemical energy, chemical reaction can result in gas production both of which result in enhancement in the amplitude of the photoacoustic effect. Here we report photoacoustic and transient grating experiments with colloidal C in mixtures of H(2)O(2) with H(2)O. The inclusion of H(2)O(2) in an aqueous C suspension changes the normally endothermic reaction of C with H(2)O into the highly exothermic reaction of C with H(2)O(2) leading to both an enhanced photoacoustic effect and an increase in light emission from the suspension. As well, laser-initiated exothermic reactions in suspensions of C with CH(3)NO(2) and particulate Hg(CNO)(2) in H(2)O are shown to result in greatly enhanced photoacoustic signal amplitudes. PMID:21456682

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

2011-03-28

333

Thermal decomposition of CF3 and the reaction of CF2 + OH --> CF2O + H.  

PubMed

The reflected shock tube technique with multipass absorption spectrometric detection (at a total path length of approximately 1.75 m) of OH-radicals at 308 nm has been used to study the dissociation of CF3-radicals [CF3 + Kr --> CF2 + F + Kr (a)] between 1,803 and 2,204 K at three pressures between approximately 230 and 680 Torr. The OH-radical concentration buildup resulted from the fast reaction F + H2O --> OH + HF (b). Hence, OH is a marker for F-atoms. To extract rate constants for reaction (a), the [OH] profiles were modeled with a chemical mechanism. The initial rise in [OH] was mostly sensitive to reactions (a) and (b), but the long time values were additionally affected by CF2 + OH --> CF2O + H (c). Over the experimental temperature range, rate constants for (a) and (c) were determined from the mechanistic fits to be kCF3+Kr = 4.61 x 10-9 exp(-30,020 K/T) and kCF2+OH = (1.6 +/- 0.6) x 10-10, both in units of cm3 molecule-1 s-1. Reaction (a), its reverse recombination reaction reaction (-a), and reaction (c) are also studied theoretically. Reactions (c) and (-a) are studied with direct CASPT2 variable reaction coordinate transition state theory. A master equation analysis for reaction (a) incorporating the ab initio determined reactive flux for reaction (-a) suggests that this reaction is close to but not quite in the low-pressure limit for the pressures studied experimentally. In contrast, reaction (c) is predicted to be in the high-pressure limit due to the high exothermicity of the products. A comparison with past and present experimental results demonstrates good agreement between the theoretical predictions and the present data for both (a) and (c). PMID:18062678

Srinivasan, N K; Su, M-C; Michael, J V; Jasper, A W; Klippenstein, S J; Harding, L B

2008-01-10

334

Chemical reactions and Schottky barrier formation at Cr\\/n-CdTe interfaces  

Microsoft Academic Search

The formation of Schottky barriers at Cr\\/n-CdTe interfaces has been investigated in detail using angle-resolved ultraviolet photo-emission, soft X-ray photo-emission and current-voltage techniques. The CdTe surfaces studied were prepared by cleaving in ultra-high vacuum, cleaving in air, and by chemical etching. The results indicate strong chemical reactions between both CdTe and its native oxide (TeO2) with evaporated Cr layers. A

I. M. Dharmadasa; M. H. Patterson; R. H. Williams

1988-01-01

335

Provenance matters: thermal reaction norms for embryo survival among sockeye salmon Oncorhynchus nerka populations.  

PubMed

Differences in thermal tolerance during embryonic development in Fraser River sockeye salmon Oncorhynchus nerka were examined among nine populations in a controlled common-garden incubation experiment. Forcing embryonic development at an extreme temperature (relative to current values) of 16° C, representing a future climate change scenario, significantly reduced survival compared to the more ecologically moderate temperature of 10° C (55% v. 93%). Survival at 14° C was intermediate between the other two temperatures (85%). More importantly, this survival response varied by provenance within and between temperature treatments. Thermal reaction norms showed an interacting response of genotype and environment (temperature), suggesting that populations of O. nerka may have adapted differentially to elevated temperatures during incubation and early development. Moreover, populations that historically experience warmer incubation temperatures at early development displayed a higher tolerance for warm temperatures. In contrast, thermal tolerance does not appear to transcend life stages as adult migration temperatures were not related to embryo thermal tolerance. The intra-population variation implies potential for thermal tolerance at the species level. The differential inter-population variation in thermal tolerance that was observed suggests, however, limited adaptive potential to thermal shifts for some populations. This infers that the intergenerational effects of increasing water temperatures may affect populations differentially, and that such thermally mediated adaptive selection may drive population, and therefore species, persistence. PMID:23557297

Whitney, C K; Hinch, S G; Patterson, D A

2013-04-01

336

Picosecond infrared spectroscopy as probe for photochemical or thermal reactions in solid matrices  

SciTech Connect

Spectroscopy in the mid-IR on timescales from pico to milliseconds has been developed for the study of laser-material interactions over broad timescales. To reach these timescales the authors have employed two configurations: (1) for the ps to ns timescale a one and a two stage difference frequency mixing setup is employed, (2) for the longer timescale, CW mid-IR laser diodes have been used. In general, they excite the sample with one pulse at 1064/266/355 nm and probe some time later in the mid IR (2900--800 cm{sup {minus}1}). In the case of photochemical reaction, they excite the sample directly in the UV. Alternatively, they initiate thermal reactions by pumping a heater dye at 1.064 {micro}m, which quickly converts the photon energy into heat. The potential of this technique to study reactions in the solid state was demonstrated for a photochemically induced (266 nm) reaction (Wolff rearrangement of a {alpha}-diazo-ketone to {alpha}-keto-ketene) in a polymer matrix. Thermal initiation resulted in a similar reaction. The position, amplitude and width of the product bands changed, they believe due to additional side reactions and temperature effects.

Lippert, T.; Funk, D.J.; Strauss, C.E.M.; Stoutland, P.O.

1998-08-01

337

CHEMICAL AND BIOLOGICAL TREATMENT OF THERMALLY CONDITIONED SLUDGE RECYCLE LIQUORS  

EPA Science Inventory

The objective of this research project was to demonstrate and evaluate the feasibility of treating undiluted heat treatment liquor prior to its rerouting back to the head of the sewage treatment plant. Chemical and biological treatment processes were studied. Chemical treatment w...

338

Determination of a reaction scheme for cardboard thermal degradation using thermal gravimetric analysis  

Microsoft Academic Search

In this paper, we present new thermogravimetic analysis on cardboard material performed at different heating rates. Several reaction schemes are proposed to serve as an interpretation basis. Considering the experiments independently, it is found that the best fitted parameters are highly sensitive upon the heating rate. In order to avoid complicated and hazardous interpolation schemes, a simplest interpretation is proposed

C. David; S. Salvador; J. L. Dirion; M. Quintard

2003-01-01

339

Ion-Molecule Reactions and Chemical Composition of Emanated from Herculane Spa Geothermal Sources  

PubMed Central

The paper presents a chemical composition analysis of the gases emanated from geothermal sources in the Herculane Spa area (Romania). The upper homologues of methane have been identified in these gases. An ion-molecule reaction mechanism could be implicated in the formation of the upper homologues of methane. The CH4+ ions that appear under the action of radiation are the starting point of these reactions. The presence of hydrogen in the emanated gases may be also a result of these reactions. PMID:19325844

Cosma, Constantin; Suciu, Ioan; Jäntschi, Lorentz; Bolboac?, Sorana D.

2008-01-01

340

Quantum-chemical approach to serine formation in the interstellar medium: A possible reaction pathway  

NASA Astrophysics Data System (ADS)

Radical-radical and radical-neutral interaction schemes are very important for the formation of comparatively complex molecules in low-temperature chemistry. The formation of amino acids, such as serine, in the interstellar medium is quite difficult. We explored the possibility of serine formation in the interstellar medium through detected interstellar molecules such as CH, CO, and OH by radical-radical and radical-neutral interactions in the gaseous phase using rigorous quantum-chemical calculations. The reaction energies, the low potential barrier and the structures of all the geometries involved in the reaction path show that serine formation is possible in interstellar space via the reaction paths.

Shivani; Singh, Amresh; Gupta, Vineet; Misra, Alka; Tandon, Poonam

2014-03-01

341

The spliceosome catalyzes debranching in competition with reverse of the first chemical reaction  

PubMed Central

Splicing of nuclear pre-mRNA occurs via two steps of the transesterification reaction, forming a lariat intermediate and product. The reactions are catalyzed by the spliceosome, a large ribonucleoprotein complex composed of five small nuclear RNAs and numerous protein factors. The spliceosome shares a similar catalytic core structure with that of fungal group II introns, which can self-splice using the same chemical mechanism. Like group II introns, both catalytic steps of pre-mRNA splicing can efficiently reverse on the affinity-purified spliceosome. The spliceosome also catalyzes a hydrolytic spliced-exon reopening reaction as observed in group II introns, indicating a strong link in their evolutionary relationship. We show here that, by arresting splicing after the first catalytic step, the purified spliceosome can catalyze debranching of lariat-intron-exon 2. The debranching reaction, although not observed in group II introns, has similar monovalent cation preferences as those for splicing catalysis of group II introns. The debranching reaction is in competition with the reverse Step 1 reaction influenced by the ionic environment and the structure of components binding near the catalytic center, suggesting that the catalytic center of the spliceosome can switch between different conformations to direct different chemical reactions. PMID:23681507

Tseng, Chi-Kang; Cheng, Soo-Chen

2013-01-01

342

The spliceosome catalyzes debranching in competition with reverse of the first chemical reaction.  

PubMed

Splicing of nuclear pre-mRNA occurs via two steps of the transesterification reaction, forming a lariat intermediate and product. The reactions are catalyzed by the spliceosome, a large ribonucleoprotein complex composed of five small nuclear RNAs and numerous protein factors. The spliceosome shares a similar catalytic core structure with that of fungal group II introns, which can self-splice using the same chemical mechanism. Like group II introns, both catalytic steps of pre-mRNA splicing can efficiently reverse on the affinity-purified spliceosome. The spliceosome also catalyzes a hydrolytic spliced-exon reopening reaction as observed in group II introns, indicating a strong link in their evolutionary relationship. We show here that, by arresting splicing after the first catalytic step, the purified spliceosome can catalyze debranching of lariat-intron-exon 2. The debranching reaction, although not observed in group II introns, has similar monovalent cation preferences as those for splicing catalysis of group II introns. The debranching reaction is in competition with the reverse Step 1 reaction influenced by the ionic environment and the structure of components binding near the catalytic center, suggesting that the catalytic center of the spliceosome can switch between different conformations to direct different chemical reactions. PMID:23681507

Tseng, Chi-Kang; Cheng, Soo-Chen

2013-07-01

343

Measurement of Helical Trajectories in Chemical Reactions by Ion Imaging  

SciTech Connect

During the first year of this grant we developed methods to measure the sense of rotation of the nitric oxide molecule (NO) using a circularly polarized laser probe and with ion imaging detection. The method was applied to the measurement of the correlation of rotational angular momentum orientation with recoil direction in the photodissociation of NO{sub 2}. [''Detection of ''ended'' NO recoil in the 355 nm NO2 photodissociation mechanism'', V.K. Nestorov and J.I. Cline, J. Chem. Phys. 111, 5287-5290 (1999)]. The photodissociation work was performed at the University of Nevada with additional, partial support from NSF. In the summer of 1999 this technique was transported to and implemented at the Combustion Research Facility at Sandia National Laboratory in Livermore, CA in a study of rotationally inelastic collisions of NO molecules with Ar atoms. The summer 1999 experiments at Sandia demonstrated that it is possible to detect collision-induced rotational alignment (preferred planes of rotation) for product molecules. During the late summer and fall of 1999 the P.I. and student James Barr developed a theoretical method for quantifying the angular momentum alignment and for extracting it from ion images. During the winter and spring of 2000 (January-May) the P.I. was in residence at Sandia National Laboratory in Livermore during a sabbatical leave from the University of Nevada. During this time the P.I. collaborated with Sandia P.I. Dr. David Chandler and Sandia postdoctorals Thomas Lorenz and Elisabeth Wade in experiments measuring both rotational alignment and rotational orientation (preferred senses of rotation) in collisions of NO with Ar. Graduate student James Barr continued these experiments at Sandia through the end of June 2000. The success of our experimental techniques for measuring collisional alignment and the theoretical methods we have developed for extracting quantitative alignment parameters from ion images. Spectroscopic probing of products by resonance-enhanced multiphoton ionization (REMPI) detected by ion imaging is a powerful method for measuring the product state-resolved differential cross section (DCS) of bimolecular scattering reactions. Polarization of the REMPI probe light also makes imaging data potentially sensitive to product angular momentum polarization, as is well known from imaging studies of photodissociation. We exploit this sensitivity to obtain the state-resolved product angular momentum polarization as a function of recoil angle. Previous measurements of molecular angular momentum polarization in bimolecular scattering have either been constrained to detection in the scattering plane or have averaged around the azimuthal angle of the recoil velocity vector in the collision frame. Imaging detection captures the entire product recoil velocity sphere, enabling a more complete determination of product angular momentum polarization than is possible for experiments of lower detection dimensionality.

Cline, Joseph I.

2003-02-10

344

Charge exchange and chemical reactions with trapped Th{sup 3+}  

SciTech Connect

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

Churchill, L. R.; DePalatis, M. V.; Chapman, M. S. [School of Physics, Georgia Institute of Technology, Atlanta, Georgia 30332-0430 (United States)

2011-01-15

345

Thermally-induced amphibole reaction rim development: EBSD insights into microlite orientation  

NASA Astrophysics Data System (ADS)

Amphibole is an important mineral present in many calc-alkaline volcanic deposits. A hydrous phase, volcanic amphibole is only stable at pressures greater than 100 MPa (approx. 4 km), temperature less than ~860-870 oC, and in melts containing at least 4 wt % H2O. When removed from their thermal and barometric stability field, amphiboles decompose to form aggregate rims of anhydrous minerals. The thickness, texture, and mineralogy of these rims are thought to be reflective of the process driving amphibole disequilibrium (e.g. heating, decompression, etc). However, significant overlap in rim thicknesses and microlite textures means that distinguishing between processes it not simple. This study employed backscatter diffraction (EBSD) to examine both experimental heating-indced amphibole reaction rims and natural amphibole reaction rim from Augustine Volcano. We collected crystal orientation maps of amphibole reaction rims to investigate if different types of disequilibrium produce different patterns of microlite orientation. We identified two types of reaction rim: Type 1- reaction rim microlites are generally oriented at random and share little or no systematic relationship with the crystallographic orientation of the host amphibole, and; Type 2- reaction rim microlites exhibit a topotactic relationship with the host amphibole (they share the same crystallographic orientation). Experimentally produced heating reaction rims are without exception Type 2. However the natural reaction rims are evenly distributed between Types 1 and 2. Further experimental data on decompression induced reaction rim formation is needed to investigate if Type 1 reaction rims resemble the breakdown of amphibole due to decompression. If so, reaction rim microlite orientation could provide a clear method for distinguishing between heating and decompression processes in amphibole bearing magmas.

De Angelis, Sarah; Lavallée, Yan; Larsen, Jessica; Mariani, Elisabetta

2014-05-01

346

Porous GaN nanowires synthesized using thermal chemical vapor deposition  

E-print Network

Porous GaN nanowires synthesized using thermal chemical vapor deposition Seung Yong Bae a , Hee Won 2003 Abstract Porous structured GaN nanowires were synthesized with a large scale by chemical vapor to 1 mm. The porous GaN nanowires consist of the wurtzite single crystal grown with the [0 1 1

Kim, Bongsoo

347

Isotopic fractionation of the major elements of molten basalt by chemical and thermal diffusion  

E-print Network

by chemical diffusion between a natural basalt and rhyolite. The thermal isotopic fractionations for isotopes of the same element. The iron isotopic mea- surements of the basalt­rhyolite diffusion couple by chemical diffusion between molten basalt and rhyolite (Richter et al., 2003) and large fractionations

Watkins, Jim

348

Role of the interfacial thermal barrier in the effective thermal diffusivity/conductivity of SiC-fiber-reinforced reaction-bonded silicon nitride  

NASA Technical Reports Server (NTRS)

Experimental thermal diffusivity data transverse to the fiber direction for composites composed of a reaction bonded silicon nitride matrix reinforced with uniaxially aligned carbon-coated silicon carbide fibers indicate the existence of a significant thermal barrier at the matrix-fiber interface. Calculations of the interfacial thermal conductances indicate that at 300 C and 1-atm N2, more than 90 percent of the heat conduction across the interface occurs by gaseous conduction. Good agreement is obtained between thermal conductance values for the oxidized composite at 1 atm calculated from the thermal conductivity of the N2 gas and those inferred from the data for the effective composite thermal conductivity.

Bhatt, Hemanshu; Donaldson, Kimberly Y.; Hasselman, D. P. H.; Bhatt, R. T.

1990-01-01

349

A Novel Approach for Modeling Chemical Reaction in Generalized Fluid System Simulation Program  

NASA Technical Reports Server (NTRS)

The Generalized Fluid System Simulation Program (GFSSP) is a computer code developed at NASA Marshall Space Flight Center for analyzing steady state and transient flow rates, pressures, temperatures, and concentrations in a complex flow network. The code, which performs system level simulation, can handle compressible and incompressible flows as well as phase change and mixture thermodynamics. Thermodynamic and thermophysical property programs, GASP, WASP and GASPAK provide the necessary data for fluids such as helium, methane, neon, nitrogen, carbon monoxide, oxygen, argon, carbon dioxide, fluorine, hydrogen, water, a hydrogen, isobutane, butane, deuterium, ethane, ethylene, hydrogen sulfide, krypton, propane, xenon, several refrigerants, nitrogen trifluoride and ammonia. The program which was developed out of need for an easy to use system level simulation tool for complex flow networks, has been used for the following purposes to name a few: Space Shuttle Main Engine (SSME) High Pressure Oxidizer Turbopump Secondary Flow Circuits, Axial Thrust Balance of the Fastrac Engine Turbopump, Pressurized Propellant Feed System for the Propulsion Test Article at Stennis Space Center, X-34 Main Propulsion System, X-33 Reaction Control System and Thermal Protection System, and International Space Station Environmental Control and Life Support System design. There has been an increasing demand for implementing a combustion simulation capability into GFSSP in order to increase its system level simulation capability of a liquid rocket propulsion system starting from the propellant tanks up to the thruster nozzle for spacecraft as well as launch vehicles. The present work was undertaken for addressing this need. The chemical equilibrium equations derived from the second law of thermodynamics and the energy conservation equation derived from the first law of thermodynamics are solved simultaneously by a Newton-Raphson method. The numerical scheme was implemented as a User Subroutine in GFSSP.

Sozen, Mehmet; Majumdar, Alok

2002-01-01

350

Chemical Kinetic Data Base for Propellant Combustion. II. Reactions Involving CN, NCO, and HNCO  

Microsoft Academic Search

This paper contains evaluated chemical kinetic data on single step elementary reactions involving small polyatomic molecules which are of importance in propellant combustion. The work consists of the collection and evaluation of mechanistic and rate information and the use of various methods for the extrapolation and estimation of rate data where information does not exist. The conditions covered range from

Wing Tsang

1992-01-01

351

Characterization of plastic deformation and chemical reaction in titanium-polytetrafluoroethylene mixture  

Microsoft Academic Search

The subject of this dissertation is the deformation process of a single metal - polymer system (titanium - polytetrafluoroethylene) and how this process leads to initiation of chemical reaction. Several different kinds of experiments were performed to characterize the behavior of this material to shock and impact. These mechanical conditions induce a rapid plastic deformation of the sample. All of

Jeffery Jon Davis

1998-01-01

352

A Dynamical Propensity Rule for Transitions in Chemical Reactions Tamiki Komatsuzaki*, and R. Stephen Berry*,  

E-print Network

A Dynamical Propensity Rule for Transitions in Chemical Reactions Tamiki Komatsuzaki*, and R, 2002; In Final Form: July 9, 2002 A new dynamical propensity rule for transitions of a system crossing the barrier from one potential minimum to one another is derived from dynamical system theory. The rule

Berry, R. Stephen

353

Temperature-compensated chemical reactions Kanaka Rajan and L. F. Abbott  

E-print Network

Temperature-compensated chemical reactions Kanaka Rajan and L. F. Abbott Center for Neurobiology of these rhythms is that their periods remain fairly constant over a wide range of physiological temperatures, a feature called temperature compensation. Although circadian rhythms have been associated with periodic

Columbia University

354

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

ERIC Educational Resources Information Center

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

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

2014-01-01

355

Constant centrifugal potential approximation for atom-diatom chemical reaction dynamics  

E-print Network

Constant centrifugal potential approximation for atom-diatom chemical reaction dynamics Kengo,Myodaiji, Okazaki 444. Japan (Received 28 September 1993; accepted 8 December 1993) The constant centrifugal of such practically useful approxima- tions the constant centrifugal potential approximation (CCPA) (or the energy

Takada, Shoji

356

Nuclear spin selection rules in chemical reactions by angular momentum algebra  

E-print Network

Nuclear spin selection rules in chemical reactions by angular momentum algebra Takeshi Oka of the representations of the permutation­inversion group for both nuclear spin and rovibronic coordinate wavefunctions, those of the rotation group for nuclear spin wavefunction only are used. The method allows more

Oka, Takeshi

357

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

E-print Network

this result to general birth-death models and demonstrate via example that similar scaling limits can yield network theory. Further, we extend this result to birth-death processes. In 1972, Horn and Jackson [16 showed that the sta- tionary distribution for the class of complex balanced chemical reaction networks

Anderson, David F.

358

DEVELOPMENT AND TESTING OF A SURROGATE SPECIES CHEMICAL REACTION MECHANISM. VOLUME 2  

EPA Science Inventory

A photochemical reaction mechanism has been updated and extensively evaluated. The testing and refinement of the surrogate species mechanism was performed in order to create an improved chemical mechanism for the atmospheric simulation models that are used to develop ozone contro...

359

DEVELOPMENT AND TESTING OF A SURROGATE SPECIES CHEMICAL REACTION MECHANISM. VOLUME 1  

EPA Science Inventory

A photochemical reaction mechanism has been updated and extensively evaluated. The testing and refinement of the surrogate species mechanism was performed in order to create an improved chemical mechanism for the atmospheric simulation models that are used to develop ozone contro...

360

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

E-print Network

Reaction ensemble molecular dynamics: Direct simulation of the dynamic equilibrium properties December 2004) A molecular simulation method to study the dynamics of chemically reacting mixtures for the simulation of both thermodynamic and transport properties. The method couples a molecular dynamics simulation

Lisal, Martin

361

Zig-Zag Thermal-Chemical 3-D Instabilities in the Mantle Wedge: Numerical Study  

NASA Astrophysics Data System (ADS)

To understand the plume initiation and propagation it is important to understand whether small-scale convection is occurring under the back-arc in the Low Viscosity Wedge(LVW) and its implication on the island-arc volcanism. Honda et al. [Honda and Saito, 2003; Honda, et al., 2007]) already deployed small- scale convection in the Low Viscosity Wedge (LVW) above a subducting slab with kinematically imposed velocity boundary condition. They have suggested that a roll (finger)-like pattern of hot and cold anomalies emerges in the mantle wedge above the subducting slab. Here, we perform three-dimensional coupled petrological-thermomechanical numerical simulations of intraoceanic one-sided subduction with spontaneously bending retreating slab characterized by weak hydrated upper interface by using multigrid approach combined with characteristics-based marker-in-cell method with conservative finite difference schemes[Gerya and Yuen, 2003a], to investigate the 3D instabilities above the slab and lateral variation along the arc. Our results show that water released from subducting slab through dehydration reactions may lower the viscosity of the mantle. It allows the existence of wave-like small-scale convection in the LVW, which is shown as roll-like structure in 2D petrological-thermomechanical numerical experiments [Gorczyk et al., 2006] using in-situ rock properties computed on the basis of Gibbs free energy minimization. However, in our 3D cases, the rolls aligning with the arc mainly occur earlier , while zig-zag small-scale thermal-chemical instabilities may episodically form above the slab at later stages, which is different from the aligning finger-like pattern in purely thermal models (Honda et al,2003;2007). Also in contrast to thermal convection chemically buoyant hydrated plumes rising from the slab in our models are actually colder then the mantle wedge [Gerya and Yuen 2003b] which also strongly modify both the convection pattern and the seismic structure in the wedge. The zig-zag wave-like 3D instabilities have another implication on the Quaternary volcanism in the Northeast Japan. References Gerya, T. V.,Yuen D. A. (2003a), Physics of The Earth and Planetary Interiors, 140, 293-318. Gerya, T.V., Yuen, D.A. (2003b), Earth and Planet Sci. Lett., 212, 47-62. Gorczyk, W., et al. (2006), Geochem. Geophys. Geosyst., 7, doi:10.1029/2005GC001075. Honda, S., Saito M. (2003), Earth and Planetary Science Letters, 216, 703-715. Honda, S., et al. (2007), Island Arc, 16(2), 214-223.

Zhu, G.; Gerya, T. V.; Arcay, D.; Yuen, D. A.

2008-12-01

362

General chemical kinetics computer program for static and flow reactions, with application to combustion and shock-tube kinetics  

NASA Technical Reports Server (NTRS)

A general chemical kinetics program is described for complex, homogeneous ideal-gas reactions in any chemical system. Its main features are flexibility and convenience in treating many different reaction conditions. The program solves numerically the differential equations describing complex reaction in either a static system or one-dimensional inviscid flow. Applications include ignition and combustion, shock wave reactions, and general reactions in a flowing or static system. An implicit numerical solution method is used which works efficiently for the extreme conditions of a very slow or a very fast reaction. The theory is described, and the computer program and users' manual are included.

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

1972-01-01

363

Ultrasensitive detection of DNA and RNA based on enzyme-free click chemical ligation chain reaction on dispersed gold nanoparticles.  

PubMed

An ultrasensitive colorimetric DNA and RNA assay using a combination of enzyme-free click chemical ligation chain reaction (CCLCR) on dispersed gold nanoparticles (GNPs) and a magnetic separation process has been developed. The click chemical ligation between an azide-containing probe DNA-modified GNP and a dibenzocyclooctyne-containing probe biotinyl DNA occurred through hybridization with target DNA (RNA) to form the biotinyl-ligated GNPs (ligated products). Eventually, both the biotinyl-ligated GNPs and target DNA (RNA) were amplified exponentially using thermal cycling. After separation of the biotinyl-ligated GNPs using streptavidin-modified magnetic beads, the change in intensity of the surface plasmon band at 525 nm in the supernatants was observed by UV/vis measurement and was also evident visually. The CCLCR assay provides ultrasensitive detection (50 zM: several copies) of target DNA that is comparable to PCR-based approaches. Note that target RNA could also be detected with similar sensitivity without the need for reverse transcription to the corresponding cDNA. The amplification efficiency of the CCLCR assay was as high as 82% due to the pseudohomogeneous reaction behavior of CCLCR on dispersed GNPs. In addition, the CCLCR assay was able to discriminate differences in single-base mismatches and to specifically detect target DNA and target RNA from the cell lysate. PMID:25256209

Kato, Daiki; Oishi, Motoi

2014-10-28

364

A Conceptual and Numerical Model for Thermal-Hydrological-Chemical Processes in the Yucca Mountain Drift Scale Test  

SciTech Connect

A numerical model was developed to predict the coupled thermal, hydrological, and chemical (THC) processes accompanying the Drift Scale Test (DST) at Yucca Mountain, NV. The DST has been closely monitored through the collection of gas, water, and mineral samples as well as thermal, hydrological, and mechanical measurements. A two-dimensional dual permeability model was developed to evaluate multiphase, multicomponent, reaction-transport processes in the fractured tuff. Comparisons between results using the TOUGHREACT code and measured water (e.g., pH, SiO2(aq), Na+, K+) and gas (CO2) compositions show that the model captures the chemical evolution in the DST. Non-reactive aqueous species (e.g., Cl) show strong dilution in fracture waters, indicating little fracture-matrix interaction. Silica concentrations are higher than in the initial pore water and show a trend of increasing reaction with fracture-lining silicates at higher temperatures. The narrow precipitation zone of predominantly amorphous silica observed above the heaters was also captured.

Sonnenthal, Eric L.; Spycher, Nicolas F.; Conrad, Mark; Apps, John

2003-07-01

365

Safety of chlorination reactions  

Microsoft Academic Search

Chlorination reactions are part of various processes in the chemical industry, to manufacture heavy chemicals, specialty chemicals, pesticides and pharmaceuticals, in inorganic and organic chemistry. They are a valuable tool in organic synthesis.The hazard of processing chlorine involves:u- Gas phase explosion;- Runaway reaction or thermal explosion in the condensed phase.Gas phase explosion hazard with chlorine as an oxidizer is present

Jean-Louis Gustin; Alexandre Fines

1996-01-01

366

Chemical synthesis of proanthocyanidins in vitro and their reactions in aging wines.  

PubMed

Proanthocyanidins are present in many fruits and plant products like grapes and wine, and contribute to their taste and health benefits. In the past decades of years, substantial progresses has been achieved in the identification of composition and structure of proanthocyanidins, but the debate concerning the existence of an enzymatic or nonenzymatic mechanism for proanthocyanidin condensation still goes on. Substantial attention has been paid to elucidating the potential mechanism of formation by means of biomimetic and chemical synthesis in vitro. The present paper aims at summarizing the research status on chemical synthesis of proanthocyanidins, including non-enzymatic synthesis of proanthocyanidin precursors, chemical synthesis of proanthocyanidins with direct condensation of flavanols and stereoselective synthesis of proanthocyanidins. Proanthocyanidin-involved reactions in aging wines are also reviewed such as direct and indirect reactions among proanthocyanidins, flavanols and anthocyanins. Topics for future research in this field are also put forward in this paper. PMID:19052525

He, Fei; Pan, Qiu-Hong; Shi, Ying; Duan, Chang-Qing

2008-01-01

367

Chemical kinetic analysis of hydrogen-air ignition and reaction times  

NASA Technical Reports Server (NTRS)

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

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

1981-01-01

368

Chemical Kinetic Reaction Mechanisms for Combustion of Hydrocarbon and Other Types of Chemical Fuels  

DOE Data Explorer

Reaction mechanisms have been tested and validated extensively through comparisons between computed results and measured data from laboratory experiments (e.g., shock tubes, laminar flames, rapid compression machines, flow reactors, stirred reactors) and from practical systems (e.g., diesel engines, spark-ignition engines, homogeneous charge, compression ignition (HCCI) engines). These kinetic models are used to examine a wide range of combustion systems.[Taken from https://www-pls.llnl.gov/?url=science_and_technology-chemistry-combustion

369

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

PubMed

Conspectus Reactions on water and ice surfaces and in other aqueous media are ubiquitous in the atmosphere, but the microscopic mechanisms of most of these processes are as yet unknown. This Account examines recent progress in atomistic simulations of such reactions and the insights provided into mechanisms and interpretation of experiments. Illustrative examples are discussed. The main computational approaches employed are classical trajectory simulations using interaction potentials derived from quantum chemical methods. This comprises both ab initio molecular dynamics (AIMD) and semiempirical molecular dynamics (SEMD), the latter referring to semiempirical quantum chemical methods. Presented examples are as follows: (i) Reaction of the (NO(+))(NO3(-)) ion pair with a water cluster to produce the atmospherically important HONO and HNO3. The simulations show that a cluster with four water molecules describes the reaction. This provides a hydrogen-bonding network supporting the transition state. The reaction is triggered by thermal structural fluctuations, and ultrafast changes in atomic partial charges play a key role. This is an example where a reaction in a small cluster can provide a model for a corresponding bulk process. The results support the proposed mechanism for production of HONO by hydrolysis of NO2 (N2O4). (ii) The reactions of gaseous HCl with N2O4 and N2O5 on liquid water surfaces. Ionization of HCl at the water/air interface is followed by nucleophilic attack of Cl(-) on N2O4 or N2O5. Both reactions proceed by an SN2 mechanism. The products are ClNO and ClNO2, precursors of atmospheric atomic chlorine. Because this mechanism cannot result from a cluster too small for HCl ionization, an extended water film model was simulated. The results explain ClNO formation experiments. Predicted ClNO2 formation is less efficient. (iii) Ionization of acids at ice surfaces. No ionization is found on ideal crystalline surfaces, but the process is efficient on isolated defects where it involves formation of H3O(+)-acid anion contact ion pairs. This behavior is found in simulations of a model of the ice quasi-liquid layer corresponding to large defect concentrations in crystalline ice. The results are in accord with experiments. (iv) Ionization of acids on wet quartz. A monolayer of water on hydroxylated silica is ordered even at room temperature, but the surface lattice constant differs significantly from that of crystalline ice. The ionization processes of HCl and H2SO4 are of high yield and occur in a few picoseconds. The results are in accord with experimental spectroscopy. (v) Photochemical reactions on water and ice. These simulations require excited state quantum chemical methods. The electronic absorption spectrum of methyl hydroperoxide adsorbed on a large ice cluster is strongly blue-shifted relative to the isolated molecule. The measured and calculated adsorption band low-frequency tails are in agreement. A simple model of photodynamics assumes prompt electronic relaxation of the excited peroxide due to the ice surface. SEMD simulations support this, with the important finding that the photochemistry takes place mainly on the ground state. In conclusion, dynamics simulations using quantum chemical potentials are a useful tool in atmospheric chemistry of water media, capable of comparison with experiment. PMID:25647299

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

2015-02-17

370

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

PubMed

Understanding the mechanisms of chemical reactions, especially catalysis, has been an important and active area of computational organic chemistry, and close collaborations between experimentalists and theorists represent a growing trend. This Perspective provides examples of such productive collaborations. The understanding of various reaction mechanisms and the insight gained from these studies are emphasized. The applications of various experimental techniques in elucidation of reaction details as well as the development of various computational techniques to meet the demand of emerging synthetic methods, e.g., C-H activation, organocatalysis, and single electron transfer, are presented along with some conventional developments of mechanistic aspects. Examples of applications are selected to demonstrate the advantages and limitations of these techniques. Some challenges in the mechanistic studies and predictions of reactions are also analyzed. PMID:25568962

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

2015-02-11

371

Chemical Reactions  

NSDL National Science Digital Library

SciPacks are 10 hour online learning experiences teachers can use to enhance their understanding of a particular scientific concept. Teachers access topics "on demand" from the Internet. Topics are based on science literacy goals in the national standards

National Science Teachers Association (NSTA)

2009-07-10

372

Chemical Reactions  

NSDL National Science Digital Library

Though titled for kids the information presented at this site is thorough and supported with hot links to related concepts as well as illustrations. Click on the blue Next Stop on the Tour button to continue learning.

2009-01-01

373

Fitness Costs of Thermal Reaction Norms for Wing Melanisation in the Large White Butterfly (Pieris brassicae)  

PubMed Central

The large white butterfly, Pieris brassicae, shows a seasonal polyphenism of wing melanisation, spring individuals being darker than summer individuals. This phenotypic plasticity is supposed to be an adaptive response for thermoregulation in natural populations. However, the variation in individuals’ response, the cause of this variation (genetic, non genetic but inheritable or environmental) and its relationship with fitness remain poorly known. We tested the relationships between thermal reaction norm of wing melanisation and adult lifespan as well as female fecundity. Butterflies were reared in cold (18°C), moderate (22°C), and hot (26°C) temperatures over three generations to investigate variation in adult pigmentation and the effects of maternal thermal environment on offspring reaction norms. We found a low heritability in wing melanisation (h2?=?0.18). Rearing families had contrasted thermal reaction norms. Adult lifespan of males and females from highly plastic families was shorter in individuals exposed to hot developmental temperature. Also, females from plastic families exhibited lower fecundity. We did not find any effect of maternal or grand-maternal developmental temperature on fitness. This study provides new evidence on the influence of phenotypic plasticity on life history-traits’ evolution, a crucial issue in the context of global change. PMID:24587196

Chaput-Bardy, Audrey; Ducatez, Simon; Legrand, Delphine; Baguette, Michel

2014-01-01

374

Analysis of parameter effects on transport phenomena in conjunction with chemical reactions in ducts relevant for methane reformers  

Microsoft Academic Search

Various transport phenomena in conjunction with chemical reactions are strongly affected by reformer configurations and properties of involved porous catalyst layers. The considered composite duct is relevant for a methane steam reformer and consists of a porous layer for the catalytic chemical reactions, the fuel gas flow duct and solid plate. In this paper, a fully three-dimensional calculation method is

Jinliang Yuan; XinRong Lv; Bengt Sundén; Dantin Yue

2007-01-01

375

Inducing All Steps of a Chemical Reaction with the Scanning Tunneling Microscope Tip: Towards Single Molecule Engineering  

Microsoft Academic Search

All elementary steps of a chemical reaction have been successfully induced on individual molecules with a scanning tunneling microscope (STM) in a controlled step-by-step manner utilizing a variety of manipulation techniques. The reaction steps involve the separation of iodine from iodobenzene by using tunneling electrons, bringing together two resultant phenyls mechanically by lateral manipulation and, finally, their chemical association to

Saw-Wai Hla; Ludwig Bartels; Gerhard Meyer; Karl-Heinz Rieder

2000-01-01

376

Utilizing carbon dioxide as a reaction medium to mitigate production of polycyclic aromatic hydrocarbons from the thermal decomposition of styrene butadiene rubber.  

PubMed

The CO(2) cofeed impact on the pyrolysis of styrene butadiene rubber (SBR) was investigated using thermogravimetric analysis (TGA) coupled to online gas chromatography/mass spectroscopy (GC/MS). The direct comparison of the chemical species evolved from the thermal degradation of SBR in N(2) and CO(2) led to a preliminary mechanistic understanding of the formation and relationship of light hydrocarbons (C(1-4)), aromatic derivatives, and polycyclic aromatic hydrocarbons (PAHs), clarifying the role of CO(2) in the thermal degradation of SBR. The identification and quantification of over 50 major and minor chemical species from hydrogen and benzo[ghi]perylene were carried out experimentally in the temperature regime between 300 and 500 °C in N(2) and CO(2). The significant amounts of benzene derivatives from the direct bond dissociation of the backbone of SBR, induced by thermal degradation, provided favorable conditions for PAHs by the gas-phase addition reaction at a relatively low temperature compared to that with conventional fuels such as coal and petroleum-derived fuels. However, the formation of PAHs in a CO(2) atmosphere was decreased considerably (i.e., ?50%) by the enhanced thermal cracking behavior, and the ultimate fates of these species were determined by different pathways in CO(2) and N(2) atmospheres. Consequently, this work has provided a new approach to mitigate PAHs by utilizing CO(2) as a reaction medium in thermochemical processes. PMID:22950720

Kwon, Eilhann E; Yi, Haakrho; Castaldi, Marco J

2012-10-01

377

CP: AN INVESTIGATION OF COEFFICIENT OF THERMAL EXPANSION, DECOMPOSITION KINETICS, AND REACTION TO VARIOUS STIMULI  

SciTech Connect

The properties of pentaamine (5-cyano-2H-tetrazolato-N2) cobalt (III) perchlorate (CP), which was first synthesized in 1968, continues to be of interest for predicting behavior in handling, shipping, aging, and thermal cook-off situations. We report coefficient of thermal expansion (CTE) values over four specific temperature ranges, decomposition kinetics using linear heating rates, and the reaction to three different types of stimuli: impact, spark, and friction. The CTE was measured using a Thermal Mechanical Analyzer (TMA) for samples that were uniaxially compressed at 10,000 psi and analyzed over a dynamic temperature range of -20 C to 70 C. Using differential scanning calorimetry, DSC, CP was decomposed at linear heating rates of 1, 3, and 7 C/min and the kinetic triplet calculated using the LLNL code Kinetics05. Values are also reported for spark, friction, and impact sensitivity.

Weese, R K; Burnham, A K; Fontes, A T

2005-03-23

378

Chemical and isotope compositions of nitric thermal water of Baikal rift zone  

NASA Astrophysics Data System (ADS)

Three types of hydrotherms (nitric, carbonaceous and methane) are distinguished within the Baikal Rift Zone. The unloading sites of nitric therms are mostly located in the central and north-eastern parts of the Rift. Several chemical types are found among nitric therms (Pinneker, Pisarsky, Lomonosov, 1968; Lomonosov, 1974, etc.). The formation of terms being various in chemical compositions is associated with effect of several factors, i.e. various chemical, mineralogical compositions of rocks, various temperatures, extent of interaction in water-rock system, etc. The ratio data of water oxygen and hydrogen isotopes of the studied thermal springs indicate that water is largely of meteoric origin. All established ratios of oxygen (?18OSMOW = -19.5‰ - -17.5‰) and hydrogen (?DSMOW = -155‰ - - 130‰) isotopes are along the line of meteoric waters. Oxygen values from -20‰ to -5‰ are characteristic of the current meteoric and surface waters in the region. The average value equals -16.5‰ in Lake Baikal. By our data, a large group with oxygen lighter isotope composition that corresponds to isotope ratio being specific for glaciers is revealed in fissure-vein waters. Significant shift toward the oxygen getting heavier is observed in some springs. It is mostly observed in the springs that form chemical composition within the area of the intrusive and metamorphic rock distribution. As a result of hydrolysis reaction of alumosilicates, heavy isotope passes from rocks into water molecule, whereas oxygen heavy isotope passes from rocks into solutes during decomposition of carbonates. High contents of fluoride and sulfate-ions are specific feature of the Baikal Rift Zone most nitric therms. Water is tapped in one of the drill holes, where fluoride-ion dominates in its anion composition (46.7 mg/dm3) and pH reaches 10, 12. The sulphate sulphur isotope composition studies carried out allow to conclude that its heavy isotope (?34SCDT = +25‰ - +30‰) prevails in the therms. Sulphate-ion enters solution not as a result of sulfide oxidation, but dissolution of sulphate minerals of may be originally sedimentary and magmatic rocks. Microelement contents in waters depend on total mineralization. In particular, this regulation is clearly observed for rare alkaline and alkaline-earth elements. We established dependence of one microelement concentrations on temperature of solutions (Sc, Al, W) and that of the other ones - on extent of water - rock (Sr, Ba) interaction. Active use of thermal water for purposes of thermal energetic can contribute to inflow of highly mineralized solutions into water collecting reservoir and result in breakdowns of heat-net work. The study has been carried out with financial support of RFBR. Grant N09-05-00726, Integration Project N87 of SB RAS.

Plyusnin, A. M.; Chernyavsky, M. K.; Peryazeva, E. G.

2010-05-01

379

STREAMING COLD COSMIC-RAY BACK-REACTION AND THERMAL INSTABILITIES ALONG THE BACKGROUND MAGNETIC FIELD  

SciTech Connect

Using a multi-fluid approach, we investigate the streaming and thermal instabilities of electron-ion-cosmic-ray astrophysical objects in which homogeneous cold cosmic rays have a drift velocity perpendicular to the background magnetic field. One-dimensional perturbations along the magnetic field are considered. The induced return current of the background plasma and back-reaction of cosmic rays are taken into account. It is shown that the cosmic-ray back-reaction results in a streaming instability with considerably higher growth rates than that due to the return current of the background plasma. This increase is by a factor of the square root of the ratio of the background plasma mass density to the cosmic-ray mass density. The maximal growth rate and the corresponding wavenumber are then found. Thermal instability is shown to be not subject to the action of cosmic rays in the model under consideration. The dispersion relation for thermal instability includes ion inertia. In the limit of a fast thermal energy exchange between electrons and ions, the isobaric and isochoric growth rates are obtained. The results can be useful for the investigation of electron-ion astrophysical objects such as galaxy clusters, including the dynamics of streaming cosmic rays.

Nekrasov, Anatoly K. [Institute of Physics of the Earth, Russian Academy of Sciences, 123995 Moscow (Russian Federation); Shadmehri, Mohsen, E-mail: anekrasov@ifz.ru, E-mail: nekrasov.anatoly@gmail.com, E-mail: m.shadmehri@gu.ac.ir [Department of Physics, Golestan University, Basij Square, Gorgan (Iran, Islamic Republic of)

2012-09-01

380

Influence of structure on chemical and thermal stability of aliphatic diesters.  

PubMed

Ester group interactions with each other and with the atoms between them were investigated in order to determine dependence of chemical and thermal stabilities of aliphatic diesters on structure. Novel glycol-derived diesters with chemical formula (C17H33COO)2C(n)H(2n) were used as model systems. Chemical stability was determined using (1)H NMR and FTIR, and thermal stability and weight-loss kinetics were examined using nonisothermal TGA. Chemical stability increased with the number of methylene units (n, carbon) between the ester groups until n = 6, and no significant improvement was observed past n > 6. It is argued that other ester-dense materials, including polyesters, would behave similarly. Evidence of a strong dependence of thermal stability on chemical stability is also provided. This work shows that the chemical and thermal stabilities of ester-dense functional materials such as diesters, oligo-esters, and polyesters can be manipulated by varying the distance between the ester groups, and hence the interactions of the electron-withdrawing ester groups with its neighbors. PMID:24171430

Raghunanan, Latchmi; Narine, Suresh S

2013-11-27

381

Role of interfacial thermal barrier in the transverse thermal conductivity of uniaxial SiC fiber-reinforced reaction bonded silicon nitride  

NASA Technical Reports Server (NTRS)

The transverse thermal conductivity of reaction-bonded Si3N4 is significantly affected by an interfacial barrier at the interface formed with SiC reinforcing fibers. A comparative study of composites with and without reinforcing-fiber carbon coatings found the coating to reduce effective thermal conductivity by a factor of about 2; this, however, is partially due to a thermal expansion-mismatch gap between fiber and matrix. HIPing of composites with coated fibers led to an enhancement of thermal conductivity via improved interfacial thermal contact and greater grain size and crystallinity of the fibers.

Bhatt, H.; Donaldson, K. Y.; Hasselman, D. P. H.; Bhatt, R. T.

1992-01-01

382

A Non-Orthogonal Block-Localized Effective Hamiltonian Approach for Chemical and Enzymatic Reactions  

PubMed Central

The effective Hamiltonian-molecular orbital and valence bond (EH-MOVB) method based on non-orthogonal block-localized fragment orbitals has been implemented into the program CHARMM for molecular dynamics simulations of chemical and enzymatic reactions, making use of semiempirical quantum mechanical models. Building upon ab initio MOVB theory, we make use of two parameters in the EH-MOVB method to fit the barrier height and the relative energy between the reactant and product state for a given chemical reaction to be in agreement with experiment or high-level ab initio or density functional results. Consequently, the EH-MOVB method provides a highly accurate and computationally efficient QM/MM model for dynamics simulation of chemical reactions in solution. The EH-MOVB method is illustrated by examination of the potential energy surface of the hydride transfer reaction from trimethylamine to a flavin cofactor model in the gas phase. In the present study, we employed the semiempirical AM1 model, which yields a reaction barrier that is more than 5 kcal/mol too high. We use a parameter calibration procedure for the EH-MOVB method similar to that employed to adjust the results of semiempirical and empirical models. Thus, the relative energy of these two diabatic states can be shifted to reproduce the experimental energy of reaction, and the barrier height is optimized to reproduce the desired (accurate) value by adding a constant to the off-diagonal matrix element. The present EH-MOVB method offers a viable approach to characterizing solvent and protein-reorganization effects in the realm of combined QM/MM simulations. PMID:20694172

Cembran, Alessandro; Payaka, Apirak; Lin, Yen-lin; Xie, Wangshen; Mo, Yirong; Song, Lingchun; Gao, Jiali

2010-01-01

383

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

E-print Network

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

Banerjee, Kinshuk

2014-01-01

384

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

USGS Publications Warehouse

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

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

1994-01-01

385

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

NASA Technical Reports Server (NTRS)

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

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

1994-01-01

386

Abiotic reduction reactions of anthropogenic organic chemicals in anaerobic systems: A critical review  

NASA Astrophysics Data System (ADS)

This review is predicated upon the need for a detailed process-level understanding of factors influencing the reduction of anthropogenic organic chemicals in natural aquatic systems. In particular, abiotic reductions of anthropogenic organic chemicals are reviewed. The most important reductive reaction is alkyl dehalogenation (replacement of chloride with hydrogen) which occurs in organisms, sediments, sewage sludge, and reduced iron porphyrin model systems. An abiotic mechanism involving a free radical intermediate has been proposed. The abstraction of vicinal dihalides (also termed dehalogenation) is another reduction that may have an abiotic component in natural systems. Reductive dehalogenation of aryl halides has recently been reported and further study of this reaction is needed. Several other degradation reactions of organohalides that occur in anaerobic environments are mentioned, the most important of which is dehydrohalogenation. The reduction of nitro groups to amines has also been thoroughly studied. The reactions can occur abiotically, and are affected by the redox conditions of the experimental system. However, a relationship between nitro-reduction rate and measured redox potential has not been clearly established. Reductive dealkylation of the N- and O-heteroatom of hydrocarbon pollutants has been observed but not investigated in detail. Azo compounds can be reduced to their hydrazo derivatives and a thorough study of this reaction indicates that it can be caused by extracellular electron transfer agents. Quinone-hydroquinone couples are important reactive groups in humic materials and similar structures in resazurin and indigo carmine make them useful as models for environmental redox conditions. The interconversion of sulfones, sulfoxides, and sulfides is a redox process and is implicated in the degradation of several pesticides though the reactions need more study. Two reductive heterocyclic cleavage reactions are also mentioned. Finally, several difficulties (both semantic and experimental) that recur in the studies reviewed are discussed. The subtle effects of various sterilization techniques on extracellular biochemicals and complex chemical reducing agents in sediment have stifled attempts to separate abiotic from biological degradation reactions. The characterization of redox conditions in a natural system is still problematic since measured redox potential is not adequate. Suggestions for future research toward a process-level understanding of abiotic chemical reductions are made.

Macalady, Donald L.; Tratnyek, Paul G.; Grundl, Timothy J.

1986-02-01

387

Influence of Alumina Reaction Tube Impurities on the Oxidation of Chemically-Vapor-Deposited Silicon Carbide  

NASA Technical Reports Server (NTRS)

Pure coupons of chemically vapor deposited (CVD) SiC were oxidized for 100 h in dry flowing oxygen at 1300 C. The oxidation kinetics were monitored using thermogravimetry (TGA). The experiments were first performed using high-purity alumina reaction tubes. The experiments were then repeated using fused quartz reaction tubes. Differences in oxidation kinetics, scale composition, and scale morphology were observed. These differences were attributed to impurities in the alumina tubes. Investigators interested in high-temperature oxidation of silica formers should be aware that high-purity alumina can have significant effects on experiment results.

Opila, Elizabeth

1995-01-01

388

Thermal and chemical structure of the Iceland plume  

Microsoft Academic Search

Basaltic lavas, forming thick offshore seaward-dipping reflector sequences (SDRS) and onshore igneous provinces around the North Atlantic margins, represent melting of anomalously hot mantle in the head of the ancestral Iceland plume. Some of these lavas are chemically and isotopically indistinguishable from recent Icelandic basalt, but others more closely resemble basalt erupted at normal segments of mid-ocean ridges (N-MORB). In

J. G. Fitton; A. D. Saunders; M. J. Norry; B. S. Hardarson; R. N. Taylor

1997-01-01

389

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

ERIC Educational Resources Information Center

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

Sattsangi, Prem D.

2011-01-01

390

Analysis of chemical-reaction-coupled mass and heat transport phenomena in a methane reformer duct for PEMFCs  

Microsoft Academic Search

Mass, heat and momentum transport processes are coupled with catalytic chemical reactions in a methane steam reforming duct. It is often found that endothermic and exothermic reactions in the ducts are strongly integrated by heat transfer from adjacent catalytic combustion ducts. In this paper, a three-dimensional calculation method is developed to simulate and analyze reforming reactions of methane, and the

Jinliang Yuan; Fuan Ren; Bengt Sundén

2007-01-01

391

Chemically homogeneous and thermally reversible oxidation of epitaxial graphene  

SciTech Connect

With its exceptional charge mobility, graphene holds great promise for applications in next-generation electronics. In an effort to tailor its properties and interfacial characteristics, the chemical functionalization of graphene is being actively pursued. The oxidation of graphene via the Hummers method is most widely used in current studies, although the chemical inhomogeneity and irreversibility of the resulting graphene oxide compromises its use in high-performance devices. Here, we present an alternative approach for oxidizing epitaxial graphene using atomic oxygen in ultrahigh vacuum. Atomic-resolution characterization with scanning tunnelling microscopy is quantitatively compared to density functional theory, showing that ultrahigh-vacuum oxidization results in uniform epoxy functionalization. Furthermore, this oxidation is shown to be fully reversible at temperatures as low as 260 8C using scanning tunnelling microscopy and spectroscopic techniques. In this manner, ultrahigh-vacuum oxidation overcomes the limitations of Hummers-method graphene oxide, thus creating new opportunities for the study and application of chemically functionalized graphene.

Hossain, Md. Zakir [Northwestern University, Evanston; Johns, James E. [Northwestern University, Evanston; Bevan, Kirk H [ORNL; Karmel, Hunter J. [Northwestern University, Evanston; Liang, Yu Teng [Northwestern University, Evanston; Yoshimoto, Shinya [University of Tokyo, Tokyo, Japan; Mukai, Kozo [University of Tokyo, Tokyo, Japan; Koitaya, Tatanori [University of Tokyo, Tokyo, Japan; Yoshinobu, Jun [University of Tokyo, Tokyo, Japan; Kawai, Maki [University of Tokyo, Tokyo, Japan; Lear, Amanda M. [Indiana University; Kesmodel, Larry L. [Indiana University; Tait, Steven L. [Indiana University; Hersam, Mark C. [Northwestern University, Evanston

2012-01-01

392

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

PubMed Central

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

Heifets, Abraham; Jurisica, Igor

2012-01-01

393

Chemical Properties of Carbon Nanotubes Prepared Using Camphoric Carbon by Thermal-CVD  

NASA Astrophysics Data System (ADS)

Chemical properties and surface study on the influence of starting carbon materials by using thermal chemical vapor deposition (Thermal-CVD) to produced carbon nanotubes (CNTs) is investigated. The CNTs derived from camphor were synthesized as the precursor material due to low sublimation temperature. The major parameters are also evaluated in order to obtain high-yield and high-quality CNTs. The prepared CNTs are examined using field emission scanning electron microscopy (FESEM) to determine the microstructure of nanocarbons. The FESEM investigation of the CNTs formed on the support catalysts provides evidence that camphor is suitable as a precursor material for nanotubes formation. The chemical properties of the CNTs were conducted using FTIR spectroscopy and PXRD analysis. The high-temperature graphitization process induced by the Thermal-CVD enables the hydrocarbons to act as carbon sources and changes the aromatic species into the layered graphite structure of CNTs.

Azira, A. A.; Rusop, M.

2010-03-01

394

Effects of quark chemical equilibration on thermal photon elliptic flow  

E-print Network

Large hadronic elliptic flow $v_2$ is considered as an evidence for the existence of a strongly-coupled QGP fluid in high-energy heavy-ion collisions. On the other hand, direct photon $v_2$ has recently been found to be much larger than hydrodynamic estimations, which is recognized as "photon $v_2$ puzzle". In this study, I discuss the implication of late production of quarks in an initially gluon-rich medium because photons are coupled to quarks. Numerical analyses imply that thermal photon $v_2$ can be visibly enhanced. This indicates that interplay of equilibration processes and collective expansion would be important.

Akihiko Monnai

2014-12-25

395

Chemical detection using the airborne thermal infrared imaging spectrometer (TIRIS)  

SciTech Connect

A methodology is described for an airborne, downlooking, longwave infrared imaging spectrometer based technique for the detection and tracking of plumes of toxic gases. Plumes can be observed in emission or absorption, depending on the thermal contrast between the vapor and the background terrain. While the sensor is currently undergoing laboratory calibration and characterization, a radiative exchange phenomenology model has been developed to predict sensor response and to facilitate the sensor design. An inverse problem model has also been developed to obtain plume parameters based on sensor measurements. These models, the sensors, and ongoing activities are described.

Gat, N.; Subramanian, S.; Sheffield, M.; Erives, H. [Opto-Knowledge Systems, Inc. (United States); Barhen, J. [Oak Ridge National Lab., TN (United States)

1997-04-01

396

An Overview of Chemical Processes That Damage Cellular DNA: Spontaneous Hydrolysis, Alkylation, and Reactions with Radicals  

PubMed Central

The sequence of heterocyclic bases on the interior of the DNA double helix constitutes the genetic code that drives the operation of all living organisms. With this said, it is not surprising that chemical modification of cellular DNA can have profound biological consequences. Therefore, the organic chemistry of DNA damage is fundamentally important to diverse fields including medicinal chemistry, toxicology, and biotechnology. This review is designed to provide a brief overview of the common types of chemical reactions that lead to DNA damage under physiological conditions. PMID:19757819

Gates, Kent S.

2009-01-01

397

Self-propelled motion of a fluid droplet under chemical reaction  

NASA Astrophysics Data System (ADS)

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

Yabunaka, S.; Ohta, T.; Yoshinaga, N.

2012-02-01

398

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

NASA Technical Reports Server (NTRS)

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

Vogel, Bernhard; Vogel, Heike; Fiedler, Franz

1994-01-01

399

Effect of thermal treatment on the chemical resistance of polydimethylsiloxane for microfluidic devices  

NASA Astrophysics Data System (ADS)

We investigated the use of thermally treated polydimethylsiloxane (PDMS) for chemically-resistant microchannels. When the PDMS underwent the thermal treatment at 300 °C, swelling was reduced and the surface of the PDMS microfluidic channel endured well in the extracting media such as dichloromethane. Furthermore, despite the small decrease in size after thermal treatment, both the channel shape and transparency were maintained without showing fluid leakage. The thermally treated PDMS had more hydrophilic properties compared to the untreated PDMS. A single step post-casting process described in this work does not require complex chemical treatments or introduction of foreign materials to the host PDMS substrate, thus expanding the application area of PDMS-based microfluidics.

Lee, Jihoon; Kim, Jungwoo; Kim, Hyoungsub; Bae, Young Min; Lee, Kyeong-Hee; Cho, Hyoung J.

2013-03-01

400

Correlation of chemical, structural and thermal properties of natural fibres for their sustainable exploitation.  

PubMed

The potential of lignocellulosic natural fibres as renewable resources for thermal conversion and material reinforcement is largely dependent on the correlation between their chemical composition, crystalline structure and thermal decomposition properties. Significant differences were observed in the chemical composition of cotton, flax, hemp, kenaf and jute natural fibres in terms of cellulose, hemicellulose and lignin content, which influence their morphology, thermal properties and pyrolysis product distribution. A suitable methodology to study the kinetics of the thermal decomposition process of lignocellulosic fibres is proposed combining different models (Friedman, Flynn-Wall-Ozawa, Criado and Coats-Redfern). Cellulose pyrolysis can be modelled with similar kinetic parameters for all the natural fibres whereas the kinetic parameters for hemicellulose pyrolysis show intrinsic differences that can be assigned to the heterogeneous hemicellulose sugar composition in each natural fibre. This study provides the ground to critically select the most promising fibres to be used either for biofuel or material applications. PMID:25129763

Moriana, Rosana; Vilaplana, Francisco; Karlsson, Sigbritt; Ribes, Amparo

2014-11-01

401

The Q-K model for gas-phase chemical reaction rates  

NASA Astrophysics Data System (ADS)

The quantum-kinetic, or Q-K, model is based on the quantum vibration model that is employed in the computation of gas flows at the molecular level by the direct simulation Monte Carlo (DSMC) method. The Q-K procedure for dissociation is physically realistic within the context of the vibration model in that the reaction occurs upon the selection of the vibrational level that corresponds to dissociation. An analogous, but entirely phenomenological, procedure has been presented for endothermic exchange and chain reactions. These procedures for the endothermic reactions have been well validated, but the existing procedures for the corresponding exothermic reactions have proved to be problematic. This paper presents new procedures for the exothermic reactions that are computationally efficient and provide a near exact match with the equilibrium constant of statistical mechanics. The Q-K model does not depend on the availability of continuum rate coefficients. Instead, the simplicity of the new DSMC procedures allows analytical expressions to be written down for the corresponding rate coefficients in an equilibrium gas. These are used to validate the Q-K model for reactions in high temperature air and in hydrogen-oxygen combustion. The development of the Q-K model has been driven by the need for efficient reaction procedures in DSMC applications that often involve the computation of billions of simulated collisions. It is not intended to compete with the modern theories for gas-phase chemical reactions that employ more accurate physical representations of real reactions. At the same time, the degree of validation of the model is such that the analytical expressions for the rate coefficients that correspond to the model should be useful in their own right.

Bird, G. A.

2011-10-01

402

Role of impact parameter in branching reactions: Chemical accelerator studies of the reaction Xe++CH4?XeCH3 ++H  

E-print Network

Integral reaction cross sections and product velocity distributions have been measured for the ion–molecule reaction Xe+(CH4,H)XeCH3 + over the relative reactant translational energy range of 0.7–5.5 eV by chemical accelerator techniques...

Miller, G. D.; Strattan, L. W.; Hierl, Peter M.

1981-01-01

403

Study of the mechanism of thermal chemical processes in the crystals of YAF tripeptides by means of mass spectrometry and solid state NMR.  

PubMed

Thermal reactions in two Tyr-Ala-Phe (YAF) tripeptide crystals with different molecular packing (monoclinic and hexagonal), distinct stereochemistry of central amino acid (D or L alanine) and specific arrangement of molecules in the crystal lattice (head-to-tail) were investigated. Samples were heated up to 180 °C, while the melting point for YAF crystals is above the 220 °C. Below the melting temperature, in both cases the chemical reactions leading to formation of cyclic dipeptides (YA diketopiperazine) and leaving of phenylalanine were observed. Two possible mechanisms of chemical reaction in the crystal lattice assuming intra- and/or intermolecular pathways were considered. (13)C and (15)N enriched YAF samples were employed to study of mechanism of solid state reactivity using mass spectrometry and advanced solid state NMR techniques (2D DARR (Dipolar Assisted Rotational Resonance) and 2D Double CP (Cross-Polarization) correlations). PMID:24070178

Drabik, Ewelina; Jeziorna, Agata; Bienias, Urszula; Trzeciak-Karlikowska, Katarzyna; Pawlak, Tomasz; Paluch, Piotr; Potrzebowski, Marek J

2013-10-31

404

Thermal, chemical, and photocatalytic inactivation of Lactobacillus plantarum bacteriophages.  

PubMed

The effect of several biocides, thermal treatments, and photocatalysis on the viability of four Lactobacillus plantarum phages was investigated. Times to achieve 99% inactivation (T99) of phages at 63, 72, and 90 degrees C were evaluated in four suspension media: deMan Rogosa Sharpe broth, reconstituted skim milk, a commercial EM-glucose medium, and Tris magnesium gelatin buffer. The four phages studied were highly resistant to 63 degrees C (T99 > 45 min); however, counts < 10 PFU/ml were achieved by heating at 90 degrees C for 5 min. Higher thermal resistance at 72 degrees C was observed when reconstituted skim milk and EM-glucose medium were assayed. Peracetic acid (0.15%, vol/vol) was an effective biocide for the complete inactivation of all phages studied within 5 min of exposure. Sodium hypochlorite (800 ppm) inactivated the phages completely within 30 min. Ethanol (100%) did not destroy phage particles even after 45 min. Isopropanol did not have any effect on phage viability. Phage counts < 50 PFU/ml were obtained within 180 min of photocatalytic treatment. The results obtained in this work are important for establishing adequate methods for inactivating phages in industrial plants and laboratory environments. PMID:19517728

Briggiler Marcó, Mariángeles; De Antoni, Graciela L; Reinheimer, Jorge A; Quiberoni, Andrea

2009-05-01

405

Headspace components that discriminate between thermal and high pressure high temperature treated green vegetables: identification and linkage to possible process-induced chemical changes.  

PubMed

For the first time in literature, this study compares the process-induced chemical reactions in three industrially relevant green vegetables: broccoli, green pepper and spinach treated with thermal and high pressure high temperature (HPHT) processing. Aiming for a fair comparison, the processing conditions were selected based on the principle of equivalence. A comprehensive integration of MS-based metabolic fingerprinting techniques, advanced data preprocessing and statistical data analysis has been implemented as untargeted/unbiased multiresponse screening tool to uncover changes in the volatile fraction. For all vegetables, thermal processing, compared to HPHT, seems to enhance Maillard and Strecker degradation reaction, triggering the formation of furanic compounds and Strecker aldehydes. In most cases, high pressure seems to accelerate (an)aerobic thermal degradation of unsaturated fatty acids leading to the formation of aliphatic aldehydes and ketones. In addition, both thermal and HPHT processing accelerated the formation of sulfur-containing compounds. This work demonstrated that the approach is effective in identifying and comparing different process-induced chemical changes, adding depth to our perspective in terms of studying a highly complex chemical changes occurring during food processing. PMID:23870866

Kebede, Biniam T; Grauwet, Tara; Tabilo-Munizaga, Gipsy; Palmers, Stijn; Vervoort, Liesbeth; Hendrickx, Marc; Van Loey, Ann

2013-12-01

406

Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation  

NASA Astrophysics Data System (ADS)

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

Ibrahim, Heide; Wales, Benji; Beaulieu, Samuel; Schmidt, Bruno E.; Thiré, Nicolas; Fowe, Emmanuel P.; Bisson, Éric; Hebeisen, Christoph T.; Wanie, Vincent; Giguére, Mathieu; Kieffer, Jean-Claude; Spanner, Michael; Bandrauk, André D.; Sanderson, Joseph; Schuurman, Michael S.; Légaré, François

2014-07-01

407

Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation.  

PubMed

The introduction of femto-chemistry has made it a primary goal to follow the nuclear and electronic evolution of a molecule in time and space as it undergoes a chemical reaction. Using Coulomb Explosion Imaging, we have shot the first high-resolution molecular movie of a to and fro isomerization process in the acetylene cation. So far, this kind of phenomenon could only be observed using vacuum ultraviolet light from a free-electron laser. Here we show that 266 nm ultrashort laser pulses are capable of initiating rich dynamics through multiphoton ionization. With our generally applicable tabletop approach that can be used for other small organic molecules, we have investigated two basic chemical reactions simultaneously: proton migration and C=C bond breaking, triggered by multiphoton ionization. The experimental results are in excellent agreement with the timescales and relaxation pathways predicted by new and quantitative ab initio trajectory simulations. PMID:25034613

Ibrahim, Heide; Wales, Benji; Beaulieu, Samuel; Schmidt, Bruno E; Thiré, Nicolas; Fowe, Emmanuel P; Bisson, Éric; Hebeisen, Christoph T; Wanie, Vincent; Giguére, Mathieu; Kieffer, Jean-Claude; Spanner, Michael; Bandrauk, André D; Sanderson, Joseph; Schuurman, Michael S; Légaré, François

2014-01-01

408

Differentiation and replication of spots in a reaction-diffusion system with many chemicals  

NASA Astrophysics Data System (ADS)

The replication and differentiation of spots in reaction-diffusion equations are studied by extending the Gray-Scott model with self-replicating spots to include many degrees of freedom needed to model systems with many chemicals. By examining many possible reaction networks, the behavior of this model is categorized into three types: replication of homogeneous fixed spots, replication of oscillatory spots, and differentiation from "multipotent spots" . These multipotent spots either replicate or differentiate into other types of spots with different fixed-point dynamics, and, as a result, an inhomogeneous pattern of spots is formed. This differentiation process of spots is analyzed in terms of the loss of chemical diversity and decrease of the local Kolmogorov-Sinai entropy. The relevance of the results to developmental cell biology and stem cells is also discussed.

Takagi, H.; Kaneko, K.

2001-10-01

409

Quantum adiabatic theorem for chemical reactions and systems with time-dependent orthogonalization  

E-print Network

A general quantum adiabatic theorem with and without the time-dependent orthogonalization is proven, which can be applied to understand the origin of activation energies in chemical reactions. Further proofs are also developed for the oscillating Schwinger Hamiltonian to establish the relationship between the internal (due to time-dependent eigenfunctions) and external (due to time-dependent Hamiltonian) time scales. We prove that this relationship needs to be taken as an independent quantum adiabatic approximation criterion. We give four examples, including logical expositions based on the spin-1/2 two-level system to address the gapped and gapless (due to energy level crossings) systems, as well as to understand how does this theorem allows one to study dynamical systems such as chemical reactions.

Andrew Das Arulsamy

2010-06-30

410

Simplified models of growth, defect formation, and thermal conductivity in diamond chemical vapor deposition  

SciTech Connect

A simplified surface reaction mechanism is presented for the CVD of diamond thin films. The mechanism also accounts for formation of point defects in the diamond lattice, an alternate, undesirable reaction pathway. Both methyl radicals and atomic C are considered as growth precursors. While not rigorous in all details, the mechanism is useful in describing the CVD diamond process over a wide range of reaction conditions. It should find utility in reactor modeling studies, for example in optimizing diamond growth rate while minimizing defect formation. This report also presents a simple model relating the diamond point-defect density to the thermal conductivity of the material.

Coltrin, M.E.; Dandy, D.S.

1996-04-01

411

Correlation between dynamic wetting behavior and chemical components of thermally modified wood  

NASA Astrophysics Data System (ADS)

In order to investigate the dynamic wetting behavior of thermally modified wood, Cathay poplar (Populus cathayana Rehd.) and Scots pine (Pinus sylvestris L.) samples were thermally modified in an oven at 160, 180, 200, 220 or 240 °C for 4 h in this study. The dynamic contact angles and droplet volumes of water droplets on modified and unmodified wood surfaces were measured by sessile drop method, and their changing rates (expression index: K value and wetting slope) calculated by wetting models were illustrated for mapping the dynamic wetting process. The surface chemical components were also measured by X-ray photoelectron spectroscopy analysis (XPS), thus the relationship between dynamic wetting behavior and chemical components of thermally modified wood were determined. The results indicated that thermal modification was capable of decreasing the dynamic wettability of wood, expressed in lowing spread and penetration speed of water droplets on wood surfaces. This change was more obvious with the increased heating temperature. The K values varied linearly with the chemical components parameter (mass loss, O/C ratio, and C1/C2 ratio), indicating a strong correlation between dynamic wetting behavior and chemical components of thermally modified wood.

Wang, Wang; Zhu, Yuan; Cao, Jinzhen; Sun, Wenjing

2015-01-01

412

Chemical compositions and classifica tion of five thermally altered carbonaceous chondrites  

NASA Astrophysics Data System (ADS)

To establish the chemical group provenance of the five thermally altered carbonaceous chondrites Asuka (A-) 881551, Asuka-882113, Elephant Moraine (EET) 96026, Mulga (west), and Northwest Africa (NWA) 3133, we quantified 44 trace elements in each of them. We also analyzed Larkman Nunatak (LAR) 04318 (CK4), Miller Range (MIL) 090001 (CR2), Roberts Massif (RBT) 03522 (CK5) as reference samples as their chemical group affinity is already recognized. We conclude that Asuka-881551, Asuka-882113, and Mulga (west) are thermally metamorphosed CK chondrites. Compositionally, Elephant Moraine 96026 most resembles the CV chondrites. NWA 3133 is the most significantly thermally altered carbonaceous chondrite in our suite of samples. It is completely recrystallized (no chondrules or matrix remain), but its bulk composition is consistent with a CV-CK clan provenance. The thermally labile element (e.g., Se, Te, Zn, and Bi) depletion in NWA 3133 indicates a chemically open system during the heating episode. It remains unclear if the heat necessary for its thermal alteration of NWA 3133 was due to the decay of 26Al or was impact related. Finally, we infer that MIL 090001, Mulga (west), and NWA 3133 show occasional compositional signatures indicative of terrestrial alteration. The alteration is especially evident within the elements Sr, Ba, La, Ce, Th, U, and possibly Sb. Despite the alteration, we can still confidently place each of the altered chondrites within an established chemical group or clan.

Noronha, Bianca A.; Friedrich, Jon M.

2014-08-01

413

Coupling of Hydrologic Transport and Chemical Reactions in a Stream Affected by Acid Mine Drainage  

Microsoft Academic Search

~~~~~ ~ Experiments in St. Kevin Gulch, an acid mine drainage stream, examined the coupling of hydrologic transport to chemical reactions affecting metal concentrations. Injec- tion of LiCl as a conservative tracer was used to determine discharge and residence time along a 1497-m reach. Transport of metals downstream from inflows of acidic, metal-rich water was evaluated based on synoptic samples

Briant A. Kimball; Robert E. Broshears; Kenneth E. Bencala; Diane M. McKnight

1994-01-01

414

Apparatus for studies of high-temperature chemical reactions in single particle systems.  

PubMed

We report a compact microgravity flight apparatus for characterization of high-temperature chemical reactions in single particle systems. The apparatus employs an infrared CO(2) laser to ignite 1-5 mm samples while video images, thermocouple measurements, laser on/off status, and XYZ accelerometer signals are synchronously recorded. Different operating modes permit preignition quenching, ignition, and combustion experiments to be performed. The apparatus was successfully utilized during microgravity experiments on board NASA research aircraft. PMID:17764350

Andrzejak, Timothy A; Shafirovich, Evgeny; Taylor, David G; Varma, Arvind

2007-08-01

415

Apparatus for studies of high-temperature chemical reactions in single particle systems  

NASA Astrophysics Data System (ADS)

We report a compact microgravity flight apparatus for characterization of high-temperature chemical reactions in single particle systems. The apparatus employs an infrared CO2 laser to ignite 1-5mm samples while video images, thermocouple measurements, laser on/off status, and XYZ accelerometer signals are synchronously recorded. Different operating modes permit preignition quenching, ignition, and combustion experiments to be performed. The apparatus was successfully utilized during microgravity experiments on board NASA research aircraft.

Andrzejak, Timothy A.; Shafirovich, Evgeny; Taylor, David G.; Varma, Arvind

2007-08-01

416

Composition, microstructure, and thermal stability of silicon carbide chemical vapor deposited at low temperatures  

Microsoft Academic Search

In this paper, the authors have examined the chemical composition, microstructure, and thermal stability of silicon carbide chemical vapor deposited at relatively low temperatures ranging from 1000 to 1300°C. Within the present deposition-temperature range, pure silicon carbide was obtained that was composed mainly of cubic-type beta silicon carbide with a small amount of hexagonal-type silicon carbide. Neither free silicon nor

Yongdong Xu; Laifei Cheng; Litong Zhang

2000-01-01

417

Thermal reaction of polycrystalline SiC with XeF{sub 2}  

SciTech Connect

Studies on the thermal reaction behavior of polycrystalline cubic silicon carbide (SiC) with effusive xenon difluoride (XeF{sub 2}) have been carried out over the sample temperature (T{sub s}) range from 300 to 900 K using molecular beam quadrupole mass spectrometry combined with a time-of-flight technique and ex situ surface analyses, i.e., x-ray photoelectron spectroscopy (XPS) and scanning Auger microscopy (SAM). Above T{sub s}=700 K, the reaction product desorbed from the SiC surface was identified as SiF{sub 4}. The flux intensity of SiF{sub 4} increases monotonically as a function of T{sub s} above 700 K. The flux intensity of XeF{sub 2} desorbed from the SiC surface decreases above T{sub s}=700 K, and at T{sub s}=900 K, approximately 10% of the incident XeF{sub 2} was found to be consumed by the thermal reaction. No ions at m/e=31 (CF{sup +}), 50 (CF{sub 2}{sup +}), and 69 (CF{sub 3}{sup +}) to be ascribed to carbon fluoride species were detected under the present experimental conditions, and thus C atoms in SiC were found to remain as residue. From the XPS and SAM observations of the SiC samples exposed to XeF{sub 2} vapor at 1.8x10{sup -4} Torr, we find that fluorination of a native oxide layer formed on the SiC surface takes place at T{sub s}=300 K. At T{sub s}=520 K, the native oxide layer was partially removed from the surface, and the presence of a reaction layer composed of partially fluorinated C atoms was observed. As T{sub s} is increased above 520 K, the reaction layer becomes thicker. Above T{sub s}=700 K, a thick reaction layer mainly composed of C atoms is formed, while only the near-surface reaction layer is fluorinated. The fast desorption of SiF{sub 4} products reduces the Si concentration in the SiC surface and the residual C atoms having comprised the SiC lattice are left as the reaction layer.

Watanabe, Morimichi; Mori, Yukimasa; Sakai, Hiroaki; Iida, Takashi; Koide, Shunsuke; Maeta, Eri; Sawabe, Kyoichi; Shobatake, Kosuke [Materials Research Laboratory, NGK INSULATORS, LTD., 2-56 Suda-cho, Mizuho, Nagoya 467-8530 (Japan); Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603 (Japan)

2005-11-15

418

Thermal reaction of polycrystalline SiC with XeF2  

NASA Astrophysics Data System (ADS)

Studies on the thermal reaction behavior of polycrystalline cubic silicon carbide (SiC) with effusive xenon difluoride (XeF2) have been carried out over the sample temperature (Ts) range from 300 to 900 K using molecular beam quadrupole mass spectrometry combined with a time-of-flight technique and ex situ surface analyses, i.e., x-ray photoelectron spectroscopy (XPS) and scanning Auger microscopy (SAM). Above Ts=700 K, the reaction product desorbed from the SiC surface was identified as SiF4. The flux intensity of SiF4 increases monotonically as a function of Ts above 700 K. The flux intensity of XeF2 desorbed from the SiC surface decreases above Ts=700 K, and at Ts=900 K, approximately 10% of the incident XeF2 was found to be consumed by the thermal reaction. No ions at m/e=31 (CF+), 50 (CF2+), and 69 (CF3+) to be ascribed to carbon fluoride species were detected under the present experimental conditions, and thus C atoms in SiC were found to remain as residue. From the XPS and SAM observations of the SiC samples exposed to XeF2 vapor at 1.8×10-4 Torr, we find that fluorination of a native oxide layer formed on the SiC surface takes place at Ts=300 K. At Ts=520 K, the native oxide layer was partially removed from the surface, and the presence of a reaction layer composed of partially fluorinated C atoms was observed. As Ts is increased above 520 K, the reaction layer becomes thicker. Above Ts=700 K, a thick reaction layer mainly composed of C atoms is formed, while only the near-surface reaction layer is fluorinated. The fast desorption of SiF4 products reduces the Si concentration in the SiC surface and the residual C atoms having comprised the SiC lattice are left as the reaction layer.

Watanabe, Morimichi; Mori, Yukimasa; Sakai, Hiroaki; Iida, Takashi; Koide, Shunsuke; Maeta, Eri; Sawabe, Kyoichi; Shobatake, Kosuke

2005-11-01

419

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

NASA Technical Reports Server (NTRS)

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

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

1951-01-01

420

Thermal effects of metamorphic reactions in a three-component slab  

NASA Astrophysics Data System (ADS)

Thermal evolution of a subducting crust is of primary importance for understanding physical properties, phase transformations, fluid migration and melting regimes at convergent plate boundaries. Various factors influencing the thermal structure of a subduction zone have been considered previously: age, geometry and rate of subducting lithosphere, shear stress across the subduction interface, radioactive heating, etc. Recently, emphasis has been placed on significant heating of the slab due to rheologically favourable convection in the mantle wedge. However, substantial heat production or consumption can occur due to metamorphic reactions, including endothermic devolatilization. We investigate enthalpy budget in a subducting slab using a self-consistent thermodynamic model. Petrological model of a subducting slab consists of three layers: oceanic subducting sediment (GLOSS), oceanic basalt (OB), and moderately serpentinized harzburgite (SHB). These layers are examined over the range of pressure-temperature conditions of interest by computing metamorphic phase diagrams and retrieving whole-rock thermodynamic properties. Our results suggest that metamorphic reactions consume a significant amount of slab heat budget and induce substantial cooling. In contrast to previous thermal models of subduction zones, actual slab temperatures may be lower by as much as 250 °C.

Chemia, Zurab; Dolejš, David; Steinle-Neumanna, Gerd

2010-05-01

421

Thermal Reactions of H2O2 on Icy Satellites and Small Bodies: Descent with Modification?  

NASA Technical Reports Server (NTRS)

Magnetospheric radiation drives surface and near-surface chemistry on Europa, but below a few meters Europa's chemistry is hidden from direct observation . As an example, surface radiation chemistry converts H2O and SO2 into H2O2 and (SO4)(sup 2-), respectively, and these species will be transported downward for possible thermally-driven reactions. However, while the infrared spectra and radiation chemistry of H2O2-containing ices are well documented, this molecule's thermally-induced solid-phase chemistry has seldom been studied. Here we report new results on thermal reactions in H2O + H2O2 + SO2 ices at 50 - 130 K. As an example of our results, we find that warming H2O + H2O2 + SO2 ices promotes SO2 oxidation to (SO4)(sup 2-). These results have implications for the survival of H2O2 as it descends, with modification, towards a subsurface ocean on Europa. We suspect that such redox chemistry may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto.

Hudson, Reggie L.; Loeffler, Mark J.

2012-01-01

422

A DAG scheduling scheme on heterogeneous computing systems using tuple-based chemical reaction optimization.  

PubMed

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

Jiang, Yuyi; Shao, Zhiqing; Guo, Yi

2014-01-01

423

Efficient exact and K-skip methods for stochastic simulation of coupled chemical reactions  

NASA Astrophysics Data System (ADS)

Gillespie's direct method (DM) [D. Gillespie, J. Chem. Phys. 81, 2340 (1977)] for exact stochastic simulation of chemical reaction systems has been widely adopted. It is easy to implement but requires large computation for relatively large systems. Recently, two more efficient methods, next reaction method (NRM) [M. A. Gibson and J. Bruck, J. Phys. Chem. A 105, 1876 (2000)] and optimized DM (ODM) [Y. Cao et al., J. Chem. Phys. 121, 4059 (2004)], have been developed to improve simulation speed. It has been demonstrated that the ODM is the state-of-the-art most efficient method for exact stochastic simulation of most practical reaction systems. In this paper, we first develop an exact stochastic simulation algorithm named ODMK that is more efficient than the ODM. We then develop an approximate method named K-skip method to further accelerate simulation. Using two chemical reaction systems, we demonstrate that our ODMK and K-skip method can save 20%-30% and 70%-80% simulation time, respectively, comparing to the ODM. We also show that our ODMK and K-skip method provide almost the same simulation accuracy as the ODM.

Cai, Xiaodong; Wen, Ji

2009-08-01

424

Using a Natural Analogue to Investigate Chemical Reactions Associated with Carbon Dioxide Sequestration  

NASA Astrophysics Data System (ADS)

Capture and storage of carbon dioxide in deep underground geologic formations (geologic carbon sequestration) is currently the most advanced technology for reducing or mitigating anthropogenic carbon dioxide emissions. There are a number of scientific challenges associated with injection and storage of large amounts of CO2 in geologic formations. Understanding the chemical reactions that can occur among reservoir rocks, aqueous fluids, and supercritical carbon dioxide ± other gasses is one of these challenges. Natural analogues to CO2 sequestration are systems where carbon dioxide has been stored over geologic time scales. By studying these analogues we can determine important chemical reactions between the host rock and stored gases. The Moxa Arch is a structural feature located in the southern end of the greater Green River Basin, Wyoming. Carbon dioxide and methane were emplaced in Paleozoic rocks, including the 1000 feet thick Mississippian age Madison Limestone, of the Moxa Arch through natural processes. Concentrations of carbon dioxide in the emplaced gas in these formations vary in the region of the Moxa Arch from 70-95% and are as low as ~ 15% in gas producing areas outside of the Moxa Arch. Methane, hydrogen sulfide and helium comprise the balance of the gas compositons. Geochemical reaction path and reactive transport models based upon the mineralogy of 12 core samples collected from three wells completed in the Madison Limestone near the Moxa Arch will be presented. These models help identify potential geochemical reactions between reservoir minerals and stored gasses.

Navarre-Sitchler, A.; Kaszuba, J.; Thyne, G.

2008-12-01

425

Novel duplex vapor: Electrochemical method for silicon solar cells. [chemical reactor for a silicon sodium reaction system  

NASA Technical Reports Server (NTRS)

The scaled up chemical reactor for a SiF4-Na reaction system is examined for increased reaction rate and production rate. The reaction system which now produces 5 kg batches of mixed Si and NaF is evaluated. The reactor design is described along with an analysis of the increased capacity of the Na chip feeder. The reactor procedure is discussed and Si coalescence in the reaction products is diagnosed.

Nanis, L.; Sanjurjo, A.; Sancier, K.

1979-01-01

426

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

NASA Technical Reports Server (NTRS)

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

Liechty, Derek S.; Lewis, Mark J.

2010-01-01

427

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

NASA Astrophysics Data System (ADS)

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

Liechty, Derek S.; Lewis, Mark J.

2011-05-01

428

Stress hysteresis during thermal cycling of plasma-enhanced chemical vapor deposited silicon oxide films  

NASA Astrophysics Data System (ADS)

The mechanical response of plasma-enhanced chemical vapor deposited SiO2 to thermal cycling is examined by substrate curvature measurement and depth-sensing indentation. Film properties of deposition stress and stress hysteresis that accompanied thermal cycling are elucidated, as well as modulus, hardness, and coefficient of thermal expansion. Thermal cycling is shown to result in major plastic deformation of the film and a switch from a compressive to a tensile state of stress; both athermal and thermal components of the net stress alter in different ways during cycling. A mechanism of hydrogen incorporation and release from as-deposited silanol groups is proposed that accounts for the change in film properties and state of stress.

Thurn, Jeremy; Cook, Robert F.

2002-02-01

429

Accelerating the Computation of Detailed Chemical Reaction Kinetics for Simulating Combustion of Complex Fuels  

SciTech Connect

Combustion of hydrocarbon fuels has been a very challenging scientific and engineering problem due to the complexity of turbulent flows and hydrocarbon reaction kinetics. There is an urgent need to develop an efficient modeling capability to accurately predict the combustion of complex fuels. Detailed chemical kinetic models for the surrogates of fuels such as gasoline, diesel and JP-8 consist of thousands of chemical species and Arrhenius reaction steps. Oxygenated fuels such as bio-fuels and heavier hydrocarbons, such as from newer fossil fuel sources, are expected to have a much more complex chemistry requiring increasingly larger chemical kinetic models. Such models are beyond current computational capability, except for homogeneous or partially stirred reactor type calculations. The advent of highly parallel multi-core processors and graphical processing units (GPUs) promises a steep increase in computational performance in the coming years. This paper will present a software framework that translates the detailed chemical kinetic models to high- performance code targeted for GPU accelerators.

Grout, Ray W [ORNL

2012-01-01

430

Accelerating the Computation of Detailed Chemical Reaction Kinetics for Simulating Combustion of Complex Fuels  

SciTech Connect

Combustion of hydrocarbon fuels has been a very challenging scientific and engineering problem due to the complexity of turbulent flows and hydrocarbon reaction kinetics. There is an urgent need to develop an efficient modeling capability to accurately predict the combustion of complex fuels. Detailed chemical kinetic models for the surrogates of fuels such as gasoline, diesel and JP-8 consist of thousands of chemical species and Arrhenius reaction steps. Oxygenated fuels such as bio-fuels and heavier hydrocarbons, such as from newer fossil fuel sources, are expected to have a much more complex chemistry requiring increasingly larger chemical kinetic models. Such models are beyond current computational capability, except for homogeneous or partially stirred reactor type calculations. The advent of highly parallel multi-core processors and graphical processing units (GPUs) promises a steep increase in computational performance in the coming years. This paper will present a software framework that translates the detailed chemical kinetic models to high-performance code targeted for GPU accelerators.

Sankaran, R.; Grout, R.

2012-01-01

431

Simulation of gas absorption into string-of-beads liquid flow with chemical reaction  

NASA Astrophysics Data System (ADS)

This study is an attempt to investigate the chemical absorption of CO2 in aqueous monoethanolamine (MEA) solution in a wetted-wire column consisting of one wire. Computational fluid dynamics method along with volume of fluid model was employed for modeling of two-phase flow, mass transfer and chemical reaction inside the column. The modeling results were compared with available experimental data and very good agreement was achieved. The simulation results showed that the diameter and intervals of liquid beads increases by increasing the gas and liquid flow rates. The beads velocity increases by increasing the liquid flow rate and decreasing mass fraction of MEA in the liquid phase. Also, mass transfer resistance in the liquid phase reduces by formation of the beads. It was concluded that the developed model is capable to predict the effect of operating and physical parameters on the investigated chemical absorption process.

Hosseini, S. M.; Alizadeh, R.; Fatehifar, E.; Alizadehdakhel, A.

2014-10-01

432

Thermal and Chemical Characterization of Non-Metallic Materials Using Coupled Thermogravimetric Analysis and Infrared Spectroscopy  

NASA Technical Reports Server (NTRS)

Thermogravimetric analysis (TGA) is widely employed in the thermal characterization of non-metallic materials, yielding valuable information on decomposition characteristics of a sample over a wide temperature range. However, a potential wealth of chemical information is lost during the process, with the evolving gases generated during thermal decomposition escaping through the exhaust line. Fourier Transform-Infrared spectroscopy (FT-IR) is a powerful analytical technique for determining many chemical constituents while in any material state, in this application, the gas phase. By linking these two techniques, evolving gases generated during the TGA process are directed into an appropriately equipped infrared spectrometer for chemical speciation. Consequently, both thermal decomposition and chemical characterization of a material may be obtained in a single sample run. In practice, a heated transfer line is employed to connect the two instruments while a purge gas stream directs the evolving gases into the FT-IR. The purge gas can be either high purity air or an inert gas such as nitrogen to allow oxidative and pyrolytic processes to be examined, respectively. The FT-IR data is collected realtime, allowing continuous monitoring of chemical compositional changes over the course of thermal decomposition. Using this coupled technique, an array of diverse materials has been examined, including composites, plastics, rubber, fiberglass epoxy resins, polycarbonates, silicones, lubricants and fluorocarbon materials. The benefit of combining these two methodologies is of particular importance in the aerospace community, where newly developing materials have little available data with which to refer. By providing both thermal and chemical data simultaneously, a more definitive and comprehensive characterization of the material is possible. Additionally, this procedure has been found to be a viable screening technique for certain materials, with the generated data useful in the selection of other appropriate analytical procedures for further material characterization.

Huff, Timothy L.

2002-01-01

433

Thermal and Chemical Characterization of Non-metallic Materials Using Coupled Thermogravimetric Analysis and Infrared Spectroscopy  

NASA Technical Reports Server (NTRS)

Thermogravimetric analysis (TGA) is widely employed in the thermal characterization of non-metallic materials, yielding valuable information on decomposition characteristics of a sample over a wide temperature range. However, a potential wealth of chemical information is lost during the process, with the evolving gases generated during thermal decomposition escaping through the exhaust line. Fourier Transform-Infrared spectroscopy (FT-IR) is a powerful analytical technique for determining many chemical constituents while in any material state, in this application, the gas phase. By linking these two techniques, evolving gases generated during the TGA process are directed into an appropriately equipped infrared spectrometer for chemical speciation. Consequently, both thermal decomposition and chemical characterization of a material may be obtained in a single sample run. In practice, a heated transfer line is employed to connect the two instruments while a purge gas stream directs the evolving gases into the FT-IR, The purge gas can be either high purity air or an inert gas such as nitrogen to allow oxidative and pyrolytic processes to be examined, respectively. The FT-IR data is collected real-time, allowing continuous monitoring of chemical compositional changes over the course of thermal decomposition. Using this coupled technique, an array of diverse materials has been examined, including composites, plastics, rubber, fiberglass epoxy resins, polycarbonates, silicones, lubricants and fluorocarbon materials. The benefit of combining these two methodologies is of particular importance in the aerospace community, where newly developing materials have little available data with which to refer. By providing both thermal and chemical data simultaneously, a more definitive and comprehensive characterization of the material is possible. Additionally, this procedure has been found to be a viable screening technique for certain materials, with the generated data useful in the selection of other appropriate analytical procedures for further material characterization.

Huff, Timothy L.; Griffin, Dennis E. (Technical Monitor)

2001-01-01

434

Comprehensive study of the chemical reactions resulting from the decomposition of chloroform in alkaline aqueous solution  

NASA Astrophysics Data System (ADS)

Chloroform (CHCl3) is a volatile liquid, which has a rather slow rate of decomposition in ground water. It is a known carcinogen and one of the most common contaminants found at toxic waste sites. The dominant degradation process for chloroform in both the atmosphere and the groundwater is the reaction with the hydroxyl radical or hydroxide ion. This process triggers a sequence of reactions which ultimately yield carbon monoxide, hydrogen chloride, and formic acid. The rate of chloroform degradation is considerably larger in solution than that in the gas phase and it increases dramatically with increasing pH. However, only one of the viable reactions had been studied previously at a high level of theory in solution. It is of great interest to gain a deeper understanding of the decomposition reaction mechanism. Quantum mechanical methods are well suited for studying the mechanism of organic reactions. However, a full quantum mechanical treatment of the entire fluid system is not computationally feasible. In this work, combined quantum mechanical and molecular mechanical (QM/MM) methods are used for studying chemical reactions in condensed phases. In these calculations, the solute molecules are treated quantum mechanically (QM), whereas the solvent molecules are approximated by empirical (MM) potential energy functions. The use of quantum mechanics and statistical sampling simulation is necessary to determine the reaction free energy profile. In the present study, the ab initio Hartree-Fock theory along with the 3-21G basis set was used in the quantum mechanical calculations to elucidate the reaction pathways of chloroform decomposition, with a focus on basic reaction conditions. Statistical mechanical Monte Carlo approach was then applied in molecular mechanical simulations, employing the empirical TIP3P model for water. We employed state-of-the-art electronic structure methods to determine the gas-phase inter-nuclear potential energy profile for all the relevant reactions. Each gas-phase potential energy profile obtained at a high level of theory was used as a post-correction of the corresponding reaction free energy profile in aqueous solution. A detailed picture of the actual mechanism driving the decomposition pathway of chloroform has emerged from these simulations.

Estevez Mews, Jorge

435

Thermal Tests of Target Materials for Nuclear Reaction-Based Interrogation Sources  

NASA Astrophysics Data System (ADS)

Compact active interrogation sources are being developed that use low-energy (kilovolt) nuclear reactions to produce high-energy (megavolt) neutrons or gamma-rays. We are evaluating target materials for these interrogation sources by performing rapid thermal load and high power density tests that reach conditions expected during source operation. Following the tests, the targets are analyzed with low and high resolution microscopes to assess whether any physical or structural damage has occurred. This paper presents results of the examinations of LiF, Li2O, LiNbO3, CaF2, B4C, and LaB6 target materials following rapid thermal and electron beam heating tests.

Provencio, P. P.; McDaniel, F. D.; Antolak, A. J.; Doyle, B. L.; Morse, D. H.

2009-03-01

436

Synthesis and structure characterization of chromium oxide prepared by solid thermal decomposition reaction.  

PubMed

Mesoporous chromium oxide (Cr2O3) nanocrystals were first synthesized by the thermal decomposition reaction of Cr(NO3)3.9H2O using citric acid monohydrate (CA) as the mesoporous template agent. The texture and chemistry of chromium oxide nanocrystals were characterized by N2 adsorption-desorption isotherms, FTIR, X-ray diffraction (XRD), UV-vis, and thermoanalytical methods. It was shown that the hydrate water and CA are the crucial factors in influencing the formation of mesoporous Cr2O3 nanocrystals in the mixture system. The decomposition of CA results in the formation of a mesoporous structure with wormlike pores. The hydrate water of the mixture provides surface hydroxyls that act as binders, making the nanocrystals aggregate. The pore structures and phases of chromium oxide are affected by the ratio of precursor-to-CA, thermal temperature, and time. PMID:16471518

Li, Li; Yan, Zi F; Lu, Gao Q; Zhu, Zhong H

2006-01-12

437

Solar thermal polymerase chain reaction for smartphone-assisted molecular diagnostics.  

PubMed

Nucleic acid-based diagnostic techniques such as polymerase chain reaction (PCR) are used extensively in medical diagnostics due to their high sensitivity, specificity and quantification capability. In settings with limited infrastructure and unreliable electricity, however, access to such devices is often limited due to the highly specialized and energy-intensive nature of the thermal cycling process required for nucleic acid amplification. Here we integrate solar heating with microfluidics to eliminate thermal cycling power requirements as well as create a simple device infrastructure for PCR. Tests are completed in less than 30 min, and power consumption is reduced to 80 mW, enabling a standard 5.5 Wh iPhone battery to provide 70 h of power to this system. Additionally, we demonstrate a complete sample-to-answer diagnostic strategy by analyzing human skin biopsies infected with Kaposi's Sarcoma herpesvirus (KSHV/HHV-8) through the combination of solar thermal PCR, HotSHOT DNA extraction and smartphone-based fluorescence detection. We believe that exploiting the ubiquity of solar thermal energy as demonstrated here could facilitate broad availability of nucleic acid-based diagnostics in resource-limited areas. PMID:24553130

Jiang, Li; Mancuso, Matthew; Lu, Zhengda; Akar, Gunkut; Cesarman, Ethel; Erickson, David

2014-01-01

438

Solar thermal polymerase chain reaction for smartphone-assisted molecular diagnostics  

PubMed Central

Nucleic acid-based diagnostic techniques such as polymerase chain reaction (PCR) are used extensively in medical diagnostics due to their high sensitivity, specificity and quantification capability. In settings with limited infrastructure and unreliable electricity, however, access to such devices is often limited due to the highly specialized and energy-intensive nature of the thermal cycling process required for nucleic acid amplification. Here we integrate solar heating with microfluidics to eliminate thermal cycling power requirements as well as create a simple device infrastructure for PCR. Tests are completed in less than 30?min, and power consumption is reduced to 80?mW, enabling a standard 5.5?Wh iPhone battery to provide 70?h of power to this system. Additionally, we demonstrate a complete sample-to-answer diagnostic strategy by analyzing human skin biopsies infected with Kaposi's Sarcoma herpesvirus (KSHV/HHV-8) through the combination of solar thermal PCR, HotSHOT DNA extraction and smartphone-based fluorescence detection. We believe that exploiting the ubiquity of solar thermal energy as demonstrated here could facilitate broad availability of nucleic acid-based diagnostics in resource-limited areas. PMID:24553130

Jiang, Li; Mancuso, Matthew; Lu, Zhengda; Akar, Gunkut; Cesarman, Ethel; Erickson, David

2014-01-01

439

Colour-temperature correspondences: when reactions to thermal stimuli are influenced by colour.  

PubMed

In our daily lives, information concerning temperature is often provided by means of colour cues, with red typically being associated with warm/hot, and blue with cold. While such correspondences have been known about for many years, they have primarily been studied using subjective report measures. Here we examined this correspondence using two more objective response measures. First, we used the Implicit Association Test (IAT), a test designed to assess the strength of automatic associations between different concepts in a given individual. Second, we used a priming task that involved speeded target discrimination in order to assess whether priming colour or thermal information could invoke the crossmodal association. The results of the IAT confirmed that the association exists at the level of response selection, thus indicating that a participant's responses to colour or thermal stimuli are influenced by the colour-temperature correspondence. The results of the priming experiment revealed that priming a colour affected thermal discrimination reaction times (RTs), but thermal cues did not influence colour discrimination responses. These results may therefore provide important clues as to the level of processing at which such colour-temperature correspondences are represented. PMID:24618675

Ho, Hsin-Ni; Van Doorn, George H; Kawabe, Takahiro; Watanabe, Junji; Spence, Charles

2014-01-01

440

Solar thermal polymerase chain reaction for smartphone-assisted molecular diagnostics  

NASA Astrophysics Data System (ADS)

Nucleic acid-based diagnostic techniques such as polymerase chain reaction (PCR) are used extensively in medical diagnostics due to their high sensitivity, specificity and quantification capability. In settings with limited infrastructure and unreliable electricity, however, access to such devices is often limited due to the highly specialized and energy-intensive nature of the thermal cycling process required for nucleic acid amplification. Here we integrate solar heating with microfluidics to eliminate thermal cycling power requirements as well as create a simple device infrastructure for PCR. Tests are completed in less than 30 min, and power consumption is reduced to 80 mW, enabling a standard 5.5 Wh iPhone battery to provide 70 h of power to this system. Additionally, we demonstrate a complete sample-to-answer diagnostic strategy by analyzing human skin biopsies infected with Kaposi's Sarcoma herpesvirus (KSHV/HHV-8) through the combination of solar thermal PCR, HotSHOT DNA extraction and smartphone-based fluorescence detection. We believe that exploiting the ubiquity of solar thermal energy as demonstrated here could facilitate broad availability of nucleic acid-based diagnostics in resource-limited areas.

Jiang, Li; Mancuso, Matthew; Lu, Zhengda; Akar, Gunkut; Cesarman, Ethel; Erickson, David

2014-02-01

441

Colour-Temperature Correspondences: When Reactions to Thermal Stimuli Are Influenced by Colour  

PubMed Central

In our daily lives, information concerning temperature is often provided by means of colour cues, with red typically being associated with warm/hot, and blue with cold. While such correspondences have been known about for many years, they have primarily been studied using subjective report measures. Here we examined this correspondence using two more objective response measures. First, we used the Implicit Association Test (IAT), a test designed to assess the strength of automatic associations between different concepts in a given individual. Second, we used a priming task that involved speeded target discrimination in order to assess whether priming colour or thermal information could invoke the crossmodal association. The results of the IAT confirmed that the association exists at the level of response selection, thus indicating that a participant’s responses to colour or thermal stimuli are influenced by the colour-temperature correspondence. The results of the priming experiment revealed that priming a colour affected thermal discrimination reaction times (RTs), but thermal cues did not influence colour discrimination responses. These results may therefore provide important clues as to the level of processing at which such colour-temperature correspondences are represented. PMID:24618675

Ho, Hsin-Ni; Van Doorn, George H.; Kawabe, Takahiro; Watanabe, Junji; Spence, Charles

2014-01-01

442

Thermal release rate studies of nuclear reaction products from polycrystalline metal matrices  

NASA Astrophysics Data System (ADS)

The thermal release rate of nuclear reaction products was investigated in offline annealing experiments. This work was motivated by the search for a high melting catcher material for recoiling products from heavy ion induced nuclear fusion reactions. Polycrystalline refractory metal foils of Ni, Y, Zr, Nb, Mo, Hf, W, and Re were investigated as catcher metals. Diffusion data for various tracer/host combinations were deduced from the measured release rates. This work focuses on the diffusion and the release rate of volatile p-elements from row 5 and 6 of the periodic table as lighter homologues of the superheavy elements with Z ? 113 to be studied in future experiments. A massive radiation damage enhancement of the diffusion velocity was observed. Diffusion trends have been established along the groups and rows of the periodic table based on the dependence of diffusion velocity on atomic sizes.

Wittwer, D.; Dressler, R.; Eichler, R.; Gäggeler, H. W.; Piguet, D.; Türler, A.

2013-02-01

443

Thin-layer chromatography and mass spectrometry coupled using proximal probe thermal desorption with electrospray or atmospheric pressure chemical ionization.  

PubMed

An atmospheric pressure proximal probe thermal desorption sampling method coupled with secondary ionization by electrospray or atmospheric pressure chemical ionization was demonstrated for the mass spectrometric analysis of a diverse set of compounds (dyestuffs, pharmaceuticals, explosives and pesticides) separated on various high-performance thin-layer chromatography plates. Line scans along or through development lanes on the plates were carried out by moving the plate relative to a stationary heated probe positioned close to or just touching the stationary phase surface. Vapors of the compounds thermally desorbed from the surface were drawn into the ionization region of a combined electrospray ionization/atmospheric pressure chemical ionization source where they merged with reagent ions and/or charged droplets from a corona discharge or an electrospray emitter and were ionized. The ionized components were then drawn through the atmospheric pressure sampling orifice into the vacuum region of a triple quadrupole mass spectrometer and detected using full scan, single ion monitoring, or selected reaction monitoring mode. Studies of variable parameters and performance metrics including the proximal probe temperature, gas flow rate into the ionization region, surface scan speed, read-out resolution, detection limits, and surface type are discussed. PMID:20499315

Ovchinnikova, Olga S; Van Berkel, Gary J

2010-06-30

444