Mixing and reactions in multiphase flow through porous media

NASA Astrophysics Data System (ADS)

Jimenez-Martinez, J.; Le Borgne, T.; Meheust, Y.; Porter, M. L.; De Anna, P.; Hyman, J.; Tabuteau, H.; Turuban, R.; Carey, J. W.; Viswanathan, H. S.

2016-12-01

The understanding and quantification of flow and transport processes in multiphase systems remains a grand scientific and engineering challenge in natural and industrial systems (e.g., soils and vadose zone, CO2 sequestration, unconventional oil and gas extraction, enhanced oil recovery). Beyond the kinetic of the chemical reactions, mixing processes in porous media play a key role in controlling both fluid-fluid and fluid-solid reactions. However, conventional continuum-scale models and theories oversimplify and/or ignore many important pore-scale processes. Multiphase flows, with the creation of highly heterogeneous fluid velocity fields (i.e., low velocities regions or stagnation zones, and high velocity regions or preferential paths), makes conservative and reactive transport more complex. We present recent multi-scale experimental developments and theoretical approaches to quantify transport, mixing, and reaction and their coupling with multiphase flows. We discuss our main findings: i) the sustained concentration gradients and enhanced reactivity in a two-phase system for a continuous injection, and the comparison with a pulse line injection; ii) the enhanced mixing by a third mobile-immiscible phase; and iii) the role that capillary forces play in the localization of the fluid-solid reactions. These experimental results are for highly-idealized geometries, however, the proposed models are related to basic porous media and unsaturated flow properties, and could be tested on more complex systems.

Predicting the enhancement of mixing-driven reactions in nonuniform flows using measures of flow topology.

PubMed

Engdahl, Nicholas B; Benson, David A; Bolster, Diogo

2014-11-01

The ability for reactive constituents to mix is often the key limiting factor for the completion of reactions across a huge range of scales in a variety of media. In flowing systems, deformation and shear enhance mixing by bringing constituents into closer proximity, thus increasing reaction potential. Accurately quantifying this enhanced mixing is key to predicting reactions and typically is done by observing or simulating scalar transport. To eliminate this computationally expensive step, we use a Lagrangian stochastic framework to derive the enhancement to reaction potential by calculating the collocation probability of particle pairs in a heterogeneous flow field accounting for deformations. We relate the enhanced reaction potential to three well known flow topology metrics and demonstrate that it is best correlated to (and asymptotically linear with) one: the largest eigenvalue of the (right) Cauchy-Green tensor.

Method of introducing additive into a reaction gas flow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michelfelder, S.; Chughtai, M.Y.

1984-04-03

A method of continuously introducing additive, which is conveyed by gaseous and/or liquid carriers, into a turbulent reaction gas flow in the combustion chamber of a steam generator having dry ash withdrawal for selective removal, in a dry manner, of environmentally harmful gaseous noxious materials, such as sulfur, chlorine, and chlorine compounds, which are contained in a hot reaction gas flow which results after a complete or incomplete flame combustion of solid, liquid, or gaseous fuels. Depending upon the additive introduced, heat is stored and/or used for decomposition reactions. The additive, is first introduced at one or more input locations,more » due to locally different pressure conditions in the combustion chamber, into one or more recirculation flows which are within the system and are closed. The additive is subsequently withdrawn from these recirculation flows and is introduced into the reaction gas flow.« less

Modeling and simulation of enzymatic gluconic acid production using immobilized enzyme and CSTR-PFTR circulation reaction system.

PubMed

Li, Can; Lin, Jianqun; Gao, Ling; Lin, Huibin; Lin, Jianqiang

2018-04-01

Production of gluconic acid by using immobilized enzyme and continuous stirred tank reactor-plug flow tubular reactor (CSTR-PFTR) circulation reaction system. A production system is constructed for gluconic acid production, which consists of a continuous stirred tank reactor (CSTR) for pH control and liquid storage and a plug flow tubular reactor (PFTR) filled with immobilized glucose oxidase (GOD) for gluconic acid production. Mathematical model is developed for this production system and simulation is made for the enzymatic reaction process. The pH inhibition effect on GOD is modeled by using a bell-type curve. Gluconic acid can be efficiently produced by using the reaction system and the mathematical model developed for this system can simulate and predict the process well.

Characterizing Strength of Chaotic Dynamics and Numerical Simulation Relevant to Modified Taylor-Couette Flow with Hourglass Geometry

NASA Astrophysics Data System (ADS)

Hou, Yu; Kowalski, Adam; Schroder, Kjell; Halmstad, Andrew; Olsen, Thomas; Wiener, Richard

2006-05-01

We characterize the strength of chaos in two different regimes of Modified Taylor-Couette flow with Hourglass Geometry: the formation of Taylor Vortices with laminar flow and with turbulent flow. We measure the strength of chaos by calculating the correlation dimension and the Kaplan-Yorke dimension based upon the Lyapunov Exponents of each system. We determine the reliability of our calculations by considering data from a chaotic electronic circuit. In order to predict the behavior of the Modified Taylor-Couette flow system, we employ simulations based upon an idealized Reaction-Diffusion model with a third order non-linearity in the reaction rate. Variation of reaction rate with length corresponds to variation of the effective Reynolds Number along the Taylor-Couette apparatus. We present preliminary results and compare to experimental data.

System Modeling for Ammonia Synthesis Energy Recovery System

NASA Astrophysics Data System (ADS)

Bran Anleu, Gabriela; Kavehpour, Pirouz; Lavine, Adrienne; Ammonia thermochemical Energy Storage Team

2015-11-01

An ammonia thermochemical energy storage system is an alternative solution to the state-of-the-art molten salt TES system for concentrating solar power. Some of the advantages of this emerging technology include its high energy density, no heat losses during the storage duration, and the possibility of long storage periods. Solar energy powers an endothermic reaction to disassociate ammonia into hydrogen and nitrogen, which can be stored for future use. The reverse reaction is carried out in the energy recovery process; a hydrogen-nitrogen mixture flowing through a catalyst bed undergoes the exothermic ammonia synthesis reaction. The goal is to use the ammonia synthesis reaction to heat supercritical steam to temperatures on the order of 650°C as required for a supercritical steam Rankine cycle. The steam will flow through channels in a combined reactor-heat exchanger. A numerical model has been developed to determine the optimal design to heat supercritical steam while maintaining a stable exothermic reaction. The model consists of a transient one dimensional concentric tube counter-flow reactor-heat exchanger. The numerical model determines the inlet mixture conditions needed to achieve various steam outlet conditions.

[Studies on a sequential injection renewable surface reflectance spectrophotometric system using a microchip flow cell].

PubMed

Wang, Jian-ya; Fang, Zhao-lun

2002-02-01

A microchip flow cell was developed for flow injection renewable surface assay by reflectance spectrophotometry. The flow cell was coupled to a sequential injection system and optical fiber photometric detection system. The flow cell featured a three-layer structure. The flow channel was cut into a silicone rubber membrance which formed the middle layer, and a porous filter was inlayed across a widened section of the channel to trap microbeads introduced into the flow cell. The area of the detection window of the flow cell was approximately 3.6 mm2, the volume of the bead trapped in the flow cell was 2.2 microL, the depth of the bead layer was 600 microns. A multistrand bifurcated optical fiber was coupled with incident light, detector and flow cell. The chromogenic reaction of Cr(VI) with 1,5-diphenylcarbohydrazide (DPC) which was adsorbed on trapped Polysorb C-18 beads was used as a model reaction to optimize the flow cell design and the experimental system. The reflectance of the renewable reaction surface was monitored at 540 nm. With 100 microL sample loaded and 1.0 mL.min-1 carrier flow rate, the linear response range was 0-0.6 microgram.mL-1 Cr(VI). A detection limit (3 sigma) of 6 ng.mL-1, precision of 1.5% RSD(n = 11), and a throughput of 64 samples per hour were achieved. Considerations in system and flow cell design, the influence of depth of the bead layer, weight of beads used, and the flow rates of carrier stream on the performance were discussed.

Generation of hazardous methyl azide and its application to synthesis of a key-intermediate of picarbutrazox, a new potent pesticide in flow.

PubMed

Ichinari, Daisuke; Nagaki, Aiichiro; Yoshida, Jun-Ichi

2017-12-01

Generation and reactions of methyl azide (MeN 3 ) were successfully performed by using a flow reactor system, demonstrating that the flow method serves as a safe method for handling hazardous explosive methyl azide. The reaction of NaN 3 and Me 2 SO 4 in a flow reactor gave a MeN 3 solution, which was used for Huisgen reaction with benzoyl cyanide in a flow reactor after minimal washing. The resulting 1-methyl-5-benzoyltetrazole serves as a key intermediate of picarbutrazox (IX), a new potent pesticide. Copyright © 2017. Published by Elsevier Ltd.

Partitioned coupling of advection-diffusion-reaction systems and Brinkman flows

NASA Astrophysics Data System (ADS)

Lenarda, Pietro; Paggi, Marco; Ruiz Baier, Ricardo

2017-09-01

We present a partitioned algorithm aimed at extending the capabilities of existing solvers for the simulation of coupled advection-diffusion-reaction systems and incompressible, viscous flow. The space discretisation of the governing equations is based on mixed finite element methods defined on unstructured meshes, whereas the time integration hinges on an operator splitting strategy that exploits the differences in scales between the reaction, advection, and diffusion processes, considering the global system as a number of sequentially linked sets of partial differential, and algebraic equations. The flow solver presents the advantage that all unknowns in the system (here vorticity, velocity, and pressure) can be fully decoupled and thus turn the overall scheme very attractive from the computational perspective. The robustness of the proposed method is illustrated with a series of numerical tests in 2D and 3D, relevant in the modelling of bacterial bioconvection and Boussinesq systems.

Prize to a Faculty Member for Research in an Undergraduate: Chaotic mixing and front propagation

NASA Astrophysics Data System (ADS)

Solomon, Tom

2014-03-01

We present results from a series of experiments - all done with undergraduate students - on chaotic fluid mixing and the effects of fluid flows on the behavior of reaction systems. Simple, well-ordered laminar fluid flows can give rise to fluid mixing with complexity far beyond that of the underlying flow, with tracers that separate exponentially in time and invariant manifolds that act as barriers to transport. Recently, we have studied how fluid mixing affects the propagation of reaction fronts in a flow. This is an issue with applications to a wide range of systems including microfluidic chemical reactors, blooms of phytoplankton in the oceans, and the spreading of a disease in a moving population. To analyze and predict the behavior of the fronts, we generalize tools developed to describe passive mixing. In particular, the concept of an invariant manifold is expanded to account for reactive burning. ``Burning invariant manifolds'' (BIMs) are predicted and measured experimentally as structures in the flow that act as one-way barriers that block the motion of reaction fronts. We test these ideas experimentally in three fluid flows: (a) and chain of alternating vortices; (b) an extended, spatially-random pattern of vortices; and (c) a time-independent, three-dimensional, nested vortex flow. The reaction fronts are produced chemically with variations of the well-known Belousov-Zhabotinsky reaction. Supported by Research Corporation and the National Science Foundation.

Optimal stretching in the reacting wake of a bluff body.

PubMed

Wang, Jinge; Tithof, Jeffrey; Nevins, Thomas D; Colón, Rony O; Kelley, Douglas H

2017-12-01

We experimentally study spreading of the Belousov-Zhabotinsky reaction behind a bluff body in a laminar flow. Locations of reacted regions (i.e., regions with high product concentration) correlate with a moderate range of Lagrangian stretching and that range is close to the range of optimal stretching previously observed in topologically different flows [T. D. Nevins and D. H. Kelley, Phys. Rev. Lett. 117, 164502 (2016)]. The previous work found optimal stretching in a closed, vortex dominated flow, but this article uses an open flow and only a small area of appreciable vorticity. We hypothesize that optimal stretching is common in advection-reaction-diffusion systems with an excitation threshold, including excitable and bistable systems, and that the optimal range depends on reaction chemistry and not on flow shape or characteristic speed. Our results may also give insight into plankton blooms behind islands in ocean currents.

Catalytic combustion of hydrogen-air mixtures in stagnation flows

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ikeda, H.; Libby, P.A.; Williams, F.A.

1993-04-01

The interaction between heterogeneous and homogeneous reactions arising when a mixture of hydrogen and air impinges on a platinum plate at elevated temperature is studied. A reasonably complete description of the kinetic mechanism for homogeneous reactions is employed along with a simplified model for heterogeneous reactions. Four regimes are identified depending on the temperature of the plate, on the rate of strain imposed on the flow adjacent to the plate and on the composition and temperature of the reactant stream: (1) surface reaction alone; (2) surface reaction inhibiting homogeneous reaction; (3) homogeneous reaction inhibiting surface reaction; and (4) homogeneous reactionmore » alone. These regimes are related to those found earlier for other chemical systems and form the basis of future experimental investigation of the chemical system considered in the present study.« less

The effect of a crosslinking chemical reaction on pattern formation in viscous fingering of miscible fluids in a Hele-Shaw cell.

PubMed

Bunton, Patrick H; Tullier, Michael P; Meiburg, Eckart; Pojman, John A

2017-10-01

Viscous fingering can occur in fluid motion whenever a high mobility fluid displaces a low mobility fluid in a Darcy type flow. When the mobility difference is primarily attributable to viscosity (e.g., flow between the two horizontal plates of a Hele-Shaw cell), viscous fingering (VF) occurs, which is sometimes termed the Saffman-Taylor instability. Alternatively, in the presence of differences in density in a gravity field, buoyancy-driven convection can occur. These instabilities have been studied for decades, in part because of their many applications in pollutant dispersal, ocean currents, enhanced petroleum recovery, and so on. More recent interest has emerged regarding the effects of chemical reactions on fingering instabilities. As chemical reactions change the key flow parameters (densities, viscosities, and concentrations), they may have either a destabilizing or stabilizing effect on the flow. Hence, new flow patterns can emerge; moreover, one can then hope to gain some control over flow instabilities through reaction rates, flow rates, and reaction products. We report effects of chemical reactions on VF in a Hele-Shaw cell for a reactive step-growth cross-linking polymerization system. The cross-linked reaction product results in a non-monotonic viscosity profile at the interface, which affects flow stability. Furthermore, three-dimensional internal flows influence the long-term pattern that results.

The effect of a crosslinking chemical reaction on pattern formation in viscous fingering of miscible fluids in a Hele-Shaw cell

NASA Astrophysics Data System (ADS)

Bunton, Patrick H.; Tullier, Michael P.; Meiburg, Eckart; Pojman, John A.

2017-10-01

Viscous fingering can occur in fluid motion whenever a high mobility fluid displaces a low mobility fluid in a Darcy type flow. When the mobility difference is primarily attributable to viscosity (e.g., flow between the two horizontal plates of a Hele-Shaw cell), viscous fingering (VF) occurs, which is sometimes termed the Saffman-Taylor instability. Alternatively, in the presence of differences in density in a gravity field, buoyancy-driven convection can occur. These instabilities have been studied for decades, in part because of their many applications in pollutant dispersal, ocean currents, enhanced petroleum recovery, and so on. More recent interest has emerged regarding the effects of chemical reactions on fingering instabilities. As chemical reactions change the key flow parameters (densities, viscosities, and concentrations), they may have either a destabilizing or stabilizing effect on the flow. Hence, new flow patterns can emerge; moreover, one can then hope to gain some control over flow instabilities through reaction rates, flow rates, and reaction products. We report effects of chemical reactions on VF in a Hele-Shaw cell for a reactive step-growth cross-linking polymerization system. The cross-linked reaction product results in a non-monotonic viscosity profile at the interface, which affects flow stability. Furthermore, three-dimensional internal flows influence the long-term pattern that results.

Effects of reaction control system jet flow field interactions on the aerodynamic characteristics of a 0.010-scale space shuttle orbiter model in the Langley Research Center 31 inch CFHT (OA85)

NASA Technical Reports Server (NTRS)

Daileda, J. J.; Marroquin, J.

1974-01-01

An experimental investigation was conducted to obtain detailed effects on supersonic vehicle hypersonic aerodynamic and stability and control characteristics of reaction control system jet flow field interactions with the local vehicle flow field. A 0.010-scale model was used. Six-component force data and wing, elevon, and body flap surface pressure data were obtained through an angle-of-attack range of -10 to +35 degrees with 0 deg angle of sideslip. The test was conducted with yaw, pitch and roll jet simulation at a free-stream Mach number of 10.3 and reaction control system plume simulation of flight dynamic pressures of 5, 10 and 20 PSF.

Effects of gas flow on oxidation reaction in liquid induced by He/O{sub 2} plasma-jet irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakajima, Atsushi; Uchida, Giichiro, E-mail: uchida@jwri.osaka-u.ac.jp; Takenaka, Kosuke

We present here analysis of oxidation reaction in liquid by a plasma-jet irradiation under various gas flow patterns such as laminar and turbulence flows. To estimate the total amount of oxidation reaction induced by reactive oxygen species (ROS) in liquid, we employ a KI-starch solution system, where the absorbance of the KI-starch solution near 600 nm behaves linear to the total amount of oxidation reaction in liquid. The laminar flow with higher gas velocity induces an increase in the ROS distribution area on the liquid surface, which results in a large amount of oxidation reaction in liquid. However, a much fastermore » gas flow conversely results in a reduction in the total amount of oxidation reaction in liquid under the following two conditions: first condition is that the turbulence flow is triggered in a gas flow channel at a high Reynolds number of gas flow, which leads to a marked change of the spatial distribution of the ROS concentration in gas phase. Second condition is that the dimpled liquid surface is formed by strong gas flow, which prevents the ROS from being transported in radial direction along the liquid surface.« less

Mass spectrometric real-time monitoring of an enzymatic phosphorylation assay using internal standards and data-handling freeware.

PubMed

Krappmann, Michael; de Boer, Arjen R; Kool, Daniël R W; Irth, Hubertus; Letzel, Thomas

2016-04-30

Continuous-flow reaction detection systems (monitoring enzymatic reactions with mass spectrometry (MS)) lack quantitative values so far. Therefore, two independent internal standards (IS) are implemented in a way that the online system stability can be observed, quantitative conversion values for substrate and product can be obtained and they can be used as mass calibration standards for high MS accuracy. An application previously developed for the MS detection of peptide phosphorylation by cAMP-dependent protein kinase A (PKA) (De Boer et al., Anal. Bioanal. Chem. 2005, 381, 647-655) was transferred to a continuous-flow reaction detection system. This enzymatic reaction, involving enzyme activation as well as the transfer of a phosphate group from ATP to a peptide substrate, was used to prove the compatibility of a quantitative enzymatic assay in a continuous-flow real-time system (connected to MS). Moreover (using internal standards), the critical parameter reaction temperature (including solution density variations depending on temperature) was studied in the continuous-flow mixing system. Furthermore, two substrates (malantide and kemptide), two enzyme types (catalytic subunit of PKA and complete PKA) and one inhibitor were tested to determine system robustness and long-term availability. Even spraying solutions that contained significant amount of MS contaminants (e.g. the polluted catalytic subunit) resulted in quantifiable MS signal intensities. Subsequent recalculations using the internal standards led to results representing the power of this application. The presented methodology and the data evaluation with available Achroma freeware enable the direct coupling of biochemical assays with quantitative MS detection. Monitoring changes such as temperature, reaction time, inhibition, or compound concentrations can be observed quantitatively and thus enzymatic activity can be calculated. Copyright © 2016 John Wiley & Sons, Ltd.

Photoreactor with self-contained photocatalyst recapture

DOEpatents

Gering, Kevin L.

2004-12-07

A system for the continuous use and recapture of a catalyst in liquid, comprising: a generally vertical reactor having a reaction zone with generally downwardly flowing liquid, and a catalyst recovery chamber adjacent the reaction zone containing a catalyst consisting of buoyant particles. The liquid in the reaction zone flows downward at a rate which exceeds the speed of upward buoyant migration of catalyst particles in the liquid, whereby catalyst particles introduced into the liquid in the reaction zone are drawn downward with the liquid. A slow flow velocity flotation chamber disposed below the reaction zone is configured to recapture the catalyst particles and allow them to float back into the catalyst recovery chamber for recycling into the reaction zone, rather than being swept downstream. A novel 3-dimensionally adjustable solar reflector directs light into the reaction zone to induce desired photocatalytic reactions within the liquid in the reaction zone.

Water, Energy, and Biogeochemical Model (WEBMOD), user’s manual, version 1

USGS Publications Warehouse

Webb, Richard M.T.; Parkhurst, David L.

2017-02-08

The Water, Energy, and Biogeochemical Model (WEBMOD) uses the framework of the U.S. Geological Survey (USGS) Modular Modeling System to simulate fluxes of water and solutes through watersheds. WEBMOD divides watersheds into model response units (MRU) where fluxes and reactions are simulated for the following eight hillslope reservoir types: canopy; snowpack; ponding on impervious surfaces; O-horizon; two reservoirs in the unsaturated zone, which represent preferential flow and matrix flow; and two reservoirs in the saturated zone, which also represent preferential flow and matrix flow. The reservoir representing ponding on impervious surfaces, currently not functional (2016), will be implemented once the model is applied to urban areas. MRUs discharge to one or more stream reservoirs that flow to the outlet of the watershed. Hydrologic fluxes in the watershed are simulated by modules derived from the USGS Precipitation Runoff Modeling System; the National Weather Service Hydro-17 snow model; and a topography-driven hydrologic model (TOPMODEL). Modifications to the standard TOPMODEL include the addition of heterogeneous vertical infiltration rates; irrigation; lateral and vertical preferential flows through the unsaturated zone; pipe flow draining the saturated zone; gains and losses to regional aquifer systems; and the option to simulate baseflow discharge by using an exponential, parabolic, or linear decrease in transmissivity. PHREEQC, an aqueous geochemical model, is incorporated to simulate chemical reactions as waters evaporate, mix, and react within the various reservoirs of the model. The reactions that can be specified for a reservoir include equilibrium reactions among water; minerals; surfaces; exchangers; and kinetic reactions such as kinetic mineral dissolution or precipitation, biologically mediated reactions, and radioactive decay. WEBMOD also simulates variations in the concentrations of the stable isotopes deuterium and oxygen-18 as a result of varying inputs, mixing, and evaporation. This manual describes the WEBMOD input and output files, along with the algorithms and procedures used to simulate the hydrology and water quality in a watershed. Examples are presented that demonstrate hydrologic processes, weathering reactions, and isotopic evolution in an alpine watershed and the effect of irrigation on water flows and salinity in an intensively farmed agricultural area.

Systematic development of reduced reaction mechanisms for dynamic modeling

NASA Technical Reports Server (NTRS)

Frenklach, M.; Kailasanath, K.; Oran, E. S.

1986-01-01

A method for systematically developing a reduced chemical reaction mechanism for dynamic modeling of chemically reactive flows is presented. The method is based on the postulate that if a reduced reaction mechanism faithfully describes the time evolution of both thermal and chain reaction processes characteristic of a more complete mechanism, then the reduced mechanism will describe the chemical processes in a chemically reacting flow with approximately the same degree of accuracy. Here this postulate is tested by producing a series of mechanisms of reduced accuracy, which are derived from a full detailed mechanism for methane-oxygen combustion. These mechanisms were then tested in a series of reactive flow calculations in which a large-amplitude sinusoidal perturbation is applied to a system that is initially quiescent and whose temperature is high enough to start ignition processes. Comparison of the results for systems with and without convective flow show that this approach produces reduced mechanisms that are useful for calculations of explosions and detonations. Extensions and applicability to flames are discussed.

Evaluation of antifungal volatile compounds on the basis of the elongation rate of a single hypha.

PubMed Central

Matsuoka, H; Ii, Y; Takekawa, Y; Teraoka, T

1990-01-01

A novel method is proposed for the evaluation of the activity of an antifungal agent administered as a gas. This system is composed of a batch-flow type reaction vessel, a gas flow system, and a microscopic observation system. The agar plate was prepared on the ceiling of the reaction vessel, and the mycelium of a fungus (Aspergillus niger or Rhizoctonia solani) was inoculated onto it. After preincubation at 25 degrees C for 24 h, the reaction vessel was connected to the gas flow system. An appropriate hypha was selected, and its elongation rate was measured. Then a sample holder containing an antifungal compound was inserted into the reaction vessel from the side hole to saturate the atmosphere inside with its vapor. The retardation or inhibition of the hypha elongation was observed on a television monitor and recorded on a video tape recorder. The antifungal compound was then removed, and the reaction vessel was flushed with air. If the hypha lived, it began to elongate again. By this method, antifungal activity of seven odor compounds could be evaluated quantitatively within several hours. Images PMID:2082824

Chemical reaction and radiation effects on MHD flow past an exponentially stretching sheet with heat sink

NASA Astrophysics Data System (ADS)

Nur Wahida Khalili, Noran; Aziz Samson, Abdul; Aziz, Ahmad Sukri Abdul; Ali, Zaileha Md

2017-09-01

In this study, the problem of MHD boundary layer flow past an exponentially stretching sheet with chemical reaction and radiation effects with heat sink is studied. The governing system of PDEs is transformed into a system of ODEs. Then, the system is solved numerically by using Runge-Kutta-Fehlberg fourth fifth order (RKF45) method available in MAPLE 15 software. The numerical results obtained are presented graphically for the velocity, temperature and concentration. The effects of various parameters are studied and analyzed. The numerical values for local Nusselt number, skin friction coefficient and local Sherwood number are tabulated and discussed. The study shows that various parameters give significant effect on the profiles of the fluid flow. It is observed that the reaction rate parameter affected the concentration profiles significantly and the concentration thickness of boundary layer decreases when reaction rate parameter increases. The analysis found is validated by comparing with the results previous work done and it is found to be in good agreement.

Comparison of Mars Science Laboratory Reaction Control System Jet Computations With Flow Visualization and Velocimetry

NASA Technical Reports Server (NTRS)

Bathel, Brett F.; Danehy, Paul M.; Johansen, Craig T.; Ashcraft, Scott W.; Novak, Luke A.

2013-01-01

Numerical predictions of the Mars Science Laboratory reaction control system jets interacting with a Mach 10 hypersonic flow are compared to experimental nitric oxide planar laser-induced fluorescence data. The steady Reynolds Averaged Navier Stokes equations using the Baldwin-Barth one-equation turbulence model were solved using the OVERFLOW code. The experimental fluorescence data used for comparison consists of qualitative two-dimensional visualization images, qualitative reconstructed three-dimensional flow structures, and quantitative two-dimensional distributions of streamwise velocity. Through modeling of the fluorescence signal equation, computational flow images were produced and directly compared to the qualitative fluorescence data.

A multipumping flow system for in vitro screening of peroxynitrite scavengers.

PubMed

Ribeiro, Marta F T; Dias, Ana C B; Santos, João L M; Fernandes, Eduarda; Lima, José L F C; Zagatto, Elias A G

2007-09-01

Peroxynitrite anion is a reactive nitrogen species formed in vivo by the rapid, controlled diffusion reaction between nitric oxide and superoxide radicals. By reacting with several biological molecules, peroxynitrite may cause important cellular and tissue deleterious effects, which have been associated with many diseases. In this work, an automated flow-based procedure for the in vitro generation of peroxynitrite and subsequent screening of the scavenging activity of selected compounds is developed. This procedure involves a multipumping flow system (MPFS) and exploits the ability of compounds such as lipoic acid, dihydrolipoic acid, cysteine, reduced glutathione, oxidized glutathione, sulindac, and sulindac sulfone to inhibit the chemiluminescent reaction of luminol with peroxynitrite under physiological simulated conditions. Peroxynitrite was generated in the MPFS by the online reaction of acidified hydrogen peroxide with nitrite, followed by a subsequent stabilization by merging with a sodium hydroxide solution to rapidly quench the developing reaction. The pulsed flow and the timed synchronized insertion of sample and reagent solutions provided by the MPFS ensure the establishment of the reaction zone only inside the flow cell, thus allowing maximum chemiluminescence emission detection. The results obtained for the assayed compounds show that, with the exception of oxidized glutathione, all are highly potent scavengers of peroxynitrite at the studied concentrations.

Multichannel quench-flow microreactor chip for parallel reaction monitoring.

PubMed

Bula, Wojciech P; Verboom, Willem; Reinhoudt, David N; Gardeniers, Han J G E

2007-12-01

This paper describes a multichannel silicon-glass microreactor which has been utilized to investigate the kinetics of a Knoevenagel condensation reaction under different reaction conditions. The reaction is performed on the chip in four parallel channels under identical conditions but with different residence times. A special topology of the reaction coils overcomes the common problem arising from the difference in pressure drop of parallel channels having different length. The parallelization of reaction coils combined with chemical quenching at specific locations results in a considerable reduction in experimental effort and cost. The system was tested and showed good reproducibility in flow properties and reaction kinetic data generation.

Rapid Catalyst Screening by a Continuous-Flow Microreactor Interfaced with Ultra High Pressure Liquid Chromatography

PubMed Central

Fang, Hui; Xiao, Qing; Wu, Fanghui; Floreancig, Paul E.; Weber, Stephen G.

2010-01-01

A high-throughput screening system for homogeneous catalyst discovery has been developed by integrating a continuous-flow capillary-based microreactor with ultra-high pressure liquid chromatography (UHPLC) for fast online analysis. Reactions are conducted in distinct and stable zones in a flow stream that allows for time and temperature regulation. UHPLC detection at high temperature allows high throughput online determination of substrate, product, and byproduct concentrations. We evaluated the efficacies of a series of soluble acid catalysts for an intramolecular Friedel-Crafts addition into an acyliminium ion intermediate within one day and with minimal material investment. The effects of catalyst loading, reaction time, and reaction temperature were also screened. This system exhibited high reproducibility for high-throughput catalyst screening and allowed several acid catalysts for the reaction to be identified. Major side products from the reactions were determined through off-line mass spectrometric detection. Er(OTf)3, the catalyst that showed optimal efficiency in the screening, was shown to be effective at promoting the cyclization reaction on a preparative scale. PMID:20666502

Reactive Fluid Flow and Applications to Diagenesis, Mineral Deposits, and Crustal Rocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rye, Danny M.; Bolton, Edward W.

2002-11-04

The objective is to initiate new: modeling of coupled fluid flow and chemical reactions of geologic environments; experimental and theoretical studies of water-rock reactions; collection and interpretation of stable isotopic and geochemical field data at many spatial scales of systems involving fluid flow and reaction in environments ranging from soils to metamorphic rocks. Theoretical modeling of coupled fluid flow and chemical reactions, involving kinetics, has been employed to understand the differences between equilibrium, steady-state, and non-steady-state behavior of the chemical evolution of open fluid-rock systems. The numerical codes developed in this project treat multi-component, finite-rate reactions combined with advective andmore » dispersive transport in multi-dimensions. The codes incorporate heat, mass, and isotopic transfer in both porous and fractured media. Experimental work has obtained the kinetic rate laws of pertinent silicate-water reactions and the rates of Sr release during chemical weathering. Ab-initio quantum mechanical techniques have been applied to obtain the kinetics and mechanisms of silicate surface reactions and isotopic exchange between water and dissolved species. Geochemical field-based studies were carried out on the Wepawaug metamorphic schist, on the Irish base-metal sediment-hosted ore system, in the Dalradian metamorphic complex in Scotland, and on weathering in the Columbia River flood basalts. The geochemical and isotopic field data, and the experimental and theoretical rate data, were used as constraints on the numerical models and to determine the length and time scales relevant to each of the field areas.« less

A chirped-pulse Fourier-transform microwave/pulsed uniform flow spectrometer. II. Performance and applications for reaction dynamics.

PubMed

Abeysekera, Chamara; Zack, Lindsay N; Park, G Barratt; Joalland, Baptiste; Oldham, James M; Prozument, Kirill; Ariyasingha, Nuwandi M; Sims, Ian R; Field, Robert W; Suits, Arthur G

2014-12-07

This second paper in a series of two reports on the performance of a new instrument for studying chemical reaction dynamics and kinetics at low temperatures. Our approach employs chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy to probe photolysis and bimolecular reaction products that are thermalized in pulsed uniform flows. Here we detail the development and testing of a new K(a)-band CP-FTMW spectrometer in combination with the pulsed flow system described in Paper I [J. M. Oldham, C. Abeysekera, B. Joalland, L. N. Zack, K. Prozument, I. R. Sims, G. B. Park, R. W. Field, and A. G. Suits, J. Chem. Phys. 141, 154202 (2014)]. This combination delivers broadband spectra with MHz resolution and allows monitoring, on the μs timescale, of the appearance of transient reaction products. Two benchmark reactive systems are used to illustrate and characterize the performance of this new apparatus: the photodissociation of SO2 at 193 nm, for which the vibrational populations of the SO product are monitored, and the reaction between CN and C2H2, for which the HCCCN product is detected in its vibrational ground state. The results show that the combination of these two well-matched techniques, which we refer to as chirped-pulse in uniform flow, also provides insight into the vibrational and rotational relaxation kinetics of the nascent reaction products. Future directions are discussed, with an emphasis on exploring the low temperature chemistry of complex polyatomic systems.

A reactive flow model with coupled reaction kinetics for detonation and combustion in non-ideal explosives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, P.J.

1996-07-01

A new reactive flow model for highly non-ideal explosives and propellants is presented. These compositions, which contain large amounts of metal, upon explosion have reaction kinetics that are characteristic of both fast detonation and slow metal combustion chemistry. A reaction model for these systems was incorporated into the two-dimensional, finite element, Lagrangian hydrodynamic code, DYNA2D. A description of how to determine the model parameters is given. The use of the model and variations are applied to AP, Al, and nitramine underwater explosive and propellant systems.

A peculiar segmented flow microfluidics for isoquercitrin biosynthesis based on coupling of reaction and separation.

PubMed

Gong, An; Gu, Shuang-Shuang; Wang, Jun; Sheng, Sheng; Wu, Fu-An

2015-10-01

A segmented flow containing a buffer-ionic liquid/solvent in a micro-channel reactor was applied to synthesize isoquercitrin by the hesperidinase-catalyzed selective hydrolysis of rutin, based on a novel system of reaction coupling with separation. Within the developed microchannel reactor with one T-shaped inlet and outlet, the maximum isoquercitrin yield (101.7 ± 2.6%) was achieved in 20 min at 30 °C and 4 μL/min. Compared with a continuous-flow reactor, reaction rate was increased 4-fold due to a glycine-sodium hydroxide:[Bmim][BF4]/glycerol triacetate (1:1, v/v) system that formed a slug flow in microchannel and significantly increased mass transfer rates. The mass transfer coefficient significantly increased and exhibited a linear relationship with the flow rate. Hesperidinase could be efficiently reused at least 5 times, without losing any activity. The bonding mechanism and secondary structure of hesperidinase indicated that hesperidinase had a greater affinity to rutin at a production rate of 4 μL/min in this segmented flow microreactor. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reaction front barriers in time aperiodic fluid flows

NASA Astrophysics Data System (ADS)

Locke, Rory; Mitchell, Kevin

2016-11-01

Many chemical and biological systems can be characterized by the propagation of a front that separates different phases or species. One approach to formalizing a general theory is to apply frameworks developed in nonlinear dynamics. It has been shown that invariant manifolds form barriers to passive transport in time-dependent or time-periodic fluid flows. More recently, analogous manifolds termed burning- invariant-manifolds (BIMs), have been shown to form one-sided barriers to reaction fronts in advection-reaction-diffusion (ARD) systems. To model more realistic time-aperiodic systems, recent theoretical work has suggested that similar one-sided barriers, termed burning Lagrangian coherent structures (bLCSs), exist for fluid velocity data prescribed over a finite time interval. In this presentation, we use a stochastic "wind" to generate time dependence in a double-vortex channel flow and demonstrate the (locally) most attracting or repelling curves are the bLCSs.

Dichotomous-noise-induced pattern formation in a reaction-diffusion system

NASA Astrophysics Data System (ADS)

Das, Debojyoti; Ray, Deb Shankar

2013-06-01

We consider a generic reaction-diffusion system in which one of the parameters is subjected to dichotomous noise by controlling the flow of one of the reacting species in a continuous-flow-stirred-tank reactor (CSTR) -membrane reactor. The linear stability analysis in an extended phase space is carried out by invoking Furutzu-Novikov procedure for exponentially correlated multiplicative noise to derive the instability condition in the plane of the noise parameters (correlation time and strength of the noise). We demonstrate that depending on the correlation time an optimal strength of noise governs the self-organization. Our theoretical analysis is corroborated by numerical simulations on pattern formation in a chlorine-dioxide-iodine-malonic acid reaction-diffusion system.

Reaction front dynamics under shear flow for arbitrary Damköhler numbers

NASA Astrophysics Data System (ADS)

Bandopadhyay, Aditya; Méheust, Yves; Le Borgne, Tanguy

2016-04-01

Reaction fronts where two reactive fluids displace one another play an important role in a range of applications, including contaminant plume transport and reaction, soil and aquifer remediation, CO2 sequestration, geothermal dipoles and the development of hotspots of reaction in mixing zones. The background flow induces enhanced mixing, and therefore reaction, through interfacial shear. Hence the coupling of fluid flow with chemical reactions is pivotal in understanding and quantifying effective reaction kinetics in reaction fronts. While this problem has been addressed in the limit of fast reactions (e.g. de Simoni 2005, Le Borgne 2014), in natural systems reactions can span a large range of Damköhler numbers since their characteristic reaction times vary over a large range of typical values. Here the coupling of shear flow and reversible chemical reactions is studied for a reaction front with initially separated reactants at arbitrary Damköhler numbers. Approximate analytical expressions for the global production rate are derived based on a reactive lamella approach. We observe three distinct regimes, each of them characterized by different scalings of the global production rate and width of the reactive zone. We describe the dependency of these scalings and the associated characteristic transition times as a function of Damköhler and Péclet numbers. These results are validated against 2D numerical simulations. The study is expected to shed light on the inherently complex cases of reactive mixing with varying reaction rates under the influence of an imposed flow. de Simoni et al. (2005) Water Resour. Res., 41, W11410 Le Borgne et al. (2014) GRL, 41(22), 7898

Multicomponent, flow diazotization/Mizoroki-Heck coupling protocol: dispelling myths about working with diazonium salts.

PubMed

Nalivela, Kumara S; Tilley, Michael; McGuire, Michael A; Organ, Michael G

2014-05-26

A single pass flow diazotization/Mizoroki-Heck protocol has been developed for the production of cinnimoyl and styryl products. The factors that govern aryl diazonium salt stability have been examined in detail leading to the development of a MeOH/DMF co-solvent system in which the diazonium salts can be generated in the presence of all other reaction components and then coupled selectively to give the desired products. Finally the key role of the reaction quench for flow reactions has been demonstrated. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Scalable synthesis of sequence-defined, unimolecular macromolecules by Flow-IEG

PubMed Central

Leibfarth, Frank A.; Johnson, Jeremiah A.; Jamison, Timothy F.

2015-01-01

We report a semiautomated synthesis of sequence and architecturally defined, unimolecular macromolecules through a marriage of multistep flow synthesis and iterative exponential growth (Flow-IEG). The Flow-IEG system performs three reactions and an in-line purification in a total residence time of under 10 min, effectively doubling the molecular weight of an oligomeric species in an uninterrupted reaction sequence. Further iterations using the Flow-IEG system enable an exponential increase in molecular weight. Incorporating a variety of monomer structures and branching units provides control over polymer sequence and architecture. The synthesis of a uniform macromolecule with a molecular weight of 4,023 g/mol is demonstrated. The user-friendly nature, scalability, and modularity of Flow-IEG provide a general strategy for the automated synthesis of sequence-defined, unimolecular macromolecules. Flow-IEG is thus an enabling tool for theory validation, structure–property studies, and advanced applications in biotechnology and materials science. PMID:26269573

Amine-Functionalized Sugarcane Bagasse: A Renewable Catalyst for Efficient Continuous Flow Knoevenagel Condensation Reaction at Room Temperature.

PubMed

Qiao, Yanhui; Teng, Junjiang; Wang, Shuangfei; Ma, Hao

2017-12-24

A biomass-based catalyst with amine groups (-NH₂), viz., amine-functionalized sugarcane bagasse (SCB-NH₂), was prepared through the amination of sugarcane bagasse (SCB) in a two-step process. The physicochemical properties of the catalyst were characterized through FT-IR, elemental analysis, XRD, TG, and SEM-EDX techniques, which confirmed the -NH₂ group was grafted onto SCB successfully. The catalytic performance of SCB-NH₂ in Knoevenagel condensation reaction was tested in the batch and continuous flow reactions. Significantly, it was found that the catalytic performance of SCB-NH₂ is better in flow system than that in batch system. Moreover, the SCB-NH₂ presented an excellent catalytic activity and stability at the high flow rate. When the flow rate is at the 1.5 mL/min, no obvious deactivation was observed and the product yield and selectivity are more than 97% and 99% after 80 h of continuous reaction time, respectively. After the recovery of solvent from the resulting solution, a white solid was obtained as a target product. As a result, the SCB-NH₂ is a promising catalyst for the synthesis of fine chemicals by Knoevenagel condensation reaction in large scale, and the modification of the renewable SCB with -NH₂ group is a potential avenue for the preparation of amine-functionalized catalytic materials in industry.

Infrared Chemiluminescence Studies of Ion-Molecule Reactions in a Flowing Afterglow.

DTIC Science & Technology

1982-01-01

reaction rate constants and branching ratios have been addressed in drift tubes and flow drift systems, and the translational energy distribution of atomic...composed of about 40 thin cylindrical sections of flow tube , separated by mylar spacers and connected by precision resistors. In the region of LIF... tube radius (Albritton, 1967). For proper operation of a drift tube , ionic species of only one polarity can be present. Efficient separation of

An accessible visible-light actinometer for the determination of photon flux and optical pathlength in flow photo microreactors.

PubMed

Roibu, Anca; Fransen, Senne; Leblebici, M Enis; Meir, Glen; Van Gerven, Tom; Kuhn, Simon

2018-04-03

Coupling photochemistry with flow microreactors enables novel synthesis strategies with higher efficiencies compared to batch systems. Improving the reproducibility and understanding of the photochemical reaction mechanisms requires quantitative tools such as chemical actinometry. However, the choice of actinometric systems which can be applied in microreactors is limited, due to their short optical pathlength in combination with a large received photon flux. Furthermore, actinometers for the characterization of reactions driven by visible light between 500 and 600 nm (e.g. photosensitized oxidations) are largely missing. In this paper, we propose a new visible-light actinometer which can be applied in flow microreactors between 480 and 620 nm. This actinometric system is based on the photoisomerization reaction of a diarylethene derivative from its closed to the open form. The experimental protocol for actinometric measurements is facile and characterized by excellent reproducibility and we also present an analytical estimation to calculate the photon flux. Furthermore, we propose an experimental methodology to determine the average pathlength in microreactors using actinometric measurements. In the context of a growing research interest on using flow microreactors for photochemical reactions, the proposed visible-light actinometer facilitates the determination of the received photon flux and average pathlength in confined geometries.

Small organic molecule based flow battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huskinson, Brian; Marshak, Michael; Aziz, Michael J.

The invention provides an electrochemical cell based on a new chemistry for a flow battery for large scale, e.g., gridscale, electrical energy storage. Electrical energy is stored chemically at an electrochemical electrode by the protonation of small organic molecules called quinones to hydroquinones. The proton is provided by a complementary electrochemical reaction at the other electrode. These reactions are reversed to deliver electrical energy. A flow battery based on this concept can operate as a closed system. The flow battery architecture has scaling advantages over solid electrode batteries for large scale energy storage.

Biochemical analysis with microfluidic systems.

PubMed

Bilitewski, Ursula; Genrich, Meike; Kadow, Sabine; Mersal, Gaber

2003-10-01

Microfluidic systems are capillary networks of varying complexity fabricated originally in silicon, but nowadays in glass and polymeric substrates. Flow of liquid is mainly controlled by use of electroosmotic effects, i.e. application of electric fields, in addition to pressurized flow, i.e. application of pressure or vacuum. Because electroosmotic flow rates depend on the charge densities on the walls of capillaries, they are influenced by substrate material, fabrication processes, surface pretreatment procedures, and buffer additives. Microfluidic systems combine the properties of capillary electrophoretic systems and flow-through analytical systems, and thus biochemical analytical assays have been developed utilizing and integrating both aspects. Proteins, peptides, and nucleic acids can be separated because of their different electrophoretic mobility; detection is achieved with fluorescence detectors. For protein analysis, in particular, interfaces between microfluidic chips and mass spectrometers were developed. Further levels of integration of required sample-treatment steps were achieved by integration of protein digestion by immobilized trypsin and amplification of nucleic acids by the polymerase chain reaction. Kinetic constants of enzyme reactions were determined by adjusting different degrees of dilution of enzyme substrates or inhibitors within a single chip utilizing mainly the properties of controlled dosing and mixing liquids within a chip. For analysis of kinase reactions, however, a combination of a reaction step (enzyme with substrate and inhibitor) and a separation step (enzyme substrate and reaction product) was required. Microfluidic chips also enable separation of analytes from sample matrix constituents, which can interfere with quantitative determination, if they have different electrophoretic mobilities. In addition to analysis of nucleic acids and enzymes, immunoassays are the third group of analytical assays performed in microfluidic chips. They utilize either affinity capillary electrophoresis as a homogeneous assay format, or immobilized antigens or antibodies in heterogeneous assays with serial supply of reagents and washing solutions.

A Stopped-Flow Apparatus with Light-Scattering Detection and Its Application to Biochemical Reactions

PubMed Central

Riesner, Detlev; Buenemann, Hans

1973-01-01

A stopped-flow apparatus utilizing light-scattering for following the progress of a reaction is described. The method is applicable to all reactions that result in a significant change of the average molecular weight. It was possible due to several modifications of a conventional stopped-flow system to obtain a sensitivity comparable to that of commercial instruments for static light-scattering measurements. Experiments on three reactions are reported: association and dissociation of mercury ligands with DNA, dissociation of the dimers of DNA-dependent RNA polymerase, and complex formation of tRNASer (yeast) with the cognate aminoacyl-tRNA synthetase. The changes in the intensities of the scattered light are calculated and compared with the measured amplitudes. PMID:4577138

Ionic Liquid Droplet Microreactor for Catalysis Reactions Not at Equilibrium.

PubMed

Zhang, Ming; Ettelaie, Rammile; Yan, Tao; Zhang, Suojiang; Cheng, Fangqin; Binks, Bernard P; Yang, Hengquan

2017-12-06

We develop a novel strategy to more effectively and controllably process continuous enzymatic or homogeneous catalysis reactions based on nonaqueous Pickering emulsions. A key element of this strategy is "bottom-up" construction of a macroscale continuous flow reaction system through packing catalyst-containing micron-sized ionic liquid (IL) droplet in oil in a column reactor. Due to the continuous influx of reactants into the droplet microreactors and the continuous release of products from the droplet microreactors, catalysis reactions in such a system can take place without limitations arising from establishment of the reaction equilibrium and catalyst separation, inherent in conventional batch reactions. As proof of the concept, enzymatic enantioselective trans-esterification and CuI-catalyzed cycloaddition reactions using this IL droplet-based flow system both exhibit 8 to 25-fold enhancement in catalysis efficiency compared to their batch counterparts, and a durability of at least 4000 h for the enantioselective trans-esterification of 1-phenylethyl alcohol, otherwise unattainable in their batch counterparts. We further establish a theoretical model for such a catalysis system working under nonequilibrium conditions, which not only supports the experimental results but also helps to predict reaction progress at a microscale level. Being operationally simple, efficient, and adaptive, this strategy provides an unprecedented platform for practical applications of enzymes and homogeneous catalysts even at a controllable level.

GCKP84-general chemical kinetics code for gas-phase flow and batch processes including heat transfer effects

NASA Technical Reports Server (NTRS)

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

1984-01-01

A general chemical kinetics code is described for complex, homogeneous ideal gas reactions in any chemical system. The main features of the GCKP84 code are flexibility, convenience, and speed of computation for many different reaction conditions. The code, which replaces the GCKP code published previously, solves numerically the differential equations for complex reaction in a batch system or one dimensional inviscid flow. It also solves numerically the nonlinear algebraic equations describing the well stirred reactor. A new state of the art numerical integration method is used for greatly increased speed in handling systems of stiff differential equations. The theory and the computer program, including details of input preparation and a guide to using the code are given.

Marginal states in a cubic autocatalytic reaction

NASA Astrophysics Data System (ADS)

Das, Debojyoti; Ghosh, Pushpita; Ray, Deb Shankar

2011-09-01

Marginal steady state belongs to a special class of states in nonlinear dynamics. To realize this state we consider a cubic autocatalytic reaction A + 2B → 3B in a continuous-stirred-tank-reactor, where the flow rate of the reactant A can be controlled to manipulate the dynamical behavior of the open system. We demonstrate that when the flow rate is weakly noisy the autocatalytic reaction admits of a steady state which is marginal in nature and is surrounded by infinite number of periodic trajectories. When the uncatalyzed reaction A → B is included in the reaction scheme, there exists a marginal steady state which is a critical state corresponding to the point of transition between the flow branch and the equilibrium branch, similar to gas-liquid critical point of transition. This state loses its stability in the weak noise limit.

The in situ generation and reactive quench of diazonium compounds in the synthesis of azo compounds in microreactors.

PubMed

Akwi, Faith M; Watts, Paul

2016-01-01

In this paper, a micro-fluidic optimized process for the continuous flow synthesis of azo compounds is presented. The continuous flow synthesis of Sudan II azo dye was used as a model reaction for the study. At found optimal azo coupling reaction temperature and pH an investigation of the optimum flow rates of the reactants for the diazotization and azo coupling reactions in Little Things Factory-MS microreactors was performed. A conversion of 98% was achieved in approximately 2.4 minutes and a small library of azo compounds was thus generated under these reaction conditions from couplers with aminated or hydroxylated aromatic systems. The scaled up synthesis of these compounds in PTFE tubing (i.d. 1.5 mm) was also investigated, where good reaction conversions ranging between 66-91% were attained.

CFD Simulation of the Space Shuttle Launch Vehicle with Booster Separation Motor and Reaction Control System Plumes

NASA Technical Reports Server (NTRS)

Gea, L. M.; Vicker, D.

2006-01-01

The primary objective of this paper is to demonstrate the capability of computational fluid dynamics (CFD) to simulate a very complicated flow field encountered during the space shuttle ascent. The flow field features nozzle plumes from booster separation motor (BSM) and reaction control system (RCS) jets with a supersonic incoming cross flow at speed of Mach 4. The overset Navier-Stokes code OVERFLOW, was used to simulate the flow field surrounding the entire space shuttle launch vehicle (SSLV) with high geometric fidelity. The variable gamma option was chosen due to the high temperature nature of nozzle flows and different plume species. CFD predicted Mach contours are in good agreement with the schlieren photos from wind tunnel test. Flow fields are discussed in detail and the results are used to support the debris analysis for the space shuttle Return To Flight (RTF) task.

Material-Efficient Microfluidic Platform for Exploratory Studies of Visible-Light Photoredox Catalysis.

PubMed

Coley, Connor W; Abolhasani, Milad; Lin, Hongkun; Jensen, Klavs F

2017-08-07

We present an automated microfluidic platform for in-flow studies of visible-light photoredox catalysis in liquid or gas-liquid reactions at the 15 μL scale. An oscillatory flow strategy enables a flexible residence time while preserving the mixing and heat transfer advantages of flow systems. The adjustable photon flux made possible with the platform is characterized using actinometry. Case studies of oxidative hydroxylation of phenylboronic acids and dimerization of thiophenol demonstrate the capabilities and advantages of the system. Reaction conditions identified through droplet screening translate directly to continuous synthesis with minor platform modifications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Systems Approach towards an Intelligent and Self-Controlling Platform for Integrated Continuous Reaction Sequences**

PubMed Central

Ingham, Richard J; Battilocchio, Claudio; Fitzpatrick, Daniel E; Sliwinski, Eric; Hawkins, Joel M; Ley, Steven V

2015-01-01

Performing reactions in flow can offer major advantages over batch methods. However, laboratory flow chemistry processes are currently often limited to single steps or short sequences due to the complexity involved with operating a multi-step process. Using new modular components for downstream processing, coupled with control technologies, more advanced multi-step flow sequences can be realized. These tools are applied to the synthesis of 2-aminoadamantane-2-carboxylic acid. A system comprising three chemistry steps and three workup steps was developed, having sufficient autonomy and self-regulation to be managed by a single operator. PMID:25377747

Space shuttle orbiter rear mounted reaction control system jet interaction study. [hypersonic wind tunnel tests

NASA Technical Reports Server (NTRS)

Rausch, J. R.

1977-01-01

The effect of interaction between the reaction control system (RCS) jets and the flow over the space shuttle orbiter in the atmosphere was investigated in the NASA Langley 31-inch continuous flow hypersonic tunnel at a nominal Mach number of 10.3 and in the AEDC continuous flow hypersonic tunnel B at a nominal Mach number of 6, using 0.01 and .0125 scale force models with aft RCS nozzles mounted both on the model and on the sting of the force model balance. The data show that RCS nozzle exit momentum ratio is the primary correlating parameter for effects where the plume impinges on an adjacent surface and mass flow ratio is the parameter when the plume interaction is primarily with the external stream. An analytic model of aft mounted RCS units was developed in which the total reaction control moments are the sum of thrust, impingement, interaction, and cross-coupling terms.

Finite-time barriers to reaction front propagation

NASA Astrophysics Data System (ADS)

Locke, Rory; Mahoney, John; Mitchell, Kevin

2015-11-01

Front propagation in advection-reaction-diffusion systems gives rise to rich geometric patterns. It has been shown for time-independent and time-periodic fluid flows that invariant manifolds, termed burning invariant manifolds (BIMs), serve as one-sided dynamical barriers to the propagation of reaction front. More recently, theoretical work has suggested that one-sided barriers, termed burning Lagrangian Coherent structures (bLCSs), exist for fluid velocity data prescribed over a finite time interval, with no assumption on the time-dependence of the flow. In this presentation, we use a time-varying fluid ``wind'' in a double-vortex channel flow to demonstrate that bLCSs form the (locally) most attracting or repelling fronts.

A flow reactor setup for photochemistry of biphasic gas/liquid reactions

PubMed Central

Schachtner, Josef; Bayer, Patrick

2016-01-01

Summary A home-built microreactor system for light-mediated biphasic gas/liquid reactions was assembled from simple commercial components. This paper describes in full detail the nature and function of the required building elements, the assembly of parts, and the tuning and interdependencies of the most important reactor and reaction parameters. Unlike many commercial thin-film and microchannel reactors, the described set-up operates residence times of up to 30 min which cover the typical rates of many organic reactions. The tubular microreactor was successfully applied to the photooxygenation of hydrocarbons (Schenck ene reaction). Major emphasis was laid on the realization of a constant and highly reproducible gas/liquid slug flow and the effective illumination by an appropriate light source. The optimized set of conditions enabled the shortening of reaction times by more than 99% with equal chemoselectivities. The modular home-made flow reactor can serve as a prototype model for the continuous operation of various other reactions at light/liquid/gas interfaces in student, research, and industrial laboratories. PMID:27829887

Invariantly propagating dissolution fingers in finite-width systems

NASA Astrophysics Data System (ADS)

Dutka, Filip; Szymczak, Piotr

2016-04-01

Dissolution fingers are formed in porous medium due to positive feedback between transport of reactant and chemical reactions [1-4]. We investigate two-dimensional semi-infinite systems, with constant width W in one direction. In numerical simulations we solve the Darcy flow problem combined with advection-dispersion-reaction equation for the solute transport to track the evolving shapes of the fingers and concentration of reactant in the system. We find the stationary, invariantly propagating finger shapes for different widths of the system, flow and reaction rates. Shape of the reaction front, turns out to be controlled by two dimensionless numbers - the (width-based) Péclet number PeW = vW/Dφ0 and Damköhler number DaW = ksW/v, where k is the reaction rate, s - specific reactive surface area, v - characteristic flow rate, D - diffusion coefficient of the solute, and φ0 - initial porosity of the rock matrix. Depending on PeW and DaW stationary shapes can be divided into seperate classes, e.g. parabolic-like and needle-like structures, which can be inferred from theoretical predictions. In addition we determine velocity of propagating fingers in time and concentration of reagent in the system. Our simulations are compared with natural forms (solution pipes). P. Ortoleva, J. Chadam, E. Merino, and A. Sen, Geochemical self-organization II: the reactive-infiltration instability, Am. J. Sci, 287, 1008-1040 (1987). M. L. Hoefner, and H. S. Fogler. Pore evolution and channel formation during flow and reaction in porous media, AIChE Journal 34, 45-54 (1988). C. E. Cohen, D. Ding, M. Quintard, and B. Bazin, From pore scale to wellbore scale: impact of geometry on wormhole growth in carbonate acidization, Chemical Engineering Science 63, 3088-3099 (2008). P. Szymczak and A. J. C. Ladd, Reactive-infiltration nstabilities in rocks. Part II: Dissolution of a porous matrix, J. Fluid Mech. 738, 591-630 (2014).

A novel simulation theory and model system for multi-field coupling pipe-flow system

NASA Astrophysics Data System (ADS)

Chen, Yang; Jiang, Fan; Cai, Guobiao; Xu, Xu

2017-09-01

Due to the lack of a theoretical basis for multi-field coupling in many system-level models, a novel set of system-level basic equations for flow/heat transfer/combustion coupling is put forward. Then a finite volume model of quasi-1D transient flow field for multi-species compressible variable-cross-section pipe flow is established by discretising the basic equations on spatially staggered grids. Combining with the 2D axisymmetric model for pipe-wall temperature field and specific chemical reaction mechanisms, a finite volume model system is established; a set of specific calculation methods suitable for multi-field coupling system-level research is structured for various parameters in this model; specific modularisation simulation models can be further derived in accordance with specific structures of various typical components in a liquid propulsion system. This novel system can also be used to derive two sub-systems: a flow/heat transfer two-field coupling pipe-flow model system without chemical reaction and species diffusion; and a chemical equilibrium thermodynamic calculation-based multi-field coupling system. The applicability and accuracy of two sub-systems have been verified through a series of dynamic modelling and simulations in earlier studies. The validity of this system is verified in an air-hydrogen combustion sample system. The basic equations and the model system provide a unified universal theory and numerical system for modelling and simulation and even virtual testing of various pipeline systems.

Command module/service module reaction control subsystem assessment

NASA Technical Reports Server (NTRS)

Weary, D. P.

1971-01-01

Detailed review of component failure histories, qualification adequacy, manufacturing flow, checkout requirements and flow, ground support equipment interfaces, subsystem interface verification, protective devices, and component design did not reveal major weaknesses in the command service module (CSM) reaction control system (RCS). No changes to the CSM RCS were recommended. The assessment reaffirmed the adequacy of the CSM RCS for future Apollo missions.

Highly effective synthesis of a cobalt(ii) metal-organic coordination polymer by using continuous flow chemistry.

PubMed

Gong, Chunhua; Zhang, Junyong; Zeng, Xianghua; Xie, Jingli

2016-12-20

The coordination polymer [Co 2 L 4 (H 2 O) 2 ]·CH 3 CN·H 2 O (HL = (E)-2-[2-(4-chlorophenyl)vinyl]-8-hydroxyquinoline) has been achieved with 95% yield by using an Asia flow synthesis system (chip reactor). Compared with the conventional batch-type methods such as diffusion, reflux and solvothermal reactions, higher yielding reactions carried out in a flow reactor have demonstrated that this technique is a powerful strategy to obtain coordination compounds.

Effect of reaction control system jet-flow field interactions on a 0.015 scale model space shuttle orbiter aerodynamic characteristics

NASA Technical Reports Server (NTRS)

Monta, W. J.; Rausch, J. R.

1973-01-01

The effects of the reaction control system (RCS) jet-flow field interactions on the space shuttle orbiter system during entry are discussed. The primary objective of the test program was to obtain data for the shuttle orbiter configuration to determine control amplification factors resulting from jet interaction between the RCS plumes and the external flow over the vehicle. A secondary objective was to provide data for comparison and improvement of analytic jet interaction prediction techniques. The test program was divided into two phases; (1) force and moment measurements were made with and without RCS blowing, investigating environment parameters (R sub e, Alpha, Beta), RCS plume parameters (Jet pressure ratio, momentum ratio and thrust level), and geometry parameters (RCS pod locations) on the orbiter model, (2) oil flow visualization tests were conducted on a dummy balance at the end of the test.

Highly simplified lateral flow-based nucleic acid sample preparation and passive fluid flow control

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cary, Robert E.

2015-12-08

Highly simplified lateral flow chromatographic nucleic acid sample preparation methods, devices, and integrated systems are provided for the efficient concentration of trace samples and the removal of nucleic acid amplification inhibitors. Methods for capturing and reducing inhibitors of nucleic acid amplification reactions, such as humic acid, using polyvinylpyrrolidone treated elements of the lateral flow device are also provided. Further provided are passive fluid control methods and systems for use in lateral flow assays.

Highly simplified lateral flow-based nucleic acid sample preparation and passive fluid flow control

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cary, Robert B.

Highly simplified lateral flow chromatographic nucleic acid sample preparation methods, devices, and integrated systems are provided for the efficient concentration of trace samples and the removal of nucleic acid amplification inhibitors. Methods for capturing and reducing inhibitors of nucleic acid amplification reactions, such as humic acid, using polyvinylpyrrolidone treated elements of the lateral flow device are also provided. Further provided are passive fluid control methods and systems for use in lateral flow assays.

Evolution of engine cycles for STOVL propulsion concepts

NASA Technical Reports Server (NTRS)

Bucknell, R. L.; Frazier, R. H.; Giulianetti, D. J.

1990-01-01

Short Take-off, Vertical Landing (STOVL) demonstrator concepts using a common ATF engine core are discussed. These concepts include a separate fan and core flow engine cycle, mixed flow STOVL cycles, separate flow cycles convertible to mixed flow, and reaction control system engine air bleed. STOVL propulsion controls are discussed.

The in situ generation and reactive quench of diazonium compounds in the synthesis of azo compounds in microreactors

PubMed Central

Akwi, Faith M

2016-01-01

Summary In this paper, a micro-fluidic optimized process for the continuous flow synthesis of azo compounds is presented. The continuous flow synthesis of Sudan II azo dye was used as a model reaction for the study. At found optimal azo coupling reaction temperature and pH an investigation of the optimum flow rates of the reactants for the diazotization and azo coupling reactions in Little Things Factory-MS microreactors was performed. A conversion of 98% was achieved in approximately 2.4 minutes and a small library of azo compounds was thus generated under these reaction conditions from couplers with aminated or hydroxylated aromatic systems. The scaled up synthesis of these compounds in PTFE tubing (i.d. 1.5 mm) was also investigated, where good reaction conversions ranging between 66–91% were attained. PMID:27829903

Determination of dipyrone in pharmaceutical preparations based on the chemiluminescent reaction of the quinolinic hydrazide-H2O2-vanadium(IV) system and flow-injection analysis.

PubMed

Pradana Pérez, Juan A; Durand Alegría, Jesús S; Hernando, Pilar Fernández; Sierra, Adolfo Narros

2012-01-01

A rapid, economic and sensitive chemiluminescent method involving flow-injection analysis was developed for the determination of dipyrone in pharmaceutical preparations. The method is based on the chemiluminescent reaction between quinolinic hydrazide and hydrogen peroxide in a strongly alkaline medium, in which vanadium(IV) acts as a catalyst. Principal chemical and physical variables involved in the flow-injection system were optimized using a modified simplex method. The variations in the quantum yield observed when dipyrone was present in the reaction medium were used to determine the concentration of this compound. The proposed method requires no preconcentration steps and reliably quantifies dipyrone over the linear range 1-50 µg/mL. In addition, a sample throughput of 85 samples/h is possible. Copyright © 2011 John Wiley & Sons, Ltd.

Functionalized Anodic Aluminum Oxide Membrane–Electrode System for Enzyme Immobilization

PubMed Central

2015-01-01

A nanoporous membrane system with directed flow carrying reagents to sequentially attached enzymes to mimic nature’s enzyme complex system was demonstrated. Genetically modified glycosylation enzyme, OleD Loki variant, was immobilized onto nanometer-scale electrodes at the pore entrances/exits of anodic aluminum oxide membranes through His6-tag affinity binding. The enzyme activity was assessed in two reactions—a one-step “reverse” sugar nucleotide formation reaction (UDP-Glc) and a two-step sequential sugar nucleotide formation and sugar nucleotide-based glycosylation reaction. For the one-step reaction, enzyme specific activity of 6–20 min–1 on membrane supports was seen to be comparable to solution enzyme specific activity of 10 min–1. UDP-Glc production efficiencies as high as 98% were observed at a flow rate of 0.5 mL/min, at which the substrate residence time over the electrode length down pore entrances was matched to the enzyme activity rate. This flow geometry also prevented an unwanted secondary product hydrolysis reaction, as observed in the test homogeneous solution. Enzyme utilization increased by a factor of 280 compared to test homogeneous conditions due to the continuous flow of fresh substrate over the enzyme. To mimic enzyme complex systems, a two-step sequential reaction using OleD Loki enzyme was performed at membrane pore entrances then exits. After UDP-Glc formation at the entrance electrode, aglycon 4-methylumbelliferone was supplied at the exit face of the reactor, affording overall 80% glycosylation efficiency. The membrane platform showed the ability to be regenerated with purified enzyme as well as directly from expression crude, thus demonstrating a single-step immobilization and purification process. PMID:25025628

The Eschenmoser coupling reaction under continuous-flow conditions

PubMed Central

Singh, Sukhdeep; Köhler, J Michael; Schober, Andreas

2011-01-01

Summary The Eschenmoser coupling is a useful carbon–carbon bond forming reaction which has been used in various different synthesis strategies. The reaction proceeds smoothly if S-alkylated ternary thioamides or thiolactames are used. In the case of S-alkylated secondary thioamides or thiolactames, the Eschenmoser coupling needs prolonged reaction times and elevated temperatures to deliver valuable yields. We have used a flow chemistry system to promote the Eschenmoser coupling under enhanced reaction conditions in order to convert the demanding precursors such as S-alkylated secondary thioamides and thiolactames in an efficient way. Under pressurized reaction conditions at about 220 °C, the desired Eschenmoser coupling products were obtained within 70 s residence time. The reaction kinetics was investigated and 15 examples of different building block combinations are given. PMID:21915222

Karst-on-a-chip: microfluidic studies of dissolution of a gypsum fracture

NASA Astrophysics Data System (ADS)

Szymczak, Piotr; Dutka, Filip; Osselin, Florian

2017-04-01

Dissolution of fractured and porous media introduces a positive feedback between fluid transport and chemical reactions at mineral surfaces leading to self-focusing of the flow in pronounced wormhole-like channels [1,2]. We study the flow-induced dissolution in a simple microfluidic setup, with a gypsum block inserted in between two polycarbonate plates, which is the simplest model of a fracture [3]. This gives us a unique opportunity to observe the evolution of the dissolution patterns in-situ and in real-time. By changing the flow rate and the aperture of the fracture we can scan a relatively wide range of Peclet and Damkohler numbers, characterizing the relative magnitude of advection, diffusion and reaction in the system. Additionally, as the aperture is increased, a transition is observed between the fractal and regular dissolution patterns. For small gaps, the patterns are ramified fractals. For larger gaps, the dissolution fingers are found to have regular forms of two different kinds: either linear (for high flow rates) or parabolic (for lower flow rates). The experiments are supplemented with numerical simulations and analytical modeling which allow for a better understanding of evolving flow patterns. In particular, we find the shapes and propagation velocities of dominant fingers for different widths of the system, flow rates and reaction rates. Finally, we comment on the link between the experimentally observed patterns and the natural karst systems - both cave conduits and epikarst solution pipes. [1] Hoefner, M. L. and Fogler, H. S. Pore evolution and channel formation during flow and reaction in porous media. AIChE J. 34, 45-54, 1988 [2] P. Szymczak, A. J. C. Ladd, Wormhole formation in dissolving fractures, J. Geophys. Res., 114, B06203, 2009 [3] F. Osselin, P. Kondratiuk, A Budek, O. Cybulski, P. Garstecki, P. Szymczak Microfluidic observation of the onset of reactive infiltration instability in an analog fracture, Geophys. Res. Lett., 43, 6907-6915, 2016

User's Guide of TOUGH2-EGS. A Coupled Geomechanical and Reactive Geochemical Simulator for Fluid and Heat Flow in Enhanced Geothermal Systems Version 1.0

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fakcharoenphol, Perapon; Xiong, Yi; Hu, Litang

TOUGH2-EGS is a numerical simulation program coupling geomechanics and chemical reactions for fluid and heat flows in porous media and fractured reservoirs of enhanced geothermal systems. The simulator includes the fully-coupled geomechanical (THM) module, the fully-coupled geochemical (THC) module, and the sequentially coupled reactive geochemistry (THMC) module. The fully-coupled flow-geomechanics model is developed from the linear elastic theory for the thermo-poro-elastic system and is formulated with the mean normal stress as well as pore pressure and temperature. The chemical reaction is sequentially coupled after solution of flow equations, which provides the flow velocity and phase saturation for the solute transportmore » calculation at each time step. In addition, reservoir rock properties, such as porosity and permeability, are subjected to change due to rock deformation and chemical reactions. The relationships between rock properties and geomechanical and chemical effects from poro-elasticity theories and empirical correlations are incorporated into the simulator. This report provides the user with detailed information on both mathematical models and instructions for using TOUGH2-EGS for THM, THC or THMC simulations. The mathematical models include the fluid and heat flow equations, geomechanical equation, reactive geochemistry equations, and discretization methods. Although TOUGH2-EGS has the capability for simulating fluid and heat flows coupled with both geomechanical and chemical effects, it is up to the users to select the specific coupling process, such as THM, THC, or THMC in a simulation. There are several example problems illustrating the applications of this program. These example problems are described in details and their input data are presented. The results demonstrate that this program can be used for field-scale geothermal reservoir simulation with fluid and heat flow, geomechanical effect, and chemical reaction in porous and fractured media.« less

Microwave plasma generation of hydrogen atoms for rocket propulsion

NASA Technical Reports Server (NTRS)

Chapman, R.; Filpus, J.; Morin, T.; Snellenberger, R.; Asmussen, J.; Hawley, M.; Kerber, R.

1981-01-01

A flow microwave plasma reaction system is used to study the conversion of hydrogen to hydrogen atoms as a function of pressure, power density, cavity tuning, cavity mode, and time in the plasma zone. Hydrogen atom concentration is measured down-stream from the plasma by NOCl titration. Extensive modeling of the plasma and recombination zones is performed with the plasma zone treated as a backmix reaction system and the recombination zone treated as a plug flow. The thermodynamics and kinetics of the recombination process are examined in detail to provide an understanding of the conversion of recombination energy to gas kinetic energy. It is found that cavity tuning, discharge stability, and optimum power coupling are critically dependent on the system pressure, but nearly independent of the flow rate.

Waterhammer Modeling for the Ares I Upper Stage Reaction Control System Cold Flow Development Test Article

NASA Technical Reports Server (NTRS)

Williams, Jonathan H.

2010-01-01

The Upper Stage Reaction Control System provides three-axis attitude control for the Ares I launch vehicle during active Upper Stage flight. The system design must accommodate rapid thruster firing to maintain the proper launch trajectory and thus allow for the possibility to pulse multiple thrusters simultaneously. Rapid thruster valve closure creates an increase in static pressure, known as waterhammer, which propagates throughout the propellant system at pressures exceeding nominal design values. A series of development tests conducted in the fall of 2009 at Marshall Space Flight Center were performed using a water-flow test article to better understand fluid performance characteristics of the Upper Stage Reaction Control System. A subset of the tests examined waterhammer along with the subsequent pressure and frequency response in the flight-representative system and provided data to anchor numerical models. This thesis presents a comparison of waterhammer test results with numerical model and analytical results. An overview of the flight system, test article, modeling and analysis are also provided.

Waterhammer modeling for the Ares I Upper Stage Reaction Control System cold flow development test article

NASA Astrophysics Data System (ADS)

Williams, Jonathan Hunter

The Upper Stage Reaction Control System provides in-flight three-axis attitude control for the Ares I Upper Stage. The system design must accommodate rapid thruster firing to maintain proper launch trajectory and thus allow for the possibility to pulse multiple thrusters simultaneously. Rapid thruster valve closure creates an increase in static pressure, known as waterhammer, which propagates throughout the propellant system at pressures exceeding nominal design values. A series of development tests conducted at Marshall Space Flight Center in 2009 were performed using a water-flow test article to better understand fluid characteristics of the Upper Stage Reaction Control System. A subset of the tests examined the waterhammer pressure and frequency response in the flight-representative system and provided data to anchor numerical models. This thesis presents a comparison of waterhammer test results with numerical model and analytical results. An overview of the flight system, test article, modeling and analysis are also provided.

A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

NASA Technical Reports Server (NTRS)

Wine, P. H.; Semmes, D. H.; Ravishankara, A. R.

1981-01-01

Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

Experimental Reacting Hydrogen Shear Layer Data at High Subsonic Mach Number

NASA Technical Reports Server (NTRS)

Chang, C. T.; Marek, C. J.; Wey, C.; Wey, C. C.

1996-01-01

The flow in a planar shear layer of hydrogen reacting with hot air was measured with a two-component laser Doppler velocimeter (LDV) system, a schlieren system, and OH fluorescence imaging. It was compared with a similar air-to-air case without combustion. The high-speed stream's flow speed was about 390 m/s, or Mach 0.71, and the flow speed ratio was 0.34. The results showed that a shear layer with reaction grows faster than one without; both cases are within the range of data scatter presented by the established data base. The coupling between the streamwise and the cross-stream turbulence components inside the shear layers was low, and reaction only increased it slightly. However, the shear layer shifted laterally into the lower speed fuel stream, and a more organized pattern of Reynolds stress was present in the reaction shear layer, likely as a result of the formation of a larger scale structure associated with shear layer corrugation from heat release. Dynamic pressure measurements suggest that coherent flow perturbations existed inside the shear layer and that this flow became more chaotic as the flow advected downstream. Velocity and thermal variable values are listed in this report for a computational fluid dynamics (CFD) benchmark.

Renewable chemiluminescence optosensors based on implementation of bead injection principle with multicommutation.

PubMed

Domínguez-Romero, Juan C; Gilbert-López, Bienvenida; Beneito-Cambra, Miriam; Molina-Díaz, Antonio

2018-05-15

In this work, the implementation of Bead Injection with multicommutation-based flow systems is reported. A surface renewable chemiluminescence (CL) flow sensor is presented based on the use of CL reaction of luminol with H 2 O 2 . Dowex 1 × 8 beads with immobilized luminol onto them were injected in the flow system by means of a six-port rotary valve and were accommodated into a 1 mm optical glass flow cell placed just in front of the rectangular photosensor window with the same size than the cell wall. Automatic computer-controlled manipulation of both reagents and sample solutions was undertaken using a multicommutated flow system which comprises five three-way solenoid valves, a home-made electronic interface and a Java-written software. Once the chemiluminescence signal was registered, sensing beads were automatically discarded out with a six-port rotary valve without needing to reverse or stop the flow. As a proof of concept and example, the enhancement of the chemiluminescence signal produced by Co(II) on the luminol-H 2 O 2 reaction in alkaline medium was used for illustrating this implementation determining vitamin B 12 in pharmaceutical preparations (after mineralization for releasing Co(II)). The analytical performance of the approach was satisfactory, showing a linear dynamic range from 1.7 to 50 µg L -1 , a detection limit of 0.5 µg L -1 , RSD (%) of 5.3%, with a sampling frequency of 11 h -1 . The proposed approach was applied to different samples and the results were consistent with those obtained with a reference method based on ICP-MS. Based on the same reaction (or re-configuring the system to accommodate it to reaction requirements) the approach can also be applied to the determination of other metal ions such as Cr(III) and Fe(II) and appropriately extended to molecules of bioanalytical interest based e.g. in CL immunoassays, given its versatility. Copyright © 2018 Elsevier B.V. All rights reserved.

Space-time least-squares finite element method for convection-reaction system with transformed variables

PubMed Central

Nam, Jaewook

2011-01-01

We present a method to solve a convection-reaction system based on a least-squares finite element method (LSFEM). For steady-state computations, issues related to recirculation flow are stated and demonstrated with a simple example. The method can compute concentration profiles in open flow even when the generation term is small. This is the case for estimating hemolysis in blood. Time-dependent flows are computed with the space-time LSFEM discretization. We observe that the computed hemoglobin concentration can become negative in certain regions of the flow; it is a physically unacceptable result. To prevent this, we propose a quadratic transformation of variables. The transformed governing equation can be solved in a straightforward way by LSFEM with no sign of unphysical behavior. The effect of localized high shear on blood damage is shown in a circular Couette-flow-with-blade configuration, and a physiological condition is tested in an arterial graft flow. PMID:21709752

Enzymatic synthesis of chiral amino‐alcohols by coupling transketolase and transaminase‐catalyzed reactions in a cascading continuous‐flow microreactor system

PubMed Central

Gruber, Pia; Carvalho, Filipe; Marques, Marco P. C.; O'Sullivan, Brian; Subrizi, Fabiana; Dobrijevic, Dragana; Ward, John; Hailes, Helen C.; Fernandes, Pedro; Wohlgemuth, Roland; Baganz, Frank

2017-01-01

Abstract Rapid biocatalytic process development and intensification continues to be challenging with currently available methods. Chiral amino‐alcohols are of particular interest as they represent key industrial synthons for the production of complex molecules and optically pure pharmaceuticals. (2S,3R)‐2‐amino‐1,3,4‐butanetriol (ABT), a building block for the synthesis of protease inhibitors and detoxifying agents, can be synthesized from simple, non‐chiral starting materials, by coupling a transketolase‐ and a transaminase‐catalyzed reaction. However, until today, full conversion has not been shown and, typically, long reaction times are reported, making process modifications and improvement challenging. In this contribution, we present a novel microreactor‐based approach based on free enzymes, and we report for the first time full conversion of ABT in a coupled enzyme cascade for both batch and continuous‐flow systems. Using the compartmentalization of the reactions afforded by the microreactor cascade, we overcame inhibitory effects, increased the activity per unit volume, and optimized individual reaction conditions. The transketolase‐catalyzed reaction was completed in under 10 min with a volumetric activity of 3.25 U ml−1. Following optimization of the transaminase‐catalyzed reaction, a volumetric activity of 10.8 U ml−1 was attained which led to full conversion of the coupled reaction in 2 hr. The presented approach illustrates how continuous‐flow microreactors can be applied for the design and optimization of biocatalytic processes. PMID:28986983

Mobile magnetic particles as solid-supports for rapid surface-based bioanalysis in continuous flow.

PubMed

Peyman, Sally A; Iles, Alexander; Pamme, Nicole

2009-11-07

An extremely versatile microfluidic device is demonstrated in which multi-step (bio)chemical procedures can be performed in continuous flow. The system operates by generating several co-laminar flow streams, which contain reagents for specific (bio)reactions across a rectangular reaction chamber. Functionalized magnetic microparticles are employed as mobile solid-supports and are pulled from one side of the reaction chamber to the other by use of an external magnetic field. As the particles traverse the co-laminar reagent streams, binding and washing steps are performed on their surface in one operation in continuous flow. The applicability of the platform was first demonstrated by performing a proof-of-principle binding assay between streptavidin coated magnetic particles and biotin in free solution with a limit of detection of 20 ng mL(-1) of free biotin. The system was then applied to a mouse IgG sandwich immunoassay as a first example of a process involving two binding steps and two washing steps, all performed within 60 s, a fraction of the time required for conventional testing.

FLOW SYSTEM FOR REACTOR

DOEpatents

Zinn, W.H.

1963-06-11

A reactor is designed with means for terminating the reaction when returning coolant is below a predetermined temperature. Coolant flowing from the reactor passes through a heat exchanger to a lower reservoir, and then circulates between the lower reservoir and an upper reservoir before being returned to the reactor. Means responsive to the temperature of the coolant in the return conduit terminate the chain reaction when the temperature reaches a predetermined minimum value. (AEC)

Heat Flow vs. Cash Flow: A Banking Analogy

NASA Astrophysics Data System (ADS)

Wynn, Charles M., Sr.

1997-04-01

An analogy is drawn between the withdrawal of money from an automated teller machine (ATM) and an exothermic chemical reaction. In the analogy the amount in an individual's account is regarded as the system and the money withdrawn is regarded as part of the surroundings. Diagrams are used to present the analogy. An analogy can be drawn also between a deposit into an account and an endothermic chemical reaction.

Multi-fluid CFD analysis in Process Engineering

NASA Astrophysics Data System (ADS)

Hjertager, B. H.

2017-12-01

An overview of modelling and simulation of flow processes in gas/particle and gas/liquid systems are presented. Particular emphasis is given to computational fluid dynamics (CFD) models that use the multi-dimensional multi-fluid techniques. Turbulence modelling strategies for gas/particle flows based on the kinetic theory for granular flows are given. Sub models for the interfacial transfer processes and chemical kinetics modelling are presented. Examples are shown for some gas/particle systems including flow and chemical reaction in risers as well as gas/liquid systems including bubble columns and stirred tanks.

Development and testing of a compartmentalized reaction network model for redox zones in contaminated aquifers

USGS Publications Warehouse

Abrams , Robert H.; Loague, Keith; Kent, Douglas B.

1998-01-01

The work reported here is the first part of a larger effort focused on efficient numerical simulation of redox zone development in contaminated aquifers. The sequential use of various electron acceptors, which is governed by the energy yield of each reaction, gives rise to redox zones. The large difference in energy yields between the various redox reactions leads to systems of equations that are extremely ill-conditioned. These equations are very difficult to solve, especially in the context of coupled fluid flow, solute transport, and geochemical simulations. We have developed a general, rational method to solve such systems where we focus on the dominant reactions, compartmentalizing them in a manner that is analogous to the redox zones that are often observed in the field. The compartmentalized approach allows us to easily solve a complex geochemical system as a function of time and energy yield, laying the foundation for our ongoing work in which we couple the reaction network, for the development of redox zones, to a model of subsurface fluid flow and solute transport. Our method (1) solves the numerical system without evoking a redox parameter, (2) improves the numerical stability of redox systems by choosing which compartment and thus which reaction network to use based upon the concentration ratios of key constituents, (3) simulates the development of redox zones as a function of time without the use of inhibition factors or switching functions, and (4) can reduce the number of transport equations that need to be solved in space and time. We show through the use of various model performance evaluation statistics that the appropriate compartment choice under different geochemical conditions leads to numerical solutions without significant error. The compartmentalized approach described here facilitates the next phase of this effort where we couple the redox zone reaction network to models of fluid flow and solute transport.

Determination of YAV-8B Reaction Control System bleed flow usage

NASA Technical Reports Server (NTRS)

Borchers, Paul F.; Moralez, Ernesto, III; Merrick, Vernon K.; Stortz, Michael W.; Eames, David J. H.

1992-01-01

Using a calibrated Rolls-Royce Pegasus engine, total Reaction Control System (RCS) bleed flow rates have been measured on a YAV-8B Harrier during typical short takeoff, transition, hover and vertical landing maneuvers. Using existing aircraft instrumentation and pressure taps located in the RCS ducts, bleed flow rates at each RCS valve were also measured directly during flight and ground tests. These data were compared with the calibrated engine data and with the RCS part of a YAV-8B mathematical model used in piloted simulation at NASA Ames Research Center. Areas of disagreement were small, being confined to the estimation of closed RCS valve leakages and the modeling of the RCS butterfly valve pressure losses.

Harnessing Thin-Film Continuous-Flow Assembly Lines.

PubMed

Britton, Joshua; Castle, Jared W; Weiss, Gregory A; Raston, Colin L

2016-07-25

Inspired by nature's ability to construct complex molecules through sequential synthetic transformations, an assembly line synthesis of α-aminophosphonates has been developed. In this approach, simple starting materials are continuously fed through a thin-film reactor where the intermediates accrue molecular complexity as they progress through the flow system. Flow chemistry allows rapid multistep transformations to occur via reaction compartmentalization, an approach not amenable to using conventional flasks. Thin film processing can also access facile in situ solvent exchange to drive reaction efficiency, and through this method, α-aminophosphonate synthesis requires only 443 s residence time to produce 3.22 g h(-1) . Assembly-line synthesis allows unprecedented reaction flexibility and processing efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

NASA Technical Reports Server (NTRS)

Fisher, John W.; Abraham, Martin

1993-01-01

The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

PHAST Version 2-A Program for Simulating Groundwater Flow, Solute Transport, and Multicomponent Geochemical Reactions

USGS Publications Warehouse

Parkhurst, David L.; Kipp, Kenneth L.; Charlton, Scott R.

2010-01-01

The computer program PHAST (PHREEQC And HST3D) simulates multicomponent, reactive solute transport in three-dimensional saturated groundwater flow systems. PHAST is a versatile groundwater flow and solute-transport simulator with capabilities to model a wide range of equilibrium and kinetic geochemical reactions. The flow and transport calculations are based on a modified version of HST3D that is restricted to constant fluid density and constant temperature. The geochemical reactions are simulated with the geochemical model PHREEQC, which is embedded in PHAST. Major enhancements in PHAST Version 2 allow spatial data to be defined in a combination of map and grid coordinate systems, independent of a specific model grid (without node-by-node input). At run time, aquifer properties are interpolated from the spatial data to the model grid; regridding requires only redefinition of the grid without modification of the spatial data. PHAST is applicable to the study of natural and contaminated groundwater systems at a variety of scales ranging from laboratory experiments to local and regional field scales. PHAST can be used in studies of migration of nutrients, inorganic and organic contaminants, and radionuclides; in projects such as aquifer storage and recovery or engineered remediation; and in investigations of the natural rock/water interactions in aquifers. PHAST is not appropriate for unsaturated-zone flow, multiphase flow, or density-dependent flow. A variety of boundary conditions are available in PHAST to simulate flow and transport, including specified-head, flux (specified-flux), and leaky (head-dependent) conditions, as well as the special cases of rivers, drains, and wells. Chemical reactions in PHAST include (1) homogeneous equilibria using an ion-association or Pitzer specific interaction thermodynamic model; (2) heterogeneous equilibria between the aqueous solution and minerals, ion exchange sites, surface complexation sites, solid solutions, and gases; and (3) kinetic reactions with rates that are a function of solution composition. The aqueous model (elements, chemical reactions, and equilibrium constants), minerals, exchangers, surfaces, gases, kinetic reactants, and rate expressions may be defined or modified by the user. A number of options are available to save results of simulations to output files. The data may be saved in three formats: a format suitable for viewing with a text editor; a format suitable for exporting to spreadsheets and postprocessing programs; and in Hierarchical Data Format (HDF), which is a compressed binary format. Data in the HDF file can be visualized on Windows computers with the program Model Viewer and extracted with the utility program PHASTHDF; both programs are distributed with PHAST.

Ceramic microsystem incorporating a microreactor with immobilized biocatalyst for enzymatic spectrophotometric assays.

PubMed

Baeza, Mireia; López, Carmen; Alonso, Julián; López-Santín, Josep; Alvaro, Gregorio

2010-02-01

Low-temperature cofired ceramics (LTCC) technology is a versatile fabrication technique used to construct microflow systems. It permits the integration of several unitary operations (pretreatment, separation, (bio)chemical reaction, and detection stage) of an analytical process in a modular or monolithic way. Moreover, because of its compatibility with biological material, LTCC is adequate for analytical applications based on enzymatic reactions. Here we present the design, construction, and evaluation of a LTCC microfluidic system that integrates a microreactor (internal volume, 24.28 microL) with an immobilized beta-galactosidase from Escherichia coli (0.479 activity units) and an optical flow cell to measure the product of the enzymatic reaction. The enzyme was immobilized on a glyoxal-agarose support, maintaining its activity along the time of the study. As a proof of concept, the LTCC-beta-galactosidase system was tested by measuring the conversion of ortho-nitrophenyl beta-D-galactopyranoside, the substrate usually employed for activity determinations. Once packed in a monolithically integrated microcolumn, the miniaturized flow system was characterized, the operational conditions optimized (flow rate and injection volume), and its performance successfully evaluated by determining the beta-galactosidase substrate concentration at the millimolar level.

Stabilization of miscible viscous fingering by a step-growth polymerization reaction

NASA Astrophysics Data System (ADS)

Bunton, Patrick; Stewart, Simone; Marin, Daniela; Tullier, Michael; Meiburg, Eckart; Pojman, John

2017-11-01

Viscous fingering is a hydrodynamic instability that occurs when a more mobile fluid displaces a fluid of lower mobility. Viscous fingering is often undesirable in industrial processes such as secondary petroleum recovery where it limits resource recovery. Linear stability analysis by Hejazi et al. (2010) has predicted that a non-monotonic viscosity profile at an otherwise unstable interface can in some instances stabilize the flow. We use step-growth polymerization at the interface between two miscible monomers as a model system. A dithiol monomer displacing a diacrylate react to form a linear polymer that behaves as a Newtonian fluid. Viscous fingering was imaged in a horizontal Hele-Shaw cell via Schlieren, which is sensitive to polymer conversion. By varying reaction rate via initiator concentration along with flow rate, we demonstrated increasing stabilization of the flow with increasing Damkohler number (ratio of the reaction rate to the flow rate). Results were compared with regions of predicted stability from the results of Hejazi et al. (2010). When the advection outran the reaction, viscous fingering occurred as usual. However, when the reaction was able to keep pace with the advection, the increased viscosity at the interface stabilized the flow. We acknowledge support from NSF CBET-1335739 and NSF CBET 1511653.

Effects of incomplete mixing on reactive transport in flows through heterogeneous porous media

NASA Astrophysics Data System (ADS)

Wright, Elise E.; Richter, David H.; Bolster, Diogo

2017-11-01

The phenomenon of incomplete mixing reduces bulk effective reaction rates in reactive transport. Many existing models do not account for these effects, resulting in the overestimation of reaction rates in laboratory and field settings. To date, most studies on incomplete mixing have focused on diffusive systems; here, we extend these to explore the role that flow heterogeneity has on incomplete mixing. To do this, we examine reactive transport using a Lagrangian reactive particle tracking algorithm in two-dimensional idealized heterogeneous porous media. Contingent on the nondimensional Peclet and Damköhler numbers in the system, it was found that near well-mixed behavior could be observed at late times in the heterogeneous flow field simulations. We look at three common flow deformation metrics that describe the enhancement of mixing in the flow due to velocity gradients: the Okubo-Weiss parameter (θ ), the largest eigenvalue of the Cauchy-Green strain tensor (λC), and the finite-time Lyapunov exponent (Λ ). Strong mixing regions in the heterogeneous flow field identified by these metrics were found to correspond to regions with higher numbers of reactions, but the infrequency of these regions compared to the large numbers of reactions occurring elsewhere in the domain imply that these strong mixing regions are insufficient in explaining the observed near well-mixed behavior. Since it was found that reactive transport in these heterogeneous flows could overcome the effects of incomplete mixing, we also search for a closure for the mean concentration. The conservative quantity u2¯, where u =CA-CB , was found to predict the late time scaling of the mean concentration, i.e., Ci¯˜u2¯ .

Scaling hyporheic exchange and its influence on biogeochemical reactions in aquatic ecosystems

USGS Publications Warehouse

O'Connor, Ben L.; Harvey, Judson W.

2008-01-01

Hyporheic exchange and biogeochemical reactions are difficult to quantify because of the range in fluid‐flow and sediment conditions inherent to streams, wetlands, and nearshore marine ecosystems. Field measurements of biogeochemical reactions in aquatic systems are impeded by the difficulty of measuring hyporheic flow simultaneously with chemical gradients in sediments. Simplified models of hyporheic exchange have been developed using Darcy's law generated by flow and bed topography at the sediment‐water interface. However, many modes of transport are potentially involved (molecular diffusion, bioturbation, advection, shear, bed mobility, and turbulence) with even simple models being difficult to apply in complex natural systems characterized by variable sediment sizes and irregular bed geometries. In this study, we synthesize information from published hyporheic exchange investigations to develop a scaling relationship for estimating mass transfer in near‐surface sediments across a range in fluid‐flow and sediment conditions. Net hyporheic exchange was quantified using an effective diffusion coefficient (De) that integrates all of the various transport processes that occur simultaneously in sediments, and dimensional analysis was used to scale De to shear stress velocity, roughness height, and permeability that describe fluid‐flow and sediment characteristics. We demonstrated the value of the derived scaling relationship by using it to quantify dissolved oxygen (DO) uptake rates on the basis of DO profiles in sediments and compared them to independent flux measurements. The results support a broad application of the De scaling relationship for quantifying coupled hyporheic exchange and biogeochemical reaction rates in streams and other aquatic ecosystems characterized by complex fluid‐flow and sediment conditions.

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

NASA Technical Reports Server (NTRS)

Chinitz, W.; Foy, E.; Rowan, G.; Goldstein, D.

1982-01-01

The use of probability theory to determine the effects of turbulent fluctuations on reaction rates in turbulent combustion systems is briefly reviewed. Results are presented for the effect of species fluctuations in particular. It is found that turbulent fluctuations of species act to reduce the reaction rates, in contrast with the temperature fluctuations previously determined to increase Arrhenius reaction rate constants. For the temperature fluctuations, a criterion is set forth for determining if, in a given region of a turbulent flow field, the temperature can be expected to exhibit ramp like fluctuations. Using the above results, along with results previously obtained, a model is described for testing the effects of turbulent fluctuations of temperature and species on reaction rates in computer programs dealing with turbulent reacting flows. An alternative model which employs three variable probability density functions (temperature and two species) and is currently being formulated is discussed as well.

Continuous Flow Science in an Undergraduate Teaching Laboratory: Bleach-Mediated Oxidation in a Biphasic System

ERIC Educational Resources Information Center

Kairouz, Vanessa; Collins, Shawn K.

2018-01-01

An undergraduate teaching laboratory experiment involving a continuous flow, bleach-mediated oxidation of aldehydes under biphasic conditions was developed that allowed students to explore concepts of mixing or mass transport, solvent sustainability, biphasic reactions, phase transfer catalysis, and continuous flow chemistry.

Three dimensional radiative flow of magnetite-nanofluid with homogeneous-heterogeneous reactions

NASA Astrophysics Data System (ADS)

Hayat, Tasawar; Rashid, Madiha; Alsaedi, Ahmed

2018-03-01

Present communication deals with the effects of homogeneous-heterogeneous reactions in flow of nanofluid by non-linear stretching sheet. Water based nanofluid containing magnetite nanoparticles is considered. Non-linear radiation and non-uniform heat sink/source effects are examined. Non-linear differential systems are computed by Optimal homotopy analysis method (OHAM). Convergent solutions of nonlinear systems are established. The optimal data of auxiliary variables is obtained. Impact of several non-dimensional parameters for velocity components, temperature and concentration fields are examined. Graphs are plotted for analysis of surface drag force and heat transfer rate.

The development and evaluation of a non-pressurised, chemical oxygen reaction generation vessel and breathing system providing emergency oxygen for an extended duration.

PubMed

Dingley, J; Williams, D; Douglas, P; Douglas, M; Douglas, J O

2016-12-01

The objective was to develop a sodium percarbonate/water/catalyst chemical oxygen generator that did not require compressed gas. Existing devices utilising this reaction have a very short duration of action. Preliminary experiments with a glass reaction vessel, water bath and electronic flowmeter indicated that many factors affected oxygen production rate including reagent formulation, temperature, water volume and agitation frequency. Having undertaken full-scale experiments using a stainless steel vessel, an optimum combination of reagents was found to be 1 litre water, 0.75 g manganese dioxide catalyst, 60 g sodium percarbonate granules and 800 g of custom pressed 7.21 (0.28) g sodium percarbonate tablets. This combination of granules and slower dissolution tablets produced a rapid initial oxygen flow to 'purge' an attached low-flow breathing system allowing immediate use, followed by a constant flow meeting metabolic requirements for a minimum of 1 h duration. © 2016 The Association of Anaesthetists of Great Britain and Ireland.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Camacho-Bunquin, Jeffrey; Shou, Heng; Aich, Payoli

An integrated atomic layer deposition-catalysis (I-ALD-CAT) tool was developed, combining an ALD manifold with a plug-flow reactor system for the synthesis of supported catalytic materials by ALD and immediate evaluation of catalyst reactivity using gas-phase probe reactions. The I-ALD-CAT system can deliver gaseous reagents comprised of 12 different metal ALD precursors, 4 oxidizing or reducing agents, and 4 catalytic reaction feeds to either of the two plug-flow reactors. The system can employ reactor pressures and temperatures in the range of 10-3–1 bar and 300–1000 K, respectively. The instrument is also equipped with a gas chromatograph and a mass spectrometer unitmore » for the detection and quantification of volatile species from ALD and catalytic reactions. In this report, we demonstrate the use of the I-ALD-CAT tool for the ALD of platinum active sites and Al2O3 overcoats, and evaluation of catalyst propylene hydrogenation activity.« less

Theoretical Investigations on the Efficiency and the Conditions for the Realization of Jet Engines

NASA Technical Reports Server (NTRS)

Roy, Maurice

1950-01-01

Contents: Preliminary notes on the efficiency of propulsion systems; Part I: Propulsion systems with direct axial reaction rockets and rockets with thrust augmentation; Part II: Helicoidal reaction propulsion systems; Appendix I: Steady flow of viscous gases; Appendix II: On the theory of viscous fluids in nozzles; and Appendix III: On the thrusts augmenters, and particularly of gas augmenters

Enzymatic synthesis of chiral amino-alcohols by coupling transketolase and transaminase-catalyzed reactions in a cascading continuous-flow microreactor system.

PubMed

Gruber, Pia; Carvalho, Filipe; Marques, Marco P C; O'Sullivan, Brian; Subrizi, Fabiana; Dobrijevic, Dragana; Ward, John; Hailes, Helen C; Fernandes, Pedro; Wohlgemuth, Roland; Baganz, Frank; Szita, Nicolas

2018-03-01

Rapid biocatalytic process development and intensification continues to be challenging with currently available methods. Chiral amino-alcohols are of particular interest as they represent key industrial synthons for the production of complex molecules and optically pure pharmaceuticals. (2S,3R)-2-amino-1,3,4-butanetriol (ABT), a building block for the synthesis of protease inhibitors and detoxifying agents, can be synthesized from simple, non-chiral starting materials, by coupling a transketolase- and a transaminase-catalyzed reaction. However, until today, full conversion has not been shown and, typically, long reaction times are reported, making process modifications and improvement challenging. In this contribution, we present a novel microreactor-based approach based on free enzymes, and we report for the first time full conversion of ABT in a coupled enzyme cascade for both batch and continuous-flow systems. Using the compartmentalization of the reactions afforded by the microreactor cascade, we overcame inhibitory effects, increased the activity per unit volume, and optimized individual reaction conditions. The transketolase-catalyzed reaction was completed in under 10 min with a volumetric activity of 3.25 U ml -1 . Following optimization of the transaminase-catalyzed reaction, a volumetric activity of 10.8 U ml -1 was attained which led to full conversion of the coupled reaction in 2 hr. The presented approach illustrates how continuous-flow microreactors can be applied for the design and optimization of biocatalytic processes. © 2017 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc.

Flow microreactor synthesis in organo-fluorine chemistry

PubMed Central

Nagaki, Aiichiro

2013-01-01

Summary Organo-fluorine compounds are the substances of considerable interest in various industrial fields due to their unique physical and chemical properties. Despite increased demand in wide fields of science, synthesis of fluoro-organic compounds is still often faced with problems such as the difficulties in handling of fluorinating reagents and in controlling of chemical reactions. Recently, flow microreactor synthesis has emerged as a new methodology for producing chemical substances with high efficiency. This review outlines the successful examples of synthesis and reactions of fluorine-containing molecules by the use of flow microreactor systems to overcome long-standing problems in fluorine chemistry. PMID:24367443

Flow microreactor synthesis in organo-fluorine chemistry.

PubMed

Amii, Hideki; Nagaki, Aiichiro; Yoshida, Jun-Ichi

2013-12-05

Organo-fluorine compounds are the substances of considerable interest in various industrial fields due to their unique physical and chemical properties. Despite increased demand in wide fields of science, synthesis of fluoro-organic compounds is still often faced with problems such as the difficulties in handling of fluorinating reagents and in controlling of chemical reactions. Recently, flow microreactor synthesis has emerged as a new methodology for producing chemical substances with high efficiency. This review outlines the successful examples of synthesis and reactions of fluorine-containing molecules by the use of flow microreactor systems to overcome long-standing problems in fluorine chemistry.

[Effect of noradrenaline and angiotensin II on the brain and kidney blood supply with changes in systemic arterial pressure].

PubMed

Beketov, A I; Korneliuk, I K

1981-01-01

Hydrogen clearance was used in experiments on anesthetized cats to demonstrate that intravenous infusions of noradrenaline induced an increase in cerebral blood supply and reduction of renal blood flow both in anesthetized animals and in the presence of hypotension. In these conditions, angiotensin II lowered the cerebral and renal blood flow. Hypotension enhanced the reactions of the cerebral and renal blood flow to the action of vasopressor agents. The intensity of the reactions was consistent with the degree of vascular autocontrol preservation in the brain and kidneys.

Six-flow operations for catalyst development in Fischer-Tropsch synthesis: Bridging the gap between high-throughput experimentation and extensive product evaluation

NASA Astrophysics Data System (ADS)

Sartipi, Sina; Jansma, Harrie; Bosma, Duco; Boshuizen, Bart; Makkee, Michiel; Gascon, Jorge; Kapteijn, Freek

2013-12-01

Design and operation of a "six-flow fixed-bed microreactor" setup for Fischer-Tropsch synthesis (FTS) is described. The unit consists of feed and mixing, flow division, reaction, separation, and analysis sections. The reactor system is made of five heating blocks with individual temperature controllers, assuring an identical isothermal zone of at least 10 cm along six fixed-bed microreactor inserts (4 mm inner diameter). Such a lab-scale setup allows running six experiments in parallel, under equal feed composition, reaction temperature, and conditions of separation and analysis equipment. It permits separate collection of wax and liquid samples (from each flow line), allowing operation with high productivities of C5+ hydrocarbons. The latter is crucial for a complete understanding of FTS product compositions and will represent an advantage over high-throughput setups with more than ten flows where such instrumental considerations lead to elevated equipment volume, cost, and operation complexity. The identical performance (of the six flows) under similar reaction conditions was assured by testing a same catalyst batch, loaded in all microreactors.

On understanding nuclear reaction network flows with branchings on directed graphs

NASA Astrophysics Data System (ADS)

Meyer, Bradley S.

2018-04-01

Nuclear reaction network flow diagrams are useful for understanding which reactions are governing the abundance changes at a particular time during nucleosynthesis. This is especially true when the flows are largely unidirectional, such as during the s-process of nucleosynthesis. In explosive nucleosynthesis, when reaction flows are large, and when forward reactions are nearly balanced by their reverses, reaction flows no longer give a clear picture of the abundance evolution in the network. This paper presents a way of understanding network evolution in terms of sums of branchings on a directed graph, which extends the concept of reaction flows to allow for multiple reaction pathways.

Seasonal dynamics of groundwater-lake interactions at Doñana National Park, Spain

USGS Publications Warehouse

Sacks, Laura A.; Herman, Janet S.; Konikow, Leonard F.; Vela, Antonio L.

1992-01-01

The hydrologic and solute budgets of a lake can be strongly influenced by transient groundwater flow. Several shallow interdunal lakes in southwest Spain are in close hydraulic connection with the shallow ground water. Two permanent lakes and one intermittent lake have chloride concentrations that differ by almost an order of magnitude. A two-dimensional solute-transport model, modified to simulate transient groundwater-lake interaction, suggests that the rising water table during the wet season leads to local flow reversals toward the lakes. Response of the individual lakes, however, varies depending on the lake's position in the regional flow system. The most dilute lake is a flow-through lake during the entire year; the through flow is driven by regional groundwater flow. The other permanent lake, which has a higher solute concentration, undergoes seasonal groundwater flow reversals at its downgradient end, resulting in complex seepage patterns and higher solute concentrations in the ground water near the lake. The solute concentration of the intermittent lake is influenced more strongly by the seasonal wetting and drying cycle than by the regional flow system. Although evaporation is the major process affecting the concentration of conservative solutes in the lakes, geochemical and biochemical reactions influence the concentration of nonconservative solutes. Probable reactions in the lakes include biological uptake of solutes and calcite precipitation; probable reactions as lake water seeps into the aquifer are sulfate reduction and calcite dissolution. Seepage reversals can result in water composition that appears inconsistent with predictions based on head measurements because, under transient flow conditions, the flow direction at any instant may not satisfactorily depict the source of the water. Understanding the dynamic nature of groundwater-lake interaction aids in the interpretation of hydrologic and chemical relations between the lakes and the ground water.

Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes

PubMed Central

Moreno-Marrodan, Carmen; Liguori, Francesca

2017-01-01

The catalytic partial hydrogenation of substituted alkynes to alkenes is a process of high importance in the manufacture of several market chemicals. The present paper shortly reviews the heterogeneous catalytic systems engineered for this reaction under continuous flow and in the liquid phase. The main contributions appeared in the literature from 1997 up to August 2016 are discussed in terms of reactor design. A comparison with batch and industrial processes is provided whenever possible. PMID:28503209

Coupled hydrological and geochemical process evolution at the Landscape Evolution Observatory

NASA Astrophysics Data System (ADS)

Troch, P. A. A.

2015-12-01

Predictions of hydrologic and biogeochemical responses to natural and anthropogenic forcing at the landscape scale are highly uncertain due to the effects of heterogeneity on the scaling of reaction, flow and transport phenomena. The physical, chemical and biological structures and processes controlling reaction, flow and transport in natural landscapes interact at multiple space and time scales and are difficult to quantify. The current paradigm of hydrological and geochemical theory is that process descriptions derived from observations at small scales in controlled systems can be applied to predict system response at much larger scales, as long as some 'equivalent' or 'effective' values of the scale-dependent parameters can be identified. Furthermore, natural systems evolve in time in a way that is hard to observe in short-run laboratory experiments or in natural landscapes with unknown initial conditions and time-variant forcing. The spatial structure of flow pathways along hillslopes determines the rate, extent and distribution of geochemical reactions (and biological colonization) that drive weathering, the transport and precipitation of solutes and sediments, and the further evolution of soil structure. The resulting evolution of structures and processes, in turn, produces spatiotemporal variability of hydrological states and flow pathways. There is thus a need for experimental research to improve our understanding of hydrology-biogeochemistry interactions and feedbacks at appropriate spatial scales larger than laboratory soil column experiments. Such research is complicated in real-world settings because of poorly constrained impacts of initial conditions, climate variability, ecosystems dynamics, and geomorphic evolution. The Landscape Evolution Observatory (LEO) at Biosphere 2 offers a unique research facility that allows real-time observations of incipient hydrologic and biogeochemical response under well-constrained initial conditions and climate forcing. The LEO allows to close the water, carbon and energy budgets at hillslope scales, thereby enabling elucidation of the tight coupling between the time water spends along subsurface flow paths and geochemical weathering reactions, including the feedbacks between flow and pedogenesis.

Towards a Model of Reactive-Cracking: the Role of Reactions, Elasticity and Surface Energy Driven Flow in Poro-elastic Media

NASA Astrophysics Data System (ADS)

Evans, O.; Spiegelman, M. W.; Wilson, C. R.; Kelemen, P. B.

2016-12-01

Many critical processes can be described by reactive fluid flow in brittle media, including hydration/alteration of oceanic plates near spreading ridges, chemical weathering, and dehydration/decarbonation of subducting plates. Such hydration reactions can produce volume changes that may induce stresses large enough to drive fracture in the rock, in turn exposing new reactive surface and modifying the permeability. A better understanding of this potentially rich feedback could also be critical in the design of engineered systems for geologic carbon sequestration. To aid understanding of these processes we have developed a macroscopic continuum description of reactive fluid flow in an elastically deformable porous media. We explore the behaviour of this model by considering a simplified hydration reaction (e.g. olivine + H20 -> serpentine + brucite). In a closed system, these hydration reactions will continue to consume available fluids until the permeability reaches zero, leaving behind it a highly stressed residuum. Our model demonstrates this limiting behaviour, and that the elastic stresses generated are large enough to cause failure/fracture of the host rock. Whilst it is understood that `reactive fracture' is an important mechanism for the continued evolution of this process, it is also proposed that imbibition/surface energy driven flow may play a role. Through a simplified set of computational experiments, we investigate the relative roles of elasticity and surface energy in both a non-reactive purely poro-elastic framework, and then in the presence of reaction. We demonstrate that surface energy can drive rapid diffusion of porosity, thus allowing the reaction to propagate over larger areas. As we expect both surface energy and fracture/failure to be of importance in these processes, we plan to integrate the current model into one that allows for fracture once critical stresses are exceeded.

Highly efficient reversible addition-fragmentation chain-transfer polymerization in ethanol/water via flow chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Piaoran; Cao, Peng -Fei; Su, Zhe

Here, utilization of a flow reactor under high pressure allows highly efficient polymer synthesis via reversible addition–fragmentation chain-transfer (RAFT) polymerization in an aqueous system. Compared with the batch reaction, the flow reactor allows the RAFT polymerization to be performed in a high-efficiency manner at the same temperature. The adjustable pressure of the system allows further elevation of the reaction temperature and hence faster polymerization. Other reaction parameters, such as flow rate and initiator concentration, were also well studied to tune the monomer conversion and the molar mass dispersity (Ð) of the obtained polymers. Gel permeation chromatography, nuclear magnetic resonance (NMR),more » and Fourier transform infrared spectroscopies (FTIR) were utilized to monitor the polymerization process. With the initiator concentration of 0.15 mmol L –1, polymerization of poly(ethylene glycol) methyl ethermethacrylate with monomer conversion of 52% at 100 °C under 73 bar can be achieved within 40 min with narrow molar mass dispersity (D) Ð (<1.25). The strategy developed here provides a method to produce well-defined polymers via RAFT polymerization with high efficiency in a continuous manner.« less

Flow-injection determination of total organic fluorine with off-line defluorination reaction on a solid sorbent bed.

PubMed

Musijowski, Jacek; Trojanowicz, Marek; Szostek, Bogdan; da Costa Lima, José Luis Fontes; Lapa, Rui; Yamashita, Hiroki; Takayanagi, Toshio; Motomizu, Shoji

2007-09-26

Considering recent reports on widespread occurrence and concerns about perfluoroalkyl substances (PFAS) in environmental and biological systems, analysis of these compounds have gained much attention in recent years. Majority of analyte-specific methods are based on a LC/MS/MS or a GC/MS detection, however many environmental or biological studies would benefit from a total organic fluorine (TOF) determination. Presented work was aimed at developing a method for TOF determination. TOF is determined as an amount of inorganic fluoride obtained after defluorination reaction conducted off-line using sodium biphenyl reagent directly on the sorbent without elution of retained analytes. Recovered fluoride was analyzed using flow-injection system with either fluorimetric or potentiometric detection. The TOF method was tested using perfluorocarboxylic acids (PFCA), including perfluorooctanoic acid (PFOA), as model compounds. Considering low concentrations of PFAS in natural samples, solid-phase extraction as a preconcentration procedure was evaluated. Several carbon-based sorbents were tested, namely multi-wall carbon nanotubes, carbon nanofibres and activated carbon. Good sorption of all analytes was achieved and defluorination reaction was possible to carry out directly on a sorbent bed. Recoveries obtained for PFCAs, adsorbed on an activated carbon sorbent, and measured as TOF, were 99.5+/-1.7, 110+/-9.4, 95+/-26, 120+/-32, 110+/-12 for C4, C6, C8, C10 and C12-PFCA, respectively. Two flow systems that would enable the defluorination reaction and fluoride determination in a single system were designed and tested.

Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

NASA Technical Reports Server (NTRS)

Abraham, Martin; Fisher, John W.

1995-01-01

The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst, prepared at The University of Tulsa, at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

Exact PDF equations and closure approximations for advective-reactive transport

DOE Office of Scientific and Technical Information (OSTI.GOV)

Venturi, D.; Tartakovsky, Daniel M.; Tartakovsky, Alexandre M.

2013-06-01

Mathematical models of advection–reaction phenomena rely on advective flow velocity and (bio) chemical reaction rates that are notoriously random. By using functional integral methods, we derive exact evolution equations for the probability density function (PDF) of the state variables of the advection–reaction system in the presence of random transport velocity and random reaction rates with rather arbitrary distributions. These PDF equations are solved analytically for transport with deterministic flow velocity and a linear reaction rate represented mathematically by a heterog eneous and strongly-correlated random field. Our analytical solution is then used to investigate the accuracy and robustness of the recentlymore » proposed large-eddy diffusivity (LED) closure approximation [1]. We find that the solution to the LED-based PDF equation, which is exact for uncorrelated reaction rates, is accurate even in the presence of strong correlations and it provides an upper bound of predictive uncertainty.« less

[Individual typological peculiarities of system blood flow, physical capacity for work and cardiac activity regulation in patients with different resistance to periodontal diseases].

PubMed

Bragin, A V

2008-01-01

From position of typological variability of physiological individuality concept-functional constitution types - the principle of organism integrity was substantiated for stomatological pathology. There were isolated typical and specific reactions of cardiac-vessel system in patients with different resistance to periodontal diseases. Each functional type - patients with different levels of usual motion activity - had their own physiological peculiarities of parameters of system blood flow, physical capacity for work and cardiac activity regulation, that determined individual typological organism reaction in cases of maxillo-facial system pathology. The received data gives the objective base for physiological approach to single out the extreme variants of norm for forming risk contingent and groups of resistant people to periodontal diseases.

Programmable flow system for automation of oxygen radical absorbance capacity assay using pyrogallol red for estimation of antioxidant reactivity.

PubMed

Ramos, Inês I; Gregório, Bruno J R; Barreiros, Luísa; Magalhães, Luís M; Tóth, Ildikó V; Reis, Salette; Lima, José L F C; Segundo, Marcela A

2016-04-01

An automated oxygen radical absorbance capacity (ORAC) method based on programmable flow injection analysis was developed for the assessment of antioxidant reactivity. The method relies on real time spectrophotometric monitoring (540 nm) of pyrogallol red (PGR) bleaching mediated by peroxyl radicals in the presence of antioxidant compounds within the first minute of reaction, providing information about their initial reactivity against this type of radicals. The ORAC-PGR assay under programmable flow format affords a strict control of reaction conditions namely reagent mixing, temperature and reaction timing, which are critical parameters for in situ generation of peroxyl radical from 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH). The influence of reagent concentrations and programmable flow conditions on reaction development was studied, with application of 37.5 µM of PGR and 125 mM of AAPH in the flow cell, guaranteeing first order kinetics towards peroxyl radicals and pseudo-zero order towards PGR. Peroxyl-scavenging reactivity of antioxidants, bioactive compounds and phenolic-rich beverages was estimated employing the proposed methodology. Recovery assays using synthetic saliva provided values of 90 ± 5% for reduced glutathione. Detection limit calculated using the standard antioxidant compound Trolox was 8 μM. RSD values were <3.4 and <4.9%, for intra and inter-assay precision, respectively. Compared to previous batch automated ORAC assays, the developed system also accounted for high sampling frequency (29 h(-1)), low operating costs and low generation of waste. Copyright © 2015 Elsevier B.V. All rights reserved.

Development of a Control System for the Teat-End Vacuum in Individual Quarter Milking Systems

PubMed Central

Ströbel, Ulrich; Rose-Meierhöfer, Sandra; Öz, Hülya; Brunsch, Reiner

2013-01-01

Progress in sensor technique and electronics has led to a decrease in the costs of electronic and sensor components. In modern dairy farms, having udders in good condition, a lower frequency of udder disease and an extended service life of dairy cows will help ensure competitiveness. The objective of this study was to develop a teat-end vacuum control system with individual quarter actor reaction. Based on a review of the literature, this system is assumed to protect the teat tissue. It reduces the mean teat-end vacuum in the maximum vacuum phase (b) to a level of 20 kPa at a flow rate of 0.25 L/min per quarter. At flow rates higher than 1.50 L/min per quarter, the teat-end vacuum can be controlled to a level of 30 kPa, because in this case it is desirable to have a higher vacuum for the transportation of the milk to the receiver. With this system it is possible for the first time to supply the teat end with low vacuum at low flow rates and with higher vacuum at increasing flow rates in a continuous process with a three second reaction-rate on individual quarter level. This system is completely automated. PMID:23765272

Initiation with an electron beam of chemical reactions of interest for visible wavelength lasers

NASA Technical Reports Server (NTRS)

Whittier, J. S.; Cool, T. A.

1976-01-01

A description is given of the first results obtained with a new shock tube-electron beam facility designed to provide a versatile means for the systematic search for laser operation among several candidate metal atom-oxidizer systems. According to the current experimental approach, metal atoms are obtained in the vapor phase by the dissociation of metal compounds. A shock tube is employed to provide a short duration flow through an array of 29 supersonic flow-mixing nozzles. A high energy electron accelerator is used for the rapid initiation of chemical reaction in a mixed flow of encapsulated metal and oxidizer.

Scope and mechanism of the highly stereoselective metal-mediated domino aldol reactions of enolates with aldehydes

PubMed Central

Engelen, Bernward; Panthöfer, Martin; Deiseroth, Hans-Jörg; Schlirf, Jens

2016-01-01

Summary A one-pot transformation, which involves the reaction of ketones with aldehydes in the presence of metal halides to furnish tetrahydro-2H-pyran-2,4-diols in a highly diastereoselective manner, is investigated thoroughly by experiments and computations. The reaction was also successfully implemented on a flow micro reactor system. PMID:27340472

Investigation of a lithium-halogen exchange flow process for the preparation of boronates by using a cryo-flow reactor.

PubMed

Newby, James A; Huck, Lena; Blaylock, D Wayne; Witt, Paul M; Ley, Steven V; Browne, Duncan L

2014-01-03

Conducting low-temperature organometallic reactions under continuous flow conditions offers the potential to more accurately control exotherms and thus provide more reproducible and scalable processes. Herein, progress towards this goal with regards to the lithium-halogen exchange/borylation reaction is reported. In addition to improving the scope of substrates available on a research scale, methods to improve reaction profiles and expedite purification of the products are also described. On moving to a continuous system, thermocouple measurements have been used to track exotherms and provide a level of safety for continuous processing of organometallic reagents. The use of an in-line continuous liquid-liquid separation device to circumvent labour intensive downstream off-line processing is also reported. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Numerical study of supersonic combustion using a finite rate chemistry model

NASA Technical Reports Server (NTRS)

Chitsomboon, T.; Tiwari, S. N.; Kumar, A.; Drummond, J. P.

1986-01-01

The governing equations of two-dimensional chemically reacting flows are presented together with a global two-step chemistry model for H2-air combustion. The explicit unsplit MacCormack finite difference algorithm is used to advance the discrete system of the governing equations in time until convergence is attained. The source terms in the species equations are evaluated implicitly to alleviate stiffness associated with fast reactions. With implicit source terms, the species equations give rise to a block-diagonal system which can be solved very efficiently on vector-processing computers. A supersonic reacting flow in an inlet-combustor configuration is calculated for the case where H2 is injected into the flow from the side walls and the strut. Results of the calculation are compared against the results obtained by using a complete reaction model.

CFD Simulation of the Space Shuttle Launch Vehicle with Booster Separation Motor and Reaction Control Plumes

NASA Technical Reports Server (NTRS)

Gea, L. M.; Vicker, D.

2006-01-01

The primary objective of this paper is to demonstrate the capability of computational fluid dynamics (CFD) to simulate a very complicated flow field encountered during the space shuttle ascent. The flow field features nozzle plumes from booster separation motor (BSM) and reaction control system (RCS) jets with a supersonic incoming cross flow at speed of Mach 4. The overset Navier-Stokes code OVERFLOW, was used to simulate the flow field surrounding the entire space shuttle launch vehicle (SSLV) with high geometric fidelity. The variable gamma option was chosen due to the high temperature nature of nozzle flows and different plume species. CFD predicted Mach contours are in good agreement with the schlieren photos from wind tunnel test. Flow fields are discussed in detail and the results are used to support the debris analysis for the space shuttle Return To Flight (RTF) task.

Radiative interactions in chemically reacting supersonic internal flows

NASA Technical Reports Server (NTRS)

Tiwari, S. N.; Chandrasekhar, R.

1991-01-01

The two-dimensional, elliptic Navier-Stokes equations are used to investigate supersonic flows with finite-rate chemistry and radiation for hydrogen-air systems. The chemistry source terms in the species equation is treated implicitly to alleviate the stiffness associated with fast reactions. The explicit, unsplit MacCormack finite-difference scheme is used to advance the governing equations in time, until convergence is achieved. The specific problem considered is the premixed flow in a channel with a ten-degree compression ramp. Three different chemistry models are used, accounting for increasing number of reactions and participating species. Two chemistry models assure nitrogen as inert, while the third model accounts for nitrogen reactions and NO(x) formation. The tangent slab approximation is used in the radiative flux formulation. A pseudo-gray model is used to represent the absorption-emission characteristics of the participating species. Results obtained for specific conditions indicate that the radiative interactions vary substantially, depending on reactions involving HO2 and NO species and that this can have a significant influence on the flowfield.

On-line Monitoring of Continuous Flow Chemical Synthesis Using a Portable, Small Footprint Mass Spectrometer

NASA Astrophysics Data System (ADS)

Bristow, Tony W. T.; Ray, Andrew D.; O'Kearney-McMullan, Anne; Lim, Louise; McCullough, Bryan; Zammataro, Alessio

2014-10-01

For on-line monitoring of chemical reactions (batch or continuous flow), mass spectrometry (MS) can provide data to (1) determine the fate of starting materials and reagents, (2) confirm the presence of the desired product, (3) identify intermediates and impurities, (4) determine steady state conditions and point of completion, and (5) speed up process optimization. Recent developments in small footprint atmospheric pressure ionization portable mass spectrometers further enable this coupling, as the mass spectrometer can be easily positioned with the reaction system to be studied. A major issue for this combination is the transfer of a sample that is representative of the reaction and also compatible with the mass spectrometer. This is particularly challenging as high concentrations of reagents and products can be encountered in organic synthesis. The application of a portable mass spectrometer for on-line characterization of flow chemical synthesis has been evaluated by coupling a Microsaic 4000 MiD to the Future Chemistry Flow Start EVO chemistry system. Specifically, the Hofmann rearrangement has been studied using the on-line mass spectrometry approach. Sample transfer from the flow reactor is achieved using a mass rate attenuator (MRA) and a sampling make-up flow from a high pressure pump. This enables the appropriate sample dilution, transfer, and preparation for electrospray ionization. The capability of this approach to provide process understanding is described using an industrial pharmaceutical process that is currently under development. The effect of a number of key experimental parameters, such as the composition of the sampling make-up flow and the dilution factor on the mass spectrometry data, is also discussed.

A simple and cost-effective molecular diagnostic system and DNA probes synthesized by light emitting diode photolithography

NASA Astrophysics Data System (ADS)

Oleksandrov, Sergiy; Kwon, Jung Ho; Lee, Ki-chang; Sujin-Ku; Paek, Mun Cheol

2014-09-01

This work introduces a novel chip to be used in the future as a simple and cost-effective method for creating DNA arrays using light emission diode (LED) photolithography. The DNA chip platform contains 24 independent reaction sites, which allows for the testing of a corresponding amount of patients' samples in hospital. An array of commercial UV LEDs and lens systems was combined with a microfluidic flow system to provide patterning of 24 individual reaction sites, each with 64 independent probes. Using the LED array instead of conventional laser exposure systems or micro-mirror systems significantly reduces the cost of equipment. The microfluidic system together with microfluidic flow cells drastically reduces the amount of used reagents, which is important due to the high cost of commercial reagents. The DNA synthesis efficiency was verified by fluorescence labeling and conventional hybridization.

Burning invariant manifolds for reaction fronts in three-dimensional fluid flows

NASA Astrophysics Data System (ADS)

Mitchell, Kevin; Solomon, Tom

2017-11-01

The geometry of reaction fronts that propagate in fully three-dimensional (3D) fluid flows is studied using the tools of dynamical systems theory. The evolution of an infinitesimal front element is modeled as a six-dimensional ODE-three dimensions for the position of the front element and three for the orientation of its unit normal. This generalizes an earlier approach to understanding front propagation in two-dimensional (2D) fluid flows. As in 2D, the 3D system exhibits prominent burning invariant manifolds (BIMs). In 3D, BIMs are two-dimensional dynamically defined surfaces that form one-way barriers to the propagation of reaction fronts within the fluid. Due to the third dimension, BIMs in 3D exhibit a richer topology than their cousins in 2D. In particular, whereas BIMs in both 2D and 3D can originate from fixed points of the dynamics, BIMs in 3D can also originate from limit cycles. Such BIMs form robust tube-like channels that guide and constrain the evolution of the front within the bulk of the fluid. Supported by NSF Grant CMMI-1201236.

A chirped-pulse Fourier-transform microwave/pulsed uniform flow spectrometer. I. The low-temperature flow system.

PubMed

Oldham, James M; Abeysekera, Chamara; Joalland, Baptiste; Zack, Lindsay N; Prozument, Kirill; Sims, Ian R; Park, G Barratt; Field, Robert W; Suits, Arthur G

2014-10-21

We report the development of a new instrument that combines chirped-pulse microwave spectroscopy with a pulsed uniform supersonic flow. This combination promises a nearly universal detection method that can deliver isomer and conformer specific, quantitative detection and spectroscopic characterization of unstable reaction products and intermediates, product vibrational distributions, and molecular excited states. This first paper in a series of two presents a new pulsed-flow design, at the heart of which is a fast, high-throughput pulsed valve driven by a piezoelectric stack actuator. Uniform flows at temperatures as low as 20 K were readily achieved with only modest pumping requirements, as demonstrated by impact pressure measurements and pure rotational spectroscopy. The proposed technique will be suitable for application in diverse fields including fundamental studies in spectroscopy, kinetics, and reaction dynamics.

Mode Reduction and Upscaling of Reactive Transport Under Incomplete Mixing

NASA Astrophysics Data System (ADS)

Lester, D. R.; Bandopadhyay, A.; Dentz, M.; Le Borgne, T.

2016-12-01

Upscaling of chemical reactions in partially-mixed fluid environments is a challenging problem due to the detailed interactions between inherently nonlinear reaction kinetics and complex spatio-temporal concentration distributions under incomplete mixing. We address this challenge via the development of an order reduction method for the advection-diffusion-reaction equation (ADRE) via projection of the reaction kinetics onto a small number N of leading eigenmodes of the advection-diffusion operator (the so-called "strange eigenmodes" of the flow) as an N-by-N nonlinear system, whilst mixing dynamics only are projected onto the remaining modes. For simple kinetics and moderate Péclet and Damkhöler numbers, this approach yields analytic solutions for the concentration mean, evolving spatio-temporal distribution and PDF in terms of the well-mixed reaction kinetics and mixing dynamics. For more complex kinetics or large Péclet or Damkhöler numbers only a small number of modes are required to accurately quantify the mixing and reaction dynamics in terms of the concentration field and PDF, facilitating greatly simplified approximation and analysis of reactive transport. Approximate solutions of this low-order nonlinear system provide quantiative predictions of the evolving concentration PDF. We demonstrate application of this method to a simple random flow and various mass-action reaction kinetics.

Six-flow operations for catalyst development in Fischer-Tropsch synthesis: Bridging the gap between high-throughput experimentation and extensive product evaluation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sartipi, Sina, E-mail: S.Sartipi@tudelft.nl, E-mail: J.Gascon@tudelft.nl; Jansma, Harrie; Bosma, Duco

2013-12-15

Design and operation of a “six-flow fixed-bed microreactor” setup for Fischer-Tropsch synthesis (FTS) is described. The unit consists of feed and mixing, flow division, reaction, separation, and analysis sections. The reactor system is made of five heating blocks with individual temperature controllers, assuring an identical isothermal zone of at least 10 cm along six fixed-bed microreactor inserts (4 mm inner diameter). Such a lab-scale setup allows running six experiments in parallel, under equal feed composition, reaction temperature, and conditions of separation and analysis equipment. It permits separate collection of wax and liquid samples (from each flow line), allowing operation with highmore » productivities of C5+ hydrocarbons. The latter is crucial for a complete understanding of FTS product compositions and will represent an advantage over high-throughput setups with more than ten flows where such instrumental considerations lead to elevated equipment volume, cost, and operation complexity. The identical performance (of the six flows) under similar reaction conditions was assured by testing a same catalyst batch, loaded in all microreactors.« less

Miniaturized flow injection analysis system

DOEpatents

Folta, James A.

1997-01-01

A chemical analysis technique known as flow injection analysis, wherein small quantities of chemical reagents and sample are intermixed and reacted within a capillary flow system and the reaction products are detected optically, electrochemically, or by other means. A highly miniaturized version of a flow injection analysis system has been fabricated utilizing microfabrication techniques common to the microelectronics industry. The microflow system uses flow capillaries formed by etching microchannels in a silicon or glass wafer followed by bonding to another wafer, commercially available microvalves bonded directly to the microflow channels, and an optical absorption detector cell formed near the capillary outlet, with light being both delivered and collected with fiber optics. The microflow system is designed mainly for analysis of liquids and currently measures 38.times.25.times.3 mm, but can be designed for gas analysis and be substantially smaller in construction.

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid.

PubMed

Aw, Alex; Fritz, Marshall; Napoline, Jonathan W; Pollet, Pamela; Liotta, Charles L

2017-11-15

Continuous flow technology has been identified as instrumental for its environmental and economic advantages leveraging superior mixing, heat transfer and cost savings through the "scaling out" strategy as opposed to the traditional "scaling up". Herein, we report the reaction of diphenyldiazomethane with p-nitrobenzoic acid in both batch and flow modes. To effectively transfer the reaction from batch to flow mode, it is essential to first conduct the reaction in batch. As a consequence, the reaction of diphenyldiazomethane was first studied in batch as a function of temperature, reaction time, and concentration to obtain kinetic information and process parameters. The glass flow reactor set-up is described and combines two types of reaction modules with "mixing" and "linear" microstructures. Finally, the reaction of diphenyldiazomethane with p-nitrobenzoic acid was successfully conducted in the flow reactor, with up to 95% conversion of the diphenyldiazomethane in 11 min. This proof of concept reaction aims to provide insight for scientists to consider flow technology's competitiveness, sustainability, and versatility in their research.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Camacho-Bunquin, Jeffrey; Shou, Heng; Marshall, Christopher L.

An integrated atomic layer deposition synthesis-catalysis (I-ALD-CAT) tool was developed. It combines an ALD manifold in-line with a plug-flow reactor system for the synthesis of supported catalytic materials by ALD and immediate evaluation of catalyst reactivity using gas-phase probe reactions. The I-ALD-CAT delivery system consists of 12 different metal ALD precursor channels, 4 oxidizing or reducing agents, and 4 catalytic reaction feeds to either of the two plug-flow reactors. The system can employ reactor pressures and temperatures in the range of 10{sup −3} to 1 bar and 300–1000 K, respectively. The instrument is also equipped with a gas chromatograph andmore » a mass spectrometer unit for the detection and quantification of volatile species from ALD and catalytic reactions. In this report, we demonstrate the use of the I-ALD-CAT tool for the synthesis of platinum active sites and Al{sub 2}O{sub 3} overcoats, and evaluation of catalyst propylene hydrogenation activity.« less

The reaction efficiency of thermal energy oxygen atoms with polymeric materials

NASA Technical Reports Server (NTRS)

Koontz, S. L.; Nordine, Paul

1990-01-01

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.

Incorporating reaction-rate dependence in reaction-front models of wellbore-cement/carbonated-brine systems

DOE PAGES

Iyer, Jaisree; Walsh, Stuart D. C.; Hao, Yue; ...

2017-03-08

Contact between wellbore cement and carbonated brine produces reaction zones that alter the cement's chemical composition and its mechanical properties. The reaction zones have profound implications on the ability of wellbore cement to serve as a seal to prevent the flow of carbonated brine. Under certain circumstances, the reactions may cause resealing of leakage pathways within the cement or at cement-interfaces; either due to fracture closure in response to mechanical weakening or due to the precipitation of calcium carbonate within the fracture. In prior work, we showed how mechanical sealing can be simulated using a diffusion-controlled reaction-front model that linksmore » the growth of the cement reaction zones to the mechanical response of the fracture. Here, we describe how such models may be extended to account for the effects of the calcite reaction-rate. We discuss how the relative rates of reaction and diffusion within the cement affect the precipitation of calcium carbonate within narrow leakage pathways, and how such behavior relates to the formation of characteristic reaction modes in the direction of flow. In addition, we compare the relative impact of precipitation and mechanical deformation on fracture sealing for a range of flow conditions and fracture apertures. Here, we conclude by considering how the prior leaching of calcium from cement may influence the sealing behavior of fractures, and the implication of prior leaching on the ability of laboratory tests to predict long-term sealing.« less

Incorporating reaction-rate dependence in reaction-front models of wellbore-cement/carbonated-brine systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iyer, Jaisree; Walsh, Stuart D. C.; Hao, Yue

Contact between wellbore cement and carbonated brine produces reaction zones that alter the cement's chemical composition and its mechanical properties. The reaction zones have profound implications on the ability of wellbore cement to serve as a seal to prevent the flow of carbonated brine. Under certain circumstances, the reactions may cause resealing of leakage pathways within the cement or at cement-interfaces; either due to fracture closure in response to mechanical weakening or due to the precipitation of calcium carbonate within the fracture. In prior work, we showed how mechanical sealing can be simulated using a diffusion-controlled reaction-front model that linksmore » the growth of the cement reaction zones to the mechanical response of the fracture. Here, we describe how such models may be extended to account for the effects of the calcite reaction-rate. We discuss how the relative rates of reaction and diffusion within the cement affect the precipitation of calcium carbonate within narrow leakage pathways, and how such behavior relates to the formation of characteristic reaction modes in the direction of flow. In addition, we compare the relative impact of precipitation and mechanical deformation on fracture sealing for a range of flow conditions and fracture apertures. Here, we conclude by considering how the prior leaching of calcium from cement may influence the sealing behavior of fractures, and the implication of prior leaching on the ability of laboratory tests to predict long-term sealing.« less

Continuous protein concentration via free-flow moving reaction boundary electrophoresis.

PubMed

Kong, Fanzhi; Zhang, Min; Chen, Jingjing; Fan, Liuyin; Xiao, Hua; Liu, Shaorong; Cao, Chengxi

2017-07-28

In this work, we developed the model and theory of free-flow moving reaction boundary electrophoresis (FFMRB) for continuous protein concentration for the first time. The theoretical results indicated that (i) the moving reaction boundary (MRB) can be quantitatively designed in free-flow electrophoresis (FFE) system; (ii) charge-to-mass ratio (Z/M) analysis could provide guidance for protein concentration optimization; and (iii) the maximum processing capacity could be predicted. To demonstrate the model and theory, three model proteins of hemoglobin (Hb), cytochrome C (Cyt C) and C-phycocyanin (C-PC) were chosen for the experiments. The experimental results verified that (i) stable MRBs with different velocities could be established in FFE apparatus with weak acid/weak base neutralization reaction system; (ii) proteins of Hb, Cyt C and C-PC were well concentrated with FFMRB; and (iii) a maximum processing capacity and recovery ratio of Cyt C enrichment were 126mL/h and 95.5% respectively, and a maximum enrichment factor was achieved 12.6 times for Hb. All of the experiments demonstrated the protein concentration model and theory. In contrast to other methods, the continuous processing ability enables FFMRB to efficiently enrich diluted protein or peptide in large volume solution. Copyright © 2017 Elsevier B.V. All rights reserved.

Anisotropic transverse mixing and its effect on reaction rates in multi-scale, 3D heterogeneous porous media

NASA Astrophysics Data System (ADS)

Engdahl, N. B.

2016-12-01

Mixing rates in porous media have been a heavily research topic in recent years covering analytic, random, and structured fields. However, there are some persistent assumptions and common features to these models that raise some questions about the generality of the results. One of these commonalities is the orientation of the flow field with respect to the heterogeneity structure, which are almost always defined to be parallel each other if there is an elongated axis of permeability correlation. Given the vastly different tortuosities for flow parallel to bedding and flow transverse to bedding, this assumption of parallel orientation may have significant effects on reaction rates when natural flows deviate from this assumed setting. This study investigates the role of orientation on mixing and reaction rates in multi-scale, 3D heterogeneous porous media with varying degrees of anisotropy in the correlation structure. Ten realizations of a small flow field, with three anisotropy levels, were simulated for flow parallel and transverse to bedding. Transport was simulated in each model with an advective-diffusive random walk and reactions were simulated using the chemical Langevin equation. The reaction system is a vertically segregated, transverse mixing problem between two mobile reactants. The results show that different transport behaviors and reaction rates are obtained by simply rotating the direction of flow relative to bedding, even when the net flux in both directions is the same. This kind of behavior was observed for three different weightings of the initial condition: 1) uniform, 2) flux-based, and 3) travel time based. The different schemes resulted in 20-50% more mass formation in the transverse direction than the longitudinal. The greatest variability in mass was observed for the flux weights and these were proportionate to the level of anisotropy. The implications of this study are that flux or travel time weights do not provide any guarantee of a fair comparison in this kind of a mixing scenario and that the role of directional tendencies on reaction rates can be significant. Further, it may be necessary to include anisotropy in future upscaled models to create robust methods that give representative reaction rates for any flow direction relative to geologic bedding.

The hard start phenomena in hypergolic engines. Volume 4: The chemistry of hydrazine fuels and nitrogen tetroxide propellant systems

NASA Technical Reports Server (NTRS)

Miron, Y.; Perlee, H. E.

1974-01-01

The various chemical reactions that occur and that could possibly occur in the RCS engines utilizing hydrazine-type fuel/nitrogen tetroxide propellant systems, prior to ignition (preignition), during combustion, and after combustion (postcombustion), and endeavors to relate the hard-start phenomenon to some of these reactions are discussed. The discussion is based on studies utilizing a variety of experimental techniques and apparatus as well as current theories of chemical reactions and reaction kinetics. The chemical reactions were studied in low pressure gas flow reactors, low temperature homogeneous- and heterogeneous-phase reactors, simulated two-dimensional (2-D) engines, and scaled and full size engines.

Dual-phase gas-permeation flow-injection thermometric analysis for the determination of carbon dioxide.

PubMed

Liu, S J; Tubino, M

1998-11-01

A flow-injection configuration based on a dual-phase gas-permeation system from a liquid donor to a gas acceptor stream with a thermistor flow-through detector is proposed for the direct analysis of the gas in the acceptor. This system was applied for the determination of carbon dioxide (in the form of carbonate) using the following chemical reaction: CO(2)(g)+2NH(3)(g)+H(2)O(g)=(NH(4))(2)CO(3)(s), with a linear response from 1x10(-3) to 50x10(-3) mol l(-1) of CO(3)(2-). Carbon dioxide was produced in the liquid donor and permeated into the gaseous acceptor stream of air/water vapor. The detection limit is 1x10(-3) mol l(-1) of carbonate, and a sampling frequency of 60 h(-1) is achieved with a relative standard deviation of 4.1% for replicate injections. The dual-phase gas-permeation flow-injection manifold, along with the membrane and phase separations, as well as the chemical reaction, provides enhanced selectivity when compared with the system employing a liquid acceptor stream, as serious interferents in this system, for instance, acetate and formate, among others, do not interfere in the proposed system.

Thermomyces lanuginosus lipase-catalyzed synthesis of natural flavor esters in a continuous flow microreactor.

PubMed

Gumel, Ahmad Mohammed; Annuar, M S M

2016-06-01

Enzymatic catalysis is considered to be among the most environmental friendly processes for the synthesis of fine chemicals. In this study, lipase from Thermomyces lanuginosus (Lecitase Ultra™) was used to catalyze the synthesis of flavor esters, i.e., methyl butanoate and methyl benzoate by esterification of the acids with methanol in a microfluidic system. Maximum reaction rates of 195 and 115 mM min -1 corresponding to catalytic efficiencies (k cat /K M ) of 0.30 and 0.24 min -1  mM -1 as well as yield conversion of 54 and 41 % were observed in methyl butanoate and methyl benzoate synthesis, respectively. Catalytic turnover (k cat ) was higher for methyl butanoate synthesis. Rate of synthesis and yield decreased with increasing flow rates. For both esters, increase in microfluidic flow rate resulted in increased advective transport over molecular diffusion and reaction rate, thus lower conversion. In microfluidic synthesis using T. lanuginosus lipase, the following reaction conditions were 40 °C, flow rate 0.1 mL min -1 , and 123 U g -1 enzyme loading found to be the optimum operating limits. The work demonstrated the application of enzyme(s) in a microreactor system for the synthesis of industrially important esters.

Kinetic studies of the yeast His-Asp phosphorelay signaling pathway

PubMed Central

Kaserer, Alla O.; Andi, Babak; Cook, Paul F.; West, Ann H.

2010-01-01

For both prokaryotic and eukaryotic His-Asp phosphorelay signaling pathways, the rates of protein phosphorylation and dephosphorylation determine the stimulus-to-response time frame. Thus, kinetic studies of phosphoryl group transfer between signaling partners are important for gaining a full understanding of how the system is regulated. In many cases, the phosphotransfer reactions are too fast for rates to be determined by manual experimentation. Rapid quench flow techniques thus provide a powerful method for studying rapid reactions that occur in the millisecond time frame. In this chapter, we describe experimental design and procedures for kinetic characterization of the yeast SLN1-YPD1-SSK1 osmoregulatory phosphorelay system using a rapid quench flow kinetic instrument. PMID:20946842

Preliminary assessment of the velocity pump reaction turbine as a geothermal total-flow expander

NASA Astrophysics Data System (ADS)

Demuth, O. J.

1984-06-01

The velocity pump reaction turbine (VPRT) was evaluated as a total flow expander in a geothermal-electric conversion cycle. Values of geofluid effectiveness of VPRT systems were estimated for conditions consisting of: a 360(F) geothermal resource, 60 F wet-bulb ambient temperature, zero and 0.003 mass concentrations of dissolved noncondensible gas in the geofluid, 100 and 120 F condensing temperatures, and engine efficiencies ranging from 0.4 to 1.0. Achievable engine efficiencies were estimated to range from 0.77, with plant geofluid effectiveness values ranging as high as 9.5 watt hr-lbm geofluid for the 360 F resource temperature. This value is competitive with magnitudes of geofluid effectiveness projected for advanced binary plants, and is on the order of 40% higher than estimates for dual-flash steam and other total flow systems reviewed. Because of its potentially high performance and relative simplicity, the VPRT system appears to warrant further investigation toward its use in a well-head geothermal plant.

Coupled alkali feldspar dissolution and secondary mineral precipitation in batch systems: 4. Numerical modeling of kinetic reaction paths

NASA Astrophysics Data System (ADS)

Zhu, Chen; Lu, Peng; Zheng, Zuoping; Ganor, Jiwchar

2010-07-01

This paper explores how dissolution and precipitation reactions are coupled in batch reactor experimental systems at elevated temperatures. This is the fourth paper in our series of "Coupled Alkali Feldspar Dissolution and Secondary Mineral Precipitation in Batch Systems". In our third paper, we demonstrated via speciation-solubility modeling that partial equilibrium between secondary minerals and aqueous solutions was not attained in feldspar hydrolysis batch reactors at 90-300 °C and that a strong coupling between dissolution and precipitation reactions follows as a consequence of the slower precipitation of secondary minerals ( Zhu and Lu, 2009). Here, we develop this concept further by using numerical reaction path models to elucidate how the dissolution and precipitation reactions are coupled. Modeling results show that a quasi-steady state was reached. At the quasi-steady state, dissolution reactions proceeded at rates that are orders of magnitude slower than the rates measured at far from equilibrium. The quasi-steady state is determined by the relative rate constants, and strongly influenced by the function of Gibbs free energy of reaction ( ΔG) in the rate laws. To explore the potential effects of fluid flow rates on the coupling of reactions, we extrapolate a batch system ( Ganor et al., 2007) to open systems and simulated one-dimensional reactive mass transport for oligoclase dissolution and kaolinite precipitation in homogeneous porous media. Different steady states were achieved at different locations along the one-dimensional domain. The time-space distribution and saturation indices (SI) at the steady states were a function of flow rates for a given kinetic model. Regardless of the differences in SI, the ratio between oligoclase dissolution rates and kaolinite precipitation rates remained 1.626, as in the batch system case ( Ganor et al., 2007). Therefore, our simulation results demonstrated coupling among dissolution, precipitation, and flow rates. Results reported in this communication lend support to our hypothesis that slow secondary mineral precipitation explains part of the well-known apparent discrepancy between lab measured and field estimated feldspar dissolution rates ( Zhu et al., 2004). Here we show how the slow secondary mineral precipitation provides a regulator to explain why the systems are held close to equilibrium and show how the most often-quoted "near equilibrium" explanation for an apparent field-lab discrepancy can work quantitatively. The substantiated hypothesis now offers the promise of reconciling part of the apparent field-lab discrepancy.

MODELING CHLORINE RESIDUALS IN DRINKING-WATER DISTRIBUTION SYSTEMS

EPA Science Inventory

A mass-transfer-based model is developed for predicting chlorine decay in drinking-water distribution networks. The model considers first-order reactions of chlorine to occur both in the bulk flow and at the pipe wall. The overall rate of the wall reaction is a function of the ...

MODELING CHLORINE RESIDUALS IN DRINKING-WATER DISTRIBUTION SYSTEMS

EPA Science Inventory

A mass transfer-based model is developed for predicting chlorine decay in drinking water distribution networks. he model considers first order reactions of chlorine to occur both in the bulk flow and at the pipe wall. he overall rate of the wall reaction is a function of the rate...

Research on Liquid Management Technology in Water Tank and Reactor for Propulsion System with Hydrogen Production System Utilizing Aluminum and Water Reaction

NASA Astrophysics Data System (ADS)

Imai, Ryoji; Imamura, Takuya; Sugioka, Masatoshi; Higashino, Kazuyuki

2017-12-01

High pressure hydrogen produced by aluminum and water reaction is considered to be applied to space propulsion system. Water tank and hydrogen production reactor in this propulsion system require gas and liquid separation function under microgravity condition. We consider to install vane type liquid acquisition device (LAD) utilizing surface tension in the water tank, and install gas-liquid separation mechanism by centrifugal force which swirling flow creates in the hydrogen reactor. In water tank, hydrophilic coating was covered on both tank wall and vane surface to improve wettability. Function of LAD in water tank and gas-liquid separation in reaction vessel were evaluated by short duration microgravity experiments using drop tower facility. In the water tank, it was confirmed that liquid was driven and acquired on the outlet due to capillary force created by vanes. In addition of this, it was found that gas-liquid separation worked well by swirling flow in hydrogen production reactor. However, collection of hydrogen gas bubble was sometimes suppressed by aluminum alloy particles, which is open problem to be solved.

[Electromagnetic radiation of non-thermal intensity and short exposition as a sub-threshold irritant for the central nervous system].

PubMed

Luk'ianova, S N

2013-01-01

This work represents generalization and the analysis of the long-term own materials characterizing reaction of the brain on electromagnetic radiation of low intensity (energy flow density in the continuous regime or in the impulse approximately 500 microW/sm2) and a short exposition (approximately 30 min). A set of the experimental results received on separate neurons, formations and brain as a whole give an idea about the reaction of the central nervous system to the studied influence. Comparison of these data with the corresponding responses to the known incentives (light, sound, electric current) testifies to the electromagnetic radiation of low energy flow density and a short exposition as a sub-threshold irritant for the central nervous system.

Survivability and Abiotic Reactions of Selected Amino Acids in Different Hydrothermal System Simulators

NASA Astrophysics Data System (ADS)

Chandru, Kuhan; Imai, Eiichi; Kaneko, Takeo; Obayashi, Yumiko; Kobayashi, Kensei

2013-04-01

We tested the stability and reaction of several amino acids using hydrothermal system simulators: an autoclave and two kinds of flow reactors at 200-250 °C. This study generally showed that there is a variation in the individual amino acids survivability in the simulators. This is mainly attributed to the following factors; heat time, cold quenching exposure, metal ions and also silica. We observed that, in a rapid heating flow reactor, high aggregation and/or condensation of amino acids could occur even during a heat exposure of 2 min. We also monitored their stability in a reflow-type of simulator for 120 min at 20 min intervals. The non-hydrolyzed and hydrolyzed samples for this system showed a similar degradation only in the absence of metal ions.

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

NASA Technical Reports Server (NTRS)

Sozen, Mehmet; Majumdar, Alok

2002-01-01

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

First experimental assessment of RCS plume-flow field interaction on Hermes leading edge thruster configuration

NASA Astrophysics Data System (ADS)

Poertner, T.

1993-11-01

Glow discharge flow visualization experiments are demonstrated which have been performed to enable a first assessment of the HERMES 1.0 leading edge thruster configuration concerning interference between the thruster plumes of the reaction control system (RCS) and the surrounding flow field. The results of the flow visualization tests are presented in exemplary selected photographs. Additional Pitot pressure measurements support assumptions concerning interference induced pressure changes that may result from the observed significant flow field disturbances.

PHAST--a program for simulating ground-water flow, solute transport, and multicomponent geochemical reactions

USGS Publications Warehouse

Parkhurst, David L.; Kipp, Kenneth L.; Engesgaard, Peter; Charlton, Scott R.

2004-01-01

The computer program PHAST simulates multi-component, reactive solute transport in three-dimensional saturated ground-water flow systems. PHAST is a versatile ground-water flow and solute-transport simulator with capabilities to model a wide range of equilibrium and kinetic geochemical reactions. The flow and transport calculations are based on a modified version of HST3D that is restricted to constant fluid density and constant temperature. The geochemical reactions are simulated with the geochemical model PHREEQC, which is embedded in PHAST. PHAST is applicable to the study of natural and contaminated ground-water systems at a variety of scales ranging from laboratory experiments to local and regional field scales. PHAST can be used in studies of migration of nutrients, inorganic and organic contaminants, and radionuclides; in projects such as aquifer storage and recovery or engineered remediation; and in investigations of the natural rock-water interactions in aquifers. PHAST is not appropriate for unsaturated-zone flow, multiphase flow, density-dependent flow, or waters with high ionic strengths. A variety of boundary conditions are available in PHAST to simulate flow and transport, including specified-head, flux, and leaky conditions, as well as the special cases of rivers and wells. Chemical reactions in PHAST include (1) homogeneous equilibria using an ion-association thermodynamic model; (2) heterogeneous equilibria between the aqueous solution and minerals, gases, surface complexation sites, ion exchange sites, and solid solutions; and (3) kinetic reactions with rates that are a function of solution composition. The aqueous model (elements, chemical reactions, and equilibrium constants), minerals, gases, exchangers, surfaces, and rate expressions may be defined or modified by the user. A number of options are available to save results of simulations to output files. The data may be saved in three formats: a format suitable for viewing with a text editor; a format suitable for exporting to spreadsheets and post-processing programs; or in Hierarchical Data Format (HDF), which is a compressed binary format. Data in the HDF file can be visualized on Windows computers with the program Model Viewer and extracted with the utility program PHASTHDF; both programs are distributed with PHAST. Operator splitting of the flow, transport, and geochemical equations is used to separate the three processes into three sequential calculations. No iterations between transport and reaction calculations are implemented. A three-dimensional Cartesian coordinate system and finite-difference techniques are used for the spatial and temporal discretization of the flow and transport equations. The non-linear chemical equilibrium equations are solved by a Newton-Raphson method, and the kinetic reaction equations are solved by a Runge-Kutta or an implicit method for integrating ordinary differential equations. The PHAST simulator may require large amounts of memory and long Central Processing Unit (CPU) times. To reduce the long CPU times, a parallel version of PHAST has been developed that runs on a multiprocessor computer or on a collection of computers that are networked. The parallel version requires Message Passing Interface, which is currently (2004) freely available. The parallel version is effective in reducing simulation times. This report documents the use of the PHAST simulator, including running the simulator, preparing the input files, selecting the output files, and visualizing the results. It also presents four examples that verify the numerical method and demonstrate the capabilities of the simulator. PHAST requires three input files. Only the flow and transport file is described in detail in this report. The other two files, the chemistry data file and the database file, are identical to PHREEQC files and the detailed description of these files is found in the PHREEQC documentation.

Parallel array of nanochannels grafted with polymer-brushes-stabilized Au nanoparticles for flow-through catalysis.

PubMed

Liu, Jianxi; Ma, Shuanhong; Wei, Qiangbing; Jia, Lei; Yu, Bo; Wang, Daoai; Zhou, Feng

2013-12-07

Smart systems on the nanometer scale for continuous flow-through reaction present fascinating advantages in heterogeneous catalysis, in which a parallel array of straight nanochannels offers a platform with high surface area for assembling and stabilizing metallic nanoparticles working as catalysts. Herein we demonstrate a method for finely modifying the nanoporous anodic aluminum oxide (AAO), and further integration of nanoreactors. By using atomic transfer radical polymerization (ATRP), polymer brushes were successfully grafted on the inner wall of the nanochannels of the AAO membrane, followed by exchanging counter ions with a precursor for nanoparticles (NPs), and used as the template for deposition of well-defined Au NPs. The membrane was used as a functional nanochannel for novel flow-through catalysis. High catalytic performance and instantaneous separation of products from the reaction system was achieved in reduction of 4-nitrophenol.

Parallel array of nanochannels grafted with polymer-brushes-stabilized Au nanoparticles for flow-through catalysis

NASA Astrophysics Data System (ADS)

Liu, Jianxi; Ma, Shuanhong; Wei, Qiangbing; Jia, Lei; Yu, Bo; Wang, Daoai; Zhou, Feng

2013-11-01

Smart systems on the nanometer scale for continuous flow-through reaction present fascinating advantages in heterogeneous catalysis, in which a parallel array of straight nanochannels offers a platform with high surface area for assembling and stabilizing metallic nanoparticles working as catalysts. Herein we demonstrate a method for finely modifying the nanoporous anodic aluminum oxide (AAO), and further integration of nanoreactors. By using atomic transfer radical polymerization (ATRP), polymer brushes were successfully grafted on the inner wall of the nanochannels of the AAO membrane, followed by exchanging counter ions with a precursor for nanoparticles (NPs), and used as the template for deposition of well-defined Au NPs. The membrane was used as a functional nanochannel for novel flow-through catalysis. High catalytic performance and instantaneous separation of products from the reaction system was achieved in reduction of 4-nitrophenol.

Practical thermodynamic quantities for aqueous vanadium- and iron-based flow batteries

DOE PAGES

Hudak, Nicholas S.

2013-12-31

A simple method for experimentally determining thermodynamic quantities for flow battery cell reactions is presented. Equilibrium cell potentials, temperature derivatives of cell potential (d E/d T), Gibbs free energies, and entropies are reported here for all-vanadium, iron–vanadium, and iron–chromium flow cells with state-of-the-art solution compositions. Proof is given that formal potentials and formal temperature coefficients can be used with modified forms of the Nernst Equation to quantify the thermodynamics of flow cell reactions as a function of state-of-charge. Such empirical quantities can be used in thermo-electrochemical models of flow batteries at the cell or system level. In most cases, themore » thermodynamic quantities measured here are significantly different from standard values reported and used previously in the literature. The data reported here are also useful in the selection of operating temperatures for flow battery systems. Because higher temperatures correspond to lower equilibrium cell potentials for the battery chemistries studied here, it can be beneficial to charge a cell at higher temperature and discharge at lower temperature. As a result, proof-of-concept of improved voltage efficiency with the use of such non-isothermal cycling is given for the all-vanadium redox flow battery, and the effect is shown to be more pronounced at lower current densities.« less

Flow through PCR module of BioBriefcase

NASA Astrophysics Data System (ADS)

Arroyo, E.; Wheeler, E. K.; Shediac, R.; Hindson, B.; Nasarabadi, S.; Vrankovich, G.; Bell, P.; Bailey, C.; Sheppod, T.; Christian, A. T.

2005-11-01

The BioBriefcase is an integrated briefcase-sized aerosol collection and analysis system for autonomous monitoring of the environment, which is currently being jointly developed by Lawrence Livermore and Sandia National Laboratories. This poster presents results from the polymerase chain reaction (PCR) module of the system. The DNA must be purified after exiting the aerosol collector to prevent inhibition of the enzymatic reaction. Traditional solid-phase extraction results in a large loss of sample. In this flow-through system, we perform sample purification, concentration and amplification in one reactor, which minimizes the loss of material. The sample from the aerosol collector is mixed with a denaturation solution prior to flowing through a capillary packed with silica beads. The DNA adheres to the silica beads allowing the environmental contaminants to be flushed to waste while effectively concentrating the DNA on the silica matrix. The adhered DNA is amplified while on the surface of the silica beads, resulting in a lower limit of detection than an equivalent eluted sample. Thus, this system is beneficial since more DNA is available for amplification, less reagents are utilized, and contamination risks are reduced.

Enhanced reaction kinetics and reactive mixing scale dynamics in mixing fronts under shear flow for arbitrary Damköhler numbers

NASA Astrophysics Data System (ADS)

Bandopadhyay, Aditya; Le Borgne, Tanguy; Méheust, Yves; Dentz, Marco

2017-02-01

Mixing fronts, where fluids of different chemical compositions mix with each other, are known to represent hotspots of chemical reaction in hydrological systems. These fronts are typically subjected to velocity gradients, ranging from the pore scale due to no slip boundary conditions at fluid solid interfaces, to the catchment scale due to permeability variations and complex geometry of the Darcy velocity streamlines. A common trait of these processes is that the mixing interface is strained by shear. Depending on the Péclet number Pe , which represents the ratio of the characteristic diffusion time to the characteristic shear time, and the Damköhler number Da , which represents the ratio of the characteristic diffusion time to the characteristic reaction time, the local reaction rates can be strongly impacted by the dynamics of the mixing interface. So far, this impact has been characterized mostly either in kinetics-limited or in mixing-limited conditions, that is, for either low or high Da. Here the coupling of shear flow and chemical reactivity is investigated for arbitrary Damköhler numbers, for a bimolecular reaction and an initial interface with separated reactants. Approximate analytical expressions for the global production rate and reactive mixing scale are derived based on a reactive lamella approach that allows for a general coupling between stretching enhanced mixing and chemical reactions. While for Pe < Da , reaction kinetics and stretching effects are decoupled, a scenario which we name "weak stretching", for Pe > Da , we uncover a "strong stretching" scenario where new scaling laws emerge from the interplay between reaction kinetics, diffusion, and stretching. The analytical results are validated against numerical simulations. These findings shed light on the effect of flow heterogeneity on the enhancement of chemical reaction and the creation of spatially localized hotspots of reactivity for a broad range of systems ranging from kinetic limited to mixing limited situations.

Direct-injection chemiluminescence detector. Properties and potential applications in flow analysis.

PubMed

Koronkiewicz, Stanislawa; Kalinowski, Slawomir

2015-02-01

We present a novel chemiluminescence detector, with a cone-shaped detection chamber where the analytical reaction takes place. The sample and appropriate reagents are injected directly into the chamber in countercurrent using solenoid-operated pulse micro-pumps. The proposed detector allows for fast measurement of the chemiluminescence signal in stop-flow conditions from the moment of reagents mixing. To evaluate potential applications of the detector the Fenton-like reaction with a luminol-H2O2 system and several transition metal ions (Co(2+), Cu(2+), Cr(3+), Fe(3+)) as a catalyst were investigated. The results demonstrate suitability of the proposed detector for quantitative analysis and for investigations of reaction kinetics, particularly rapid reactions. A multi-pumping flow system was designed and optimized. The developed methodology demonstrated that the shape of the analytical signals strongly depends on the type and concentration of the metal ions. The application of the detector in quantitative analysis was assessed for determination of Fe(III). The direct-injection chemiluminescence detector allows for a sensitive and repeatable (R.S.D. 2%) determination. The intensity of chemiluminescence increased linearly in the range from about 0.5 to 10 mg L(-1) Fe(III) with the detection limit of 0.025 mg L(-1). The time of analysis depended mainly on reaction kinetics. It is possible to achieve the high sampling rate of 144 samples per hour. Copyright © 2014 Elsevier B.V. All rights reserved.

STUDY OF MERCURY OXIDATION BY SCR CATALYST IN AN ENTRAINED-FLOW REACTOR UNDER SIMULATED PRB CONDITIONS

EPA Science Inventory

A bench-scale entrained-flow reactor system was constructed for studying elemental mercury oxidation under selective catalytic reduction (SCR) reaction conditions. Simulated flue gas was doped with fly ash collected from a subbituminous Powder River Basin (PRB) coal-fired boiler ...

Miniaturized flow injection analysis system

DOEpatents

Folta, J.A.

1997-07-01

A chemical analysis technique known as flow injection analysis is described, wherein small quantities of chemical reagents and sample are intermixed and reacted within a capillary flow system and the reaction products are detected optically, electrochemically, or by other means. A highly miniaturized version of a flow injection analysis system has been fabricated utilizing microfabrication techniques common to the microelectronics industry. The microflow system uses flow capillaries formed by etching microchannels in a silicon or glass wafer followed by bonding to another wafer, commercially available microvalves bonded directly to the microflow channels, and an optical absorption detector cell formed near the capillary outlet, with light being both delivered and collected with fiber optics. The microflow system is designed mainly for analysis of liquids and currently measures 38{times}25{times}3 mm, but can be designed for gas analysis and be substantially smaller in construction. 9 figs.

Modeling chemical gradients in sediments under losing and gaining flow conditions: The GRADIENT code

NASA Astrophysics Data System (ADS)

Boano, Fulvio; De Falco, Natalie; Arnon, Shai

2018-02-01

Interfaces between sediments and water bodies often represent biochemical hotspots for nutrient reactions and are characterized by steep concentration gradients of different reactive solutes. Vertical profiles of these concentrations are routinely collected to obtain information on nutrient dynamics, and simple codes have been developed to analyze these profiles and determine the magnitude and distribution of reaction rates within sediments. However, existing publicly available codes do not consider the potential contribution of water flow in the sediments to nutrient transport, and their applications to field sites with significant water-borne nutrient fluxes may lead to large errors in the estimated reaction rates. To fill this gap, the present work presents GRADIENT, a novel algorithm to evaluate distributions of reaction rates from observed concentration profiles. GRADIENT is a Matlab code that extends a previously published framework to include the role of nutrient advection, and provides robust estimates of reaction rates in sediments with significant water flow. This work discusses the theoretical basis of the method and shows its performance by comparing the results to a series of synthetic data and to laboratory experiments. The results clearly show that in systems with losing or gaining fluxes, the inclusion of such fluxes is critical for estimating local and overall reaction rates in sediments.

Mass spectrometric directed system for the continuous-flow synthesis and purification of diphenhydramine.

PubMed

Loren, Bradley P; Wleklinski, Michael; Koswara, Andy; Yammine, Kathryn; Hu, Yanyang; Nagy, Zoltan K; Thompson, David H; Cooks, R Graham

2017-06-01

A highly integrated approach to the development of a process for the continuous synthesis and purification of diphenhydramine is reported. Mass spectrometry (MS) is utilized throughout the system for on-line reaction monitoring, off-line yield quantitation, and as a reaction screening module that exploits reaction acceleration in charged microdroplets for high throughput route screening. This effort has enabled the discovery and optimization of multiple routes to diphenhydramine in glass microreactors using MS as a process analytical tool (PAT). The ability to rapidly screen conditions in charged microdroplets was used to guide optimization of the process in a microfluidic reactor. A quantitative MS method was developed and used to measure the reaction kinetics. Integration of the continuous-flow reactor/on-line MS methodology with a miniaturized crystallization platform for continuous reaction monitoring and controlled crystallization of diphenhydramine was also achieved. Our findings suggest a robust approach for the continuous manufacture of pharmaceutical drug products, exemplified in the particular case of diphenhydramine, and optimized for efficiency and crystal size, and guided by real-time analytics to produce the agent in a form that is readily adapted to continuous synthesis.

Remote calorimetric detection of urea via flow injection analysis

PubMed Central

Gaddes, David E.; Demirel, Melik C.; Reeves, W. Brian; Tadigadapa, Srinivas

2017-01-01

The design and development of a calorimetric biosensing system enabling relatively high throughput sample analysis are reported. The calorimetric biosensor system consists of a thin (~20 μm) micromachined Y-cut quartz crystal resonator (QCR) as a temperature sensor placed in close proximity to a fluidic chamber packed with an immobilized enzyme. Layer by layer enzyme immobilization of urease is demonstrated and its activity as a function of the number of layers, pH, and time has been evaluated. This configuration enables a sensing system where a transducer element is physically separated from the analyte solution of interest and is thereby free from fouling effects typically associated with biochemical reactions occuring on the sensor surface. The performance of this biosensing system is demonstrated by detection of 1–200 mM urea in phosphate buffer via a flow injection analysis (FIA) technique. Miniaturized fluidic systems were used to provide continuous flow through a reaction column. Under this configuration the biosensor has an ultimate resolution of less than 1 mM urea and showed a linear response between 0–50 mM. This work demonstrates a sensing modality in which the sensor itself is not fouled or contaminated by the solution of interest and the enzyme immobilized Kapton® fluidic reaction column can be used as a disposable cartridge. Such a system enables reuse and reliability for long term sampling measurements. Based on this concept a biosensing system is envisioned which can perform rapid measurements to detect biomarkers such as glucose, creatinine, cholesterol, urea and lactate in urine and blood continuously over extended periods of time. PMID:26479269

Remote calorimetric detection of urea via flow injection analysis.

PubMed

Gaddes, David E; Demirel, Melik C; Reeves, W Brian; Tadigadapa, Srinivas

2015-12-07

The design and development of a calorimetric biosensing system enabling relatively high throughput sample analysis are reported. The calorimetric biosensor system consists of a thin (∼20 μm) micromachined Y-cut quartz crystal resonator (QCR) as a temperature sensor placed in close proximity to a fluidic chamber packed with an immobilized enzyme. Layer by layer enzyme immobilization of urease is demonstrated and its activity as a function of the number of layers, pH, and time has been evaluated. This configuration enables a sensing system where a transducer element is physically separated from the analyte solution of interest and is thereby free from fouling effects typically associated with biochemical reactions occuring on the sensor surface. The performance of this biosensing system is demonstrated by detection of 1-200 mM urea in phosphate buffer via a flow injection analysis (FIA) technique. Miniaturized fluidic systems were used to provide continuous flow through a reaction column. Under this configuration the biosensor has an ultimate resolution of less than 1 mM urea and showed a linear response between 0-50 mM. This work demonstrates a sensing modality in which the sensor itself is not fouled or contaminated by the solution of interest and the enzyme immobilized Kapton® fluidic reaction column can be used as a disposable cartridge. Such a system enables reuse and reliability for long term sampling measurements. Based on this concept a biosensing system is envisioned which can perform rapid measurements to detect biomarkers such as glucose, creatinine, cholesterol, urea and lactate in urine and blood continuously over extended periods of time.

Optimization of information content in a mass spectrometry based flow-chemistry system by investigating different ionization approaches.

PubMed

Martha, Cornelius T; Hoogendoorn, Jan-Carel; Irth, Hubertus; Niessen, Wilfried M A

2011-05-15

Current development in catalyst discovery includes combinatorial synthesis methods for the rapid generation of compound libraries combined with high-throughput performance-screening methods to determine the associated activities. Of these novel methodologies, mass spectrometry (MS) based flow chemistry methods are especially attractive due to the ability to combine sensitive detection of the formed reaction product with identification of introduced catalyst complexes. Recently, such a mass spectrometry based continuous-flow reaction detection system was utilized to screen silver-adducted ferrocenyl bidentate catalyst complexes for activity in a multicomponent synthesis of a substituted 2-imidazoline. Here, we determine the merits of different ionization approaches by studying the combination of sensitive detection of product formation in the continuous-flow system with the ability to simultaneous characterize the introduced [ferrocenyl bidentate+Ag](+) catalyst complexes. To this end, we study the ionization characteristics of electrospray ionization (ESI), atmospheric-pressure chemical ionization (APCI), no-discharge APCI, dual ESI/APCI, and dual APCI/no-discharge APCI. Finally, we investigated the application potential of the different ionization approaches by the investigation of ferrocenyl bidentate catalyst complex responses in different solvents. Copyright © 2011 Elsevier B.V. All rights reserved.

Small-volume, ultrahigh-vacuum-compatible high-pressure reaction cell for combined kinetic and in situ IR spectroscopic measurements on planar model catalysts

NASA Astrophysics Data System (ADS)

Zhao, Z.; Diemant, T.; Häring, T.; Rauscher, H.; Behm, R. J.

2005-12-01

We describe the design and performance of a high-pressure reaction cell for simultaneous kinetic and in situ infrared reflection (IR) spectroscopic measurements on model catalysts at elevated pressures, between 10-3 and 103mbars, which can be operated both as batch reactor and as flow reactor with defined gas flow. The cell is attached to an ultrahigh-vacuum (UHV) system, which is used for sample preparation and also contains facilities for sample characterization. Specific for this design is the combination of a small cell volume, which allows kinetic measurements with high sensitivity under batch or continuous flow conditions, the complete isolation of the cell from the UHV part during UHV measurements, continuous temperature control during both UHV and high-pressure operation, and rapid transfer between UHV and high-pressure stage. Gas dosing is performed by a designed gas-handling system, which allows operation as flow reactor with calibrated gas flows at adjustable pressures. To study the kinetics of reactions on the model catalysts, a quadrupole mass spectrometer is connected to the high-pressure cell. IR measurements are possible in situ by polarization-modulation infrared reflection-absorption spectroscopy, which also allows measurements at elevated pressures. The performance of the setup is demonstrated by test measurements on the kinetics for CO oxidation and the CO adsorption on a Au /TiO2/Ru(0001) model catalyst film at 1-50 mbar total pressure.

CFD propels NASP propulsion progress

NASA Technical Reports Server (NTRS)

Povinelli, Louis A.; Dwoyer, Douglas L.; Green, Michael J.

1990-01-01

The most complex aerothermodynamics encountered in the National Aerospace Plane (NASP) propulsion system are associated with the fuel-mixing and combustion-reaction flows of its combustor section; adequate CFD tools must be developed to model shock-wave systems, turbulent hydrogen/air mixing, flow separation, and combustion. Improvements to existing CFD codes have involved extension from two dimensions to three, as well as the addition of finite-rate hydrogen-air chemistry. A novel CFD code for the treatment of reacting flows throughout the NASP, designated GASP, uses the most advanced upwind-differencing technology.

CFD propels NASP propulsion progress

NASA Astrophysics Data System (ADS)

Povinelli, Louis A.; Dwoyer, Douglas L.; Green, Michael J.

1990-07-01

The most complex aerothermodynamics encountered in the National Aerospace Plane (NASP) propulsion system are associated with the fuel-mixing and combustion-reaction flows of its combustor section; adequate CFD tools must be developed to model shock-wave systems, turbulent hydrogen/air mixing, flow separation, and combustion. Improvements to existing CFD codes have involved extension from two dimensions to three, as well as the addition of finite-rate hydrogen-air chemistry. A novel CFD code for the treatment of reacting flows throughout the NASP, designated GASP, uses the most advanced upwind-differencing technology.

MERCURY REACTIONS IN THE PRESENCE OF CHLORINE SPECIES: HOMOGENOUS GAS PHASE AND HETEROGENOUS GAS-SOLID PHASE

EPA Science Inventory

The kinetics of mercury chlorination (with HC1) were studied using a flow reactor system with an on-line Hg analyzer and spciation sampling using a set of impingers. Kinetic parameters, such as reaction order (a), activation energy (Eu) and the overall rate constant (k') were es...

Renewable Wood Pulp Paper Reactor with Hierarchical Micro/Nanopores for Continuous-Flow Nanocatalysis.

PubMed

Koga, Hirotaka; Namba, Naoko; Takahashi, Tsukasa; Nogi, Masaya; Nishina, Yuta

2017-06-22

Continuous-flow nanocatalysis based on metal nanoparticle catalyst-anchored flow reactors has recently provided an excellent platform for effective chemical manufacturing. However, there has been limited progress in porous structure design and recycling systems for metal nanoparticle-anchored flow reactors to create more efficient and sustainable catalytic processes. In this study, traditional paper is used for a highly efficient, recyclable, and even renewable flow reactor by tailoring the ultrastructures of wood pulp. The "paper reactor" offers hierarchically interconnected micro- and nanoscale pores, which can act as convective-flow and rapid-diffusion channels, respectively, for efficient access of reactants to metal nanoparticle catalysts. In continuous-flow, aqueous, room-temperature catalytic reduction of 4-nitrophenol to 4-aminophenol, a gold nanoparticle (AuNP)-anchored paper reactor with hierarchical micro/nanopores provided higher reaction efficiency than state-of-the-art AuNP-anchored flow reactors. Inspired by traditional paper materials, successful recycling and renewal of AuNP-anchored paper reactors were also demonstrated while high reaction efficiency was maintained. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Renewable Wood Pulp Paper Reactor with Hierarchical Micro/Nanopores for Continuous‐Flow Nanocatalysis

PubMed Central

Namba, Naoko; Takahashi, Tsukasa; Nogi, Masaya; Nishina, Yuta

2017-01-01

Abstract Continuous‐flow nanocatalysis based on metal nanoparticle catalyst‐anchored flow reactors has recently provided an excellent platform for effective chemical manufacturing. However, there has been limited progress in porous structure design and recycling systems for metal nanoparticle‐anchored flow reactors to create more efficient and sustainable catalytic processes. In this study, traditional paper is used for a highly efficient, recyclable, and even renewable flow reactor by tailoring the ultrastructures of wood pulp. The “paper reactor” offers hierarchically interconnected micro‐ and nanoscale pores, which can act as convective‐flow and rapid‐diffusion channels, respectively, for efficient access of reactants to metal nanoparticle catalysts. In continuous‐flow, aqueous, room‐temperature catalytic reduction of 4‐nitrophenol to 4‐aminophenol, a gold nanoparticle (AuNP)‐anchored paper reactor with hierarchical micro/nanopores provided higher reaction efficiency than state‐of‐the‐art AuNP‐anchored flow reactors. Inspired by traditional paper materials, successful recycling and renewal of AuNP‐anchored paper reactors were also demonstrated while high reaction efficiency was maintained. PMID:28394501

A Pilot Study of Ion - Molecule Reactions at Temperatures Relevant to the Atmosphere of Titan.

PubMed

Zymak, Illia; Žabka, Ján; Polášek, Miroslav; Španěl, Patrik; Smith, David

2016-11-01

Reliable theoretical models of the chemical kinetics of the ionosphere of Saturn's moon, Titan, is highly dependent on the precision of the rates of the reactions of ambient ions with hydrocarbon molecules at relevant temperatures. A Variable Temperature Selected Ions Flow Tube technique, which has been developed primarily to study these reactions at temperatures within the range of 200-330 K, is briefly described. The flow tube temperature regulation system and the thermalisation of ions are also discussed. Preliminary studies of two reactions have been carried out to check the reliability and efficacy of kinetics measurements: (i) Rate constants of the reaction of CH 3 + ions with molecular oxygen were measured at different temperatures, which indicate values in agreement with previous ion cyclotron resonance measurements ostensibly made at 300 K. (ii) Formation of CH 3 + ions in the reaction of N 2 + ions with CH 4 molecules were studied at temperatures within the range 240-310 K which showed a small but statistically significant decrease of the ratio of product CH 3 + ions to reactant N 2 + ions with reaction temperature.

Continuous formation of N-chloro-N,N-dialkylamine solutions in well-mixed meso-scale flow reactors

PubMed Central

Jolley, Katherine E

2015-01-01

Summary The continuous flow synthesis of a range of organic solutions of N,N-dialkyl-N-chloramines is described using either a bespoke meso-scale tubular reactor with static mixers or a continuous stirred tank reactor. Both reactors promote the efficient mixing of a biphasic solution of N,N-dialkylamine in organic solvent, and aqueous sodium hypochlorite to achieve near quantitative conversions, in 72–100% in situ yields, and useful productivities of around 0.05 mol/h with residence times from 3 to 20 minutes. Initial calorimetric studies have been carried out to inform on reaction exotherms, rates and safe operation. Amines which partition mainly in the organic phase require longer reaction times, provided by the CSTR, to compensate for low mass transfer rates in the biphasic system. The green metrics of the reaction have been assessed and compared to existing procedures and have shown the continuous process is improved over previous procedures. The organic solutions of N,N-dialkyl-N-chloramines produced continuously will enable their use in tandem flow reactions with a range of nucleophilic substrates. PMID:26734089

Subnanogram determination of aniracetam in pharmaceutical preparations and biofluids by flow injection analysis with chemiluminescence detection based on its enhancement of the myoglobin-luminol reaction.

PubMed

Shao, Xiaodong; Li, Ying; Li, Fagen; Liu, Yangqin; Song, Zhenghua

2011-01-01

A novel flow injection chemiluminescence method with a myoglobin-luminol system is described for determining aniracetam. Myoglobin-bound aniracetam produced a complex that catalyzed the chemiluminescence reaction between luminol and myoglobin, leading to fast chemiluminescence. The chemiluminescence intensity in the presence of aniracetam was remarkably enhanced compared with that in the absence of aniracetam. Under the optimum reaction conditions the chemiluminescence increment produced was proportional to the concentration of aniracetam in the range of 0.1-1000.0 ng/mL (R2 = 0.9992), with a detection limit of 0.03 ng/mL (3delta). At a flow rate of 2.0 mL/min, the whole process, including sampling and washing, could be completed in 0.5 min, offering a sampling efficiency of 120/h; the RSD was less than 3.0% (n = 5). The method was satisfactory for determination of aniracetam in pharmaceutical preparations and human urine and serum samples. A possible mechanism of the reaction is also discussed.

Melting Heat in Radiative Flow of Carbon Nanotubes with Homogeneous-Heterogeneous Reactions

NASA Astrophysics Data System (ADS)

Hayat, Tasawar; Muhammad, Khursheed; Muhammad, Taseer; Alsaedi, Ahmed

2018-04-01

The present article provides mathematical modeling for melting heat and thermal radiation in stagnation-point flow of carbon nanotubes towards a nonlinear stretchable surface of variable thickness. The process of homogeneous-heterogeneous reactions is considered. Diffusion coefficients are considered equal for both reactant and autocatalyst. Water and gasoline oil are taken as base fluids. The conversion of partial differential system to ordinary differential system is done by suitable transformations. Optimal homotopy technique is employed for the solutions development of velocity, temperature, concentration, skin friction and local Nusselt number. Graphical results for various values of pertinent parameters are displayed and discussed. Our results indicate that the skin friction coefficient and local Nusselt number are enhanced for larger values of nanoparticles volume fraction.

Solute transport with equilibrium aqueous complexation and either sorption or ion exchange: Simulation methodology and applications

USGS Publications Warehouse

Lewis, F.M.; Voss, C.I.; Rubin, J.

1987-01-01

Methodologies that account for specific types of chemical reactions in the simulation of solute transport can be developed so they are compatible with solution algorithms employed in existing transport codes. This enables the simulation of reactive transport in complex multidimensional flow regimes, and provides a means for existing codes to account for some of the fundamental chemical processes that occur among transported solutes. Two equilibrium-controlled reaction systems demonstrate a methodology for accommodating chemical interaction into models of solute transport. One system involves the sorption of a given chemical species, as well as two aqueous complexations in which the sorbing species is a participant. The other reaction set involves binary ion exchange coupled with aqueous complexation involving one of the exchanging species. The methodology accommodates these reaction systems through the addition of nonlinear terms to the transport equations for the sorbing species. Example simulation results show (1) the effect equilibrium chemical parameters have on the spatial distributions of concentration for complexing solutes; (2) that an interrelationship exists between mechanical dispersion and the various reaction processes; (3) that dispersive parameters of the porous media cannot be determined from reactive concentration distributions unless the reaction is accounted for or the influence of the reaction is negligible; (4) how the concentration of a chemical species may be significantly affected by its participation in an aqueous complex with a second species which also sorbs; and (5) that these coupled chemical processes influencing reactive transport can be demonstrated in two-dimensional flow regimes. ?? 1987.

Combustion chamber analysis code

NASA Technical Reports Server (NTRS)

Przekwas, A. J.; Lai, Y. G.; Krishnan, A.; Avva, R. K.; Giridharan, M. G.

1993-01-01

A three-dimensional, time dependent, Favre averaged, finite volume Navier-Stokes code has been developed to model compressible and incompressible flows (with and without chemical reactions) in liquid rocket engines. The code has a non-staggered formulation with generalized body-fitted-coordinates (BFC) capability. Higher order differencing methodologies such as MUSCL and Osher-Chakravarthy schemes are available. Turbulent flows can be modeled using any of the five turbulent models present in the code. A two-phase, two-liquid, Lagrangian spray model has been incorporated into the code. Chemical equilibrium and finite rate reaction models are available to model chemically reacting flows. The discrete ordinate method is used to model effects of thermal radiation. The code has been validated extensively against benchmark experimental data and has been applied to model flows in several propulsion system components of the SSME and the STME.

Synthesis of carbon nanofibers by catalytic CVD of chlorobenzene over bulk nickel alloy

NASA Astrophysics Data System (ADS)

Kenzhin, Roman M.; Bauman, Yuri I.; Volodin, Alexander M.; Mishakov, Ilya V.; Vedyagin, Aleksey A.

2018-01-01

Catalytic chemical vapor deposition (CCVD) of chlorobenzene over bulk nickel alloy (nichrome) was studied. The bulk Ni-containing samples being exposed to a contact with aggressive reaction medium undergo self-disintegration followed by growth of carbon nanofibers. This process, also known as a metal dusting, requires the simultaneous presence of chlorine and hydrogen sources in the reaction mixture. Molecule of chlorobenzene complies with these requirements. The experiments on CCVD were performed in a flow-through reactor system. The initial stages of nickel disintegration process were investigated in a closed system under Autogenic Pressure at Elevated Temperature (RAPET) conditions. Scanning and transmission electron microscopies and ferromagnetic resonance spectroscopy were applied to examine the samples after their interaction with chlorobenzene. Introduction of additional hydrogen into the flow-through system was shown to affect the morphology of grown carbon nanofibers.

Identifying the Oscillatory Mechanism of the Glucose Oxidase-Catalase Coupled Enzyme System.

PubMed

Muzika, František; Jurašek, Radovan; Schreiberová, Lenka; Radojković, Vuk; Schreiber, Igor

2017-10-12

We provide experimental evidence of periodic and aperiodic oscillations in an enzymatic system of glucose oxidase-catalase in a continuous-flow stirred reactor coupled by a membrane with a continuous-flow reservoir supplied with hydrogen peroxide. To describe such dynamics, we formulate a detailed mechanism based on partial results in the literature. Finally, we introduce a novel method for estimation of unknown kinetic parameters. The method is based on matching experimental data at an oscillatory instability with stoichiometric constraints of the mechanism formulated by applying the stability theory of reaction networks. This approach has been used to estimate rate coefficients in the catalase part of the mechanism. Remarkably, model simulations show good agreement with the observed oscillatory dynamics, including apparently chaotic intermittent behavior. Our method can be applied to any reaction system with an experimentally observable dynamical instability.

Flow-driven pattern formation in the calcium-oxalate system.

PubMed

Bohner, Bíborka; Endrődi, Balázs; Horváth, Dezső; Tóth, Ágota

2016-04-28

The precipitation reaction of calcium oxalate is studied experimentally in the presence of spatial gradients by controlled flow of calcium into oxalate solution. The density difference between the reactants leads to strong convection in the form of a gravity current that drives the spatiotemporal pattern formation. The phase diagram of the system is constructed, the evolving precipitate patterns are analyzed and quantitatively characterized by their diameters and the average height of the gravity flow. The compact structures of calcium oxalate monohydrate produced at low flow rates are replaced by the thermodynamically unstable calcium oxalate dihydrate favored in the presence of a strong gravity current.

Redox flow batteries having multiple electroactive elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Wei; Li, Liyu; Yang, Zhenguo

Introducing multiple redox reactions with a suitable voltage range can improve the energy density of redox flow battery (RFB) systems. One example includes RFB systems utilizing multiple redox pairs in the positive half cell, the negative half cell, or in both. Such RFB systems can have a negative electrolyte, a positive electrolyte, and a membrane between the negative electrolyte and the positive electrolyte, in which at least two electrochemically active elements exist in the negative electrolyte, the positive electrolyte, or both.

PLIF Imaging of Capsule RCS Jets, Shear Layers, and Simulated Forebody Ablation

NASA Technical Reports Server (NTRS)

Inman, Jennifer A.; Danehy, Paul M.; Alderfer, David W.; Buck, Gregory M.; McCrea, Andrew

2008-01-01

Planar laser-induced fluorescence (PLIF) has been used to investigate hypersonic flows associated with capsule reentry vehicles. These flows included reaction control system (RCS) jets, shear layer flow, and simulated forebody heatshield ablation. Pitch, roll, and yaw RCS jets were studied. PLIF obtained planar slices in these flowfields. These slices could be viewed individually or they could be combined using computer visualization techniques to reconstruct the three dimensional shape of the flow. The tests described herein were conducted in the 31-Inch Mach 10 Air Tunnel at NASA Langley Research Center. Improvements to many facets of the imaging system increased the efficiency and quality of both data acquisition, in addition to increasing the overall robustness of the system.

Chemically generated convective transport in microfluidic system

NASA Astrophysics Data System (ADS)

Shklyaev, Oleg; Das, Sambeeta; Altemose, Alicia; Shum, Henry; Balazs, Anna; Sen, Ayusman

High precision manipulation of small volumes of fluid, containing suspended micron sized objects like cells, viruses, and large molecules, is one of the main goals in designing modern lab-on-a-chip devices which can find a variety of chemical and biological applications. To transport the cargo toward sensing elements, typical microfluidic devices often use pressure driven flows. Here, we propose to use enzymatic chemical reactions which decompose reagent into less dense products and generate flows that can transport particles. Density variations that lead to flow in the assigned direction are created between the place where reagent is fed into the solution and the location where it is decomposed by enzymes attached to the surface of the microchannel. When the reagent is depleted, the fluid motion stops and particles sediment to the bottom. We demonstrate how the choice of chemicals, leading to specific reaction rates, can affect the transport properties. In particular, we show that the intensity of the fluid flow, the final location of cargo, and the time for cargo delivery are controlled by the amount and type of reagent in the system.

Microchemical Pen: An Open Microreactor for Region-Selective Surface Modification.

PubMed

Mao, Sifeng; Sato, Chiho; Suzuki, Yuma; Yang, Jianmin; Zeng, Hulie; Nakajima, Hizuru; Yang, Ming; Lin, Jin-Ming; Uchiyama, Katsumi

2016-10-18

Various micro surface-modification approaches including photolithography, dip-pen lithography and ink-jet systems have been developed and used to extend the functionalities of solid surfaces. While those approaches work in the "open space", push-pull systems which work in solutions have recently drawn considerable attention. However, the confining flows performed by push-pull systems have realized only the dispense process, while microscale, region-selective chemical reactions have remained unattainable. This study reports a microchemical pen that enables region-selective chemical reactions for the micro surface modification/patterning. The chemical pen is based on the principle of microfluidic laminar flows and the resulting mixing of reagents by the mutual diffusion. The tiny diffusion layer performs as the working region. This report represents the first demonstration of an open microreactor in which two different reagents react on a real solid sample. The multifunctional characteristics of the microchemical pen are confirmed by different types of reactions in many research areas, including inorganic chemistry, polymer science, electrochemistry and biological sample treatment. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical pump study for Pioneer Venus program

NASA Technical Reports Server (NTRS)

Rotheram, M.

1973-01-01

Two chemical pumps were designed for the Pioneer Venus large probe mass spectrometer. Factors involved in the design selection are reviewed. One pump is designed to process a sample of the Venus atmosphere to remove the major component, carbon dioxide, so that the minor, inert components may be measured with greater sensitivity. The other pump is designed to promote flow of atmospheric gas through a pressure reduction inlet system. This pump, located downstream from the mass spectrometer sampling point, provides the pressure differential required for flow through the inlet system. Both pumps utilize the reaction of carbon dioxide with lithium hydroxide. The available data for this reaction was reviewed with respect to the proposed applications, and certain deficiencies in reaction rate data at higher carbon dioxide pressures noted. The chemical pump designed for the inert gas experiment has an estimated volume of 30 cu cm and weight of 80 grams, exclusive of the four valves required for the operation. The chemical pump for the pressure reduction inlet system is designed for a total sample of 0.3 bar liter during the Venus descent.

Pumping power considerations in the designs of NASA-Redox flow cells

NASA Technical Reports Server (NTRS)

Hoberecht, M. A.

1981-01-01

Pressure drop data for six different cell geometries of various flow port, manifold, and cavity dimensions are presented. The redox/energy/storage system uses two fully soluble redox couples as anode and cathode fluids. Both fluids are pumped through a redox cell, or stack of cells, where the electrochemical reactions take place at porous carbon felt electrodes. Pressure drop losses are therefore associated with this system due to the continuous flow of reactant solutions. The exact pressure drop within a redox flow cell is directly dependent on the flow rate as well as the various cell dimensions. Pumping power requirements for a specific set of cell operating conditions are found for various cell geometries once the flow rate and pressure drop are determined. These pumping power requirements contribute to the overall system parasitic energy losses which must be minimized, the choice of cell geometry becomes critical.

Automated Water-Purification System

NASA Technical Reports Server (NTRS)

Ahlstrom, Harlow G.; Hames, Peter S.; Menninger, Fredrick J.

1988-01-01

Reverse-osmosis system operates and maintains itself with minimal human attention, using programmable controller. In purifier, membranes surround hollow cores through which clean product water flows out of reverse-osmosis unit. No chemical reactions or phase changes involved. Reject water, in which dissolved solids concentrated, emerges from outer membrane material on same side water entered. Flow controls maintain ratio of 50 percent product water and 50 percent reject water. Membranes expected to last from 3 to 15 years.

Heat and mass transfer in unsteady rotating fluid flow with binary chemical reaction and activation energy.

PubMed

Awad, Faiz G; Motsa, Sandile; Khumalo, Melusi

2014-01-01

In this study, the Spectral Relaxation Method (SRM) is used to solve the coupled highly nonlinear system of partial differential equations due to an unsteady flow over a stretching surface in an incompressible rotating viscous fluid in presence of binary chemical reaction and Arrhenius activation energy. The velocity, temperature and concentration distributions as well as the skin-friction, heat and mass transfer coefficients have been obtained and discussed for various physical parametric values. The numerical results obtained by (SRM) are then presented graphically and discussed to highlight the physical implications of the simulations.

Numerical study for melting heat transfer and homogeneous-heterogeneous reactions in flow involving carbon nanotubes

NASA Astrophysics Data System (ADS)

Hayat, Tasawar; Muhammad, Khursheed; Alsaedi, Ahmed; Asghar, Saleem

2018-03-01

Present work concentrates on melting heat transfer in three-dimensional flow of nanofluid over an impermeable stretchable surface. Analysis is made in presence of porous medium and homogeneous-heterogeneous reactions. Single and multi-wall CNTs (carbon nanotubes) are considered. Water is chosen as basefluid. Adequate transformations yield the non-linear ordinary differential systems. Solution of emerging problems is obtained using shooting method. Impacts of influential variables on velocity and temperature are discussed graphically. Skin friction coefficient and Nusselt number are numerically discussed. The results for MWCNTs and SWCNTs are compared and examined.

Heat and Mass Transfer in Unsteady Rotating Fluid Flow with Binary Chemical Reaction and Activation Energy

PubMed Central

Awad, Faiz G.; Motsa, Sandile; Khumalo, Melusi

2014-01-01

In this study, the Spectral Relaxation Method (SRM) is used to solve the coupled highly nonlinear system of partial differential equations due to an unsteady flow over a stretching surface in an incompressible rotating viscous fluid in presence of binary chemical reaction and Arrhenius activation energy. The velocity, temperature and concentration distributions as well as the skin-friction, heat and mass transfer coefficients have been obtained and discussed for various physical parametric values. The numerical results obtained by (SRM) are then presented graphically and discussed to highlight the physical implications of the simulations. PMID:25250830

Numerical analysis of MHD Carreau fluid flow over a stretching cylinder with homogenous-heterogeneous reactions

NASA Astrophysics Data System (ADS)

Khan, Imad; Ullah, Shafquat; Malik, M. Y.; Hussain, Arif

2018-06-01

The current analysis concentrates on the numerical solution of MHD Carreau fluid flow over a stretching cylinder under the influences of homogeneous-heterogeneous reactions. Modelled non-linear partial differential equations are converted into ordinary differential equations by using suitable transformations. The resulting system of equations is solved with the aid of shooting algorithm supported by fifth order Runge-Kutta integration scheme. The impact of non-dimensional governing parameters on the velocity, temperature, skin friction coefficient and local Nusselt number are comprehensively delineated with the help of graphs and tables.

Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

PubMed

Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

2015-10-01

Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Effect of Gravity on the Combustion Synthesis of Porous Ceramics and Metal Matrix Composites

NASA Technical Reports Server (NTRS)

Moore, J. J.; Woodger, T. C.; Wolanski, T.; Yi, H. C.; Guigne, J. Y.

1997-01-01

Combustion synthesis (self propagating, high temperature synthesis-SHS) is a novel technique that is capable of producing many advanced materials. The ignition temperature (Tig) of such combustion synthesis reactions is often coincident with that of the lowest melting point reactant. The resultant liquid metal wets and spreads around the other solid reactant particles of higher melting points, thereby improving the reactant contact and kinetics, followed by formation of the required compounds. This ignition initiates a combustion propagating wave whose narrow reaction front rapidly travels through the reactants. Since this process is highly exothermic, the heat released by combustion often melts the reactant particles ahead of the combustion front and ignites the adjacent reactant layer, resulting in a self-sustaining reaction. Whenever a fluid phase (liquid or gas) is generated by the reaction system, gravity-driven phenomena can occur. Such phenomena include convective flows of fluid by conventional or unstable convection and settling of the higher density phases. A combustion process is often associated with various kinds of fluid flow. For instance, if the SHS reaction is carried out under inert or reactive gas atmospheres, or a volatile, e.g., B2O3, is deliberately introduced as a reactant, convective flows of the gas will occur due to a temperature gradient existing in the atmosphere when a combustion wave is initiated. The increased gas flow will produce a porous (or expanded) SHS product. Owing to the highly exothermic nature of many SHS reactions, liquid phase(s) can also form before, at, or after the combustion front. The huge temperature gradient at the combustion front can induce convective flows (conventional or unstable) of the liquid phase. Each of these types of convective fluid flow can change the combustion behavior of the synthesizing reaction, and, therefore, the resultant product microstructure. In addition, when two or more phases of different density are produced at or ahead of the propagating combustion front settling of the higher density phase will occur resulting in a non-uniform product microstructure and properties.

Unity and diversity in mixing: Stretching, diffusion, breakup, and aggregation in chaotic flows

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ottino, J.M.

1991-05-01

Experiments and theory have produced a reasonably good qualitative understanding of the evolution of chaotic mixing of passive tracers, especially in two-dimensional time-periodic flow fields. Such an understanding forms a fabric for the evolution of breakup, aggregation, and diffusion-controlled reactions in more complex flows. These systems can be viewed as a population of microstructures'' whose behavior is dictated by iterations of a chaotic flow; microstructures break, diffuse, and aggregate, causing the population to evolve in space and time. This paper presents simple physical models for such processes. Self-similarity is common to all the problems; examples arise in the context ofmore » the distribution of stretchings within chaotic flows, in the asymptotic evolution of diffusion-reaction processes at striation thickness scales, in the equilibrium distribution of drop sizes generated upon mixing of immiscible fluids, in the equations describing mean-field kinetics of coagulation, in the sequence of actions necessary for the destruction of islands in two-dimensional flow, and in the fractal structure of clusters produced upon aggregation in chaotic flows.« less

Numerical analysis of exhaust jet secondary combustion in hypersonic flow field

NASA Astrophysics Data System (ADS)

Yang, Tian-Peng; Wang, Jiang-Feng; Zhao, Fa-Ming; Fan, Xiao-Feng; Wang, Yu-Han

2018-05-01

The interaction effect between jet and control surface in supersonic and hypersonic flow is one of the key problems for advanced flight control system. The flow properties of exhaust jet secondary combustion in a hypersonic compression ramp flow field were studied numerically by solving the Navier-Stokes equations with multi-species and combustion reaction effects. The analysis was focused on the flow field structure and the force amplification factor under different jet conditions. Numerical results show that a series of different secondary combustion makes the flow field structure change regularly, and the temperature increases rapidly near the jet exit.

Immobilised enzyme microreactor for screening of multi-step bioconversions: characterisation of a de novo transketolase-ω-transaminase pathway to synthesise chiral amino alcohols.

PubMed

Matosevic, S; Lye, G J; Baganz, F

2011-09-20

Complex molecules are synthesised via a number of multi-step reactions in living cells. In this work, we describe the development of a continuous flow immobilized enzyme microreactor platform for use in evaluation of multi-step bioconversion pathways demonstrating a de novo transketolase/ω-transaminase-linked asymmetric amino alcohol synthesis. The prototype dual microreactor is based on the reversible attachment of His₆-tagged enzymes via Ni-NTA linkage to two surface derivatised capillaries connected in series. Kinetic parameters established for the model transketolase (TK)-catalysed conversion of lithium-hydroxypyruvate (Li-HPA) and glycolaldehyde (GA) to L-erythrulose using a continuous flow system with online monitoring of reaction output was in good agreement with kinetic parameters determined for TK in stop-flow mode. By coupling the transketolase catalysed chiral ketone forming reaction with the biocatalytic addition of an amine to the TK product using a transaminase (ω-TAm) it is possible to generate chiral amino alcohols from achiral starting compounds. We demonstrated this in a two-step configuration, where the TK reaction was followed by the ω-TAm-catalysed amination of L-erythrulose to synthesise 2-amino-1,3,4-butanetriol (ABT). Synthesis of the ABT product via the dual reaction and the on-line monitoring of each component provided a full profile of the de novo two-step bioconversion and demonstrated the utility of this microreactor system to provide in vitro multi-step pathway evaluation. Copyright © 2011 Elsevier B.V. All rights reserved.

Thermodynamics and combustion modeling

NASA Technical Reports Server (NTRS)

Zeleznik, Frank J.

1986-01-01

Modeling fluid phase phenomena blends the conservation equations of continuum mechanics with the property equations of thermodynamics. The thermodynamic contribution becomes especially important when the phenomena involve chemical reactions as they do in combustion systems. The successful study of combustion processes requires (1) the availability of accurate thermodynamic properties for both the reactants and the products of reaction and (2) the computational capabilities to use the properties. A discussion is given of some aspects of the problem of estimating accurate thermodynamic properties both for reactants and products of reaction. Also, some examples of the use of thermodynamic properties for modeling chemically reacting systems are presented. These examples include one-dimensional flow systems and the internal combustion engine.

A compositional framework for reaction networks

NASA Astrophysics Data System (ADS)

Baez, John C.; Pollard, Blake S.

Reaction networks, or equivalently Petri nets, are a general framework for describing processes in which entities of various kinds interact and turn into other entities. In chemistry, where the reactions are assigned ‘rate constants’, any reaction network gives rise to a nonlinear dynamical system called its ‘rate equation’. Here we generalize these ideas to ‘open’ reaction networks, which allow entities to flow in and out at certain designated inputs and outputs. We treat open reaction networks as morphisms in a category. Composing two such morphisms connects the outputs of the first to the inputs of the second. We construct a functor sending any open reaction network to its corresponding ‘open dynamical system’. This provides a compositional framework for studying the dynamics of reaction networks. We then turn to statics: that is, steady state solutions of open dynamical systems. We construct a ‘black-boxing’ functor that sends any open dynamical system to the relation that it imposes between input and output variables in steady states. This extends our earlier work on black-boxing for Markov processes.

A fluorescence-based centrifugal microfluidic system for parallel detection of multiple allergens

NASA Astrophysics Data System (ADS)

Chen, Q. L.; Ho, H. P.; Cheung, K. L.; Kong, S. K.; Suen, Y. K.; Kwan, Y. W.; Li, W. J.; Wong, C. K.

2010-02-01

This paper reports a robust polymer based centrifugal microfluidic analysis system that can provide parallel detection of multiple allergens in vitro. Many commercial food products (milk, bean, pollen, etc.) may introduce allergy to people. A low-cost device for rapid detection of allergens is highly desirable. With this as the objective, we have studied the feasibility of using a rotating disk device incorporating centrifugal microfluidics for performing actuationfree and multi-analyte detection of different allergen species with minimum sample usage and fast response time. Degranulation in basophils or mast cells is an indicator to demonstrate allergic reaction. In this connection, we used acridine orange (AO) to demonstrate degranulation in KU812 human basophils. It was found that the AO was released from granules when cells were stimulated by ionomycin, thus signifying the release of histamine which accounts for allergy symptoms [1-2]. Within this rotating optical platform, major microfluidic components including sample reservoirs, reaction chambers, microchannel and flow-control compartments are integrated into a single bio-compatible polydimethylsiloxane (PDMS) substrate. The flow sequence and reaction time can be controlled precisely. Sequentially through varying the spinning speed, the disk may perform a variety of steps on sample loading, reaction and detection. Our work demonstrates the feasibility of using centrifugation as a possible immunoassay system in the future.

Redox flow cell energy storage systems

NASA Technical Reports Server (NTRS)

Thaller, L. H.

1979-01-01

NASA-Redox systems are electrochemical storage devices that use two fully soluble Redox couples, anode and cathode fluids, as active electrode materials separated by a highly selective ion exchange membrane. The reactants are contained in large storage tanks and pumped through a stack of Redox flow cells where the electrochemical reactions (reduction and oxidation) take place at porous carbon felt electrodes. A string or stack of these power producing cells is connected in series in a bipolar manner. Redox energy storage systems promise to be inexpensive and possess many features that provide for flexible design, long life, high reliability and minimal operation and maintenance costs. These features include independent sizing of power and storage capacity requirements and inclusion within the cell stack of a cell that monitors the state of charge of the system as a whole, and a rebalance cell which permits continuous correction to be made for minor side reactions that would tend to result in the anode fluid and cathode fluids becoming electrochemically out of balance. These system features are described and discussed.

Methodologies for extracting kinetic constants for multiphase reacting flow simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, S.L.; Lottes, S.A.; Golchert, B.

1997-03-01

Flows in industrial reactors often involve complex reactions of many species. A computational fluid dynamics (CFD) computer code, ICRKFLO, was developed to simulate multiphase, multi-species reacting flows. The ICRKFLO uses a hybrid technique to calculate species concentration and reaction for a large number of species in a reacting flow. This technique includes a hydrodynamic and reacting flow simulation with a small but sufficient number of lumped reactions to compute flow field properties followed by a calculation of local reaction kinetics and transport of many subspecies (order of 10 to 100). Kinetic rate constants of the numerous subspecies chemical reactions aremore » difficult to determine. A methodology has been developed to extract kinetic constants from experimental data efficiently. A flow simulation of a fluid catalytic cracking (FCC) riser was successfully used to demonstrate this methodology.« less

Analytical Solution for Transport with Bimolecular Reactions in Fracture-Matrix Systems with Application to In-Situ Chemical Oxidation

NASA Astrophysics Data System (ADS)

Rajaram, H.; Arshadi, M.

2016-12-01

In-situ chemical oxidation (ISCO) is an effective strategy for remediation of DNAPL contamination in fractured rock. During ISCO, an oxidant (e.g. permanganate) is typically injected through fractures and is consumed by bimolecular reactions with DNAPLs such as TCE and natural organic matter in the fracture and the adjacent rock matrix. Under these conditions, moving reaction fronts form and propagate along the fracture and into the rock matrix. The propagation of these reaction fronts is strongly influenced by the heterogeneity/discontinuity across the fracture-matrix interface (advective transport dominates in the fractures, while diffusive transport dominates in the rock matrix). We present analytical solutions for the concentrations of the oxidant, TCE and natural organic matter; and the propagation of the reaction fronts in a fracture-matrix system. Our approximate analytical solutions assume advection and reaction dominate over diffusion/dispersion in the fracture and neglect the latter. Diffusion and reaction with both TCE and immobile natural organic matter in the rock matrix are considered. The behavior of the reaction-diffusion equations in the rock matrix is posed as a Stefan problem where the diffusing oxidant reacts with both diffusing (TCE) and immobile (natural organic matter) reductants. Our analytical solutions establish that the reaction fronts propagate diffusively (i.e. as the square root of time) in both the matrix and the fracture. Our analytical solutions agree very well with numerical simulations for the case of uniform advection in the fracture. We also present extensions of our analytical solutions to non-uniform flows in the fracture by invoking a travel-time transformation. The non-uniform flow solutions are relevant to field applications of ISCO. The approximate analytical solutions are relevant to a broad class of reactive transport problems in fracture-matrix systems where moving reaction fronts occur.

Numerical simulations of turbulent jet ignition and combustion

NASA Astrophysics Data System (ADS)

Validi, Abdoulahad; Irannejad, Abolfazl; Jaberi, Farhad

2013-11-01

The ignition and combustion of a homogeneous lean hydrogen-air mixture by a turbulent jet flow of hot combustion products injected into a colder gas mixture are studied by a high fidelity numerical model. Turbulent jet ignition can be considered as an efficient method for starting and controlling the reaction in homogeneously charged combustion systems used in advanced internal combustion and gas turbine engines. In this work, we study in details the physics of turbulent jet ignition in a fundamental flow configuration. The flow and combustion are modeled with the hybrid large eddy simulation/filtered mass density function (LES/FMDF) approach, in which the filtered form the compressible Navier-Stokes equations are solved with a high-order finite difference scheme for the turbulent velocity and the FMDF transport equations are solved with a Lagrangian stochastic method to obtain the scalar (temperature and species mass fractions) field. The hydrogen oxidation is described by a detailed reaction mechanism with 37 elementary reactions and 9 species.

Interfacial Area Development in Two-Phase Fluid Flow: Transient vs. Quasi-Static Flow Conditions

NASA Astrophysics Data System (ADS)

Meisenheimer, D. E.; Wildenschild, D.

2017-12-01

Fluid-fluid interfaces are important in multiphase flow systems in the environment (e.g. groundwater remediation, geologic CO2 sequestration) and industry (e.g. air stripping, fuel cells). Interfacial area controls mass transfer, and therefore reaction efficiency, between the different phases in these systems but they also influence fluid flow processes. There is a need to better understand this relationship between interfacial area and fluid flow processes so that more robust theories and models can be built for engineers and policy makers to improve the efficacy of many multiphase flow systems important to society. Two-phase flow experiments were performed in glass bead packs under transient and quasi-static flow conditions. Specific interfacial area was calculated from 3D images of the porous media obtained using the fast x-ray microtomography capability at the Advanced Photon Source. We present data suggesting a direct relationship between the transient nature of the fluid-flow experiment (fewer equilibrium points) and increased specific interfacial area. The effect of flow condition on Euler characteristic (a representative measure of fluid topology) will also be presented.

A Catalyst-Free Amination of Functional Organolithium Reagents by Flow Chemistry.

PubMed

Kim, Heejin; Yonekura, Yuya; Yoshida, Jun-Ichi

2018-04-03

Reported is the electrophilic amination of functional organolithium intermediates with well-designed aminating reagents under mild reaction conditions using flow microreactors. The aminating reagents were optimized to achieve efficient C-N bond formation without using any catalyst. The electrophilic amination reactions of functionalized aryllithiums were successfully conducted under mild reaction conditions, within 1 minute, by using flow microreactors. The aminating reagent was also prepared by the flow method. Based on stopped-flow NMR analysis, the reaction time for the preparation of the aminating reagent was quickly optimized without the necessity of work-up. Integrated one-flow synthesis consisting of the generation of an aryllithium, the preparation of an aminating reagent, and their combined reaction was successfully achieved to give the desired amine within 5 minutes of total reaction time. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemiluminescence from an oxidation reaction of rhodamine B with cerium(IV) in a reversed micellar medium of cetyltrimethylammonium chloride in 1-hexanol-cyclohexane/water.

PubMed

Hasanin, Tamer H A; Tsunemine, Yusuke; Tsukahara, Satoshi; Okamoto, Yasuaki; Fujiwara, Terufumi

2011-01-01

The chemiluminescence (CL) emission, observed when rhodamine B (RB) in 1-hexanol-cyclohexane was mixed with cerium(IV) sulfate in sulfuric acid dispersed in a reversed micellar medium of cetyltrimethylammonium chloride (CTAC) in 1-hexanol-cyclohexane/water, was investigated using a flow-injection system. The CL emission from the oxidation reaction of RB with Ce(IV) was found to be stronger in the CTAC reversed micellar solution compared with an aqueous solution. Bearing on the enhancement effect of the CTAC reverse micelles on the RB-Ce(IV) CL, several studies including stopped-flow, fluorescence and electron spin resonance (ESR) spectrometries were performed. Rapid spectral changes of an intermediate in the RB-Ce(IV) reaction in the aqueous and reversed micellar solutions were successfully observed using a stopped-flow method. The effect of the experimental variables, i.e., oxidant concentration, sulfuric acid concentration, the mole fraction of 1-hexanol, water-to-surfactant molar concentration ratio, flow rate, upon the CL intensity was evaluated. Under the experimental conditions optimized for a flow-injection determination of RB based on the new reversed micellar-mediated CL reaction with Ce(IV), a detection limit of 0.08 µmol dm(-3) RB was achieved, and a linear calibration graph was obtained with a dynamic range from 0.5 to 20 µmol dm(-3). The relative standard deviation (n = 6) obtained at an RB concentration of 3 µmol dm(-3) was 3%.

Development of a chemiluminescent and bioluminescent system for the detection of bacteria in wastewater effluent

NASA Technical Reports Server (NTRS)

Thomas, R. R.

1975-01-01

Automated chemiluminescent and bioluminescent sensors were developed for continuous monitoring of microbial levels in wastewater effluent. Development of the chemiluminescent system included optimization of reagent concentrations as well as two new techniques which will allow for increased sensitivity and specificity. The optimal reagent concentrations are 0.0025 M luminol and 0.0125 M sodium perborate in 0.75N sodium hydroxide before addition of sample. The methods developed to increase specificity include (1) extraction of porphyrins from bacteria collected in a filter using 0.1N NaOH - 50 percent Ethanol, and (2) use of the specific reaction rate characteristics for the different luminol catalysts. Since reaction times are different for each catalyst, the reaction can be made specific for bacteria by measuring only the light emission from the particular reaction time zone specific for bacteria. Developments of the bioluminescent firefly luciferase system were in the area of flow system design.

Double stratification effects in chemically reactive squeezed Sutterby fluid flow with thermal radiation and mixed convection

NASA Astrophysics Data System (ADS)

Ahmad, S.; Farooq, M.; Javed, M.; Anjum, Aisha

2018-03-01

A current analysis is carried out to study theoretically the mixed convection characteristics in squeezing flow of Sutterby fluid in squeezed channel. The constitutive equation of Sutterby model is utilized to characterize the rheology of squeezing phenomenon. Flow characteristics are explored with dual stratification. In flowing fluid which contains heat and mass transport, the first order chemical reaction and radiative heat flux affect the transport phenomenon. The systems of non-linear governing equations have been modulating which then solved by mean of convergent approach (Homotopy Analysis Method). The graphs are reported and illustrated for emerging parameters. Through graphical explanations, drag force, rate of heat and mass transport are conversed for different pertinent parameters. It is found that heat and mass transport rate decays with dominant double stratified parameters and chemical reaction parameter. The present two-dimensional examination is applicable in some of the engineering processes and industrial fluid mechanics.

A two-dimensional numerical simulation of a supersonic, chemically reacting mixing layer

NASA Technical Reports Server (NTRS)

Drummond, J. Philip

1988-01-01

Research has been undertaken to achieve an improved understanding of physical phenomena present when a supersonic flow undergoes chemical reaction. A detailed understanding of supersonic reacting flows is necessary to successfully develop advanced propulsion systems now planned for use late in this century and beyond. In order to explore such flows, a study was begun to create appropriate physical models for describing supersonic combustion, and to develop accurate and efficient numerical techniques for solving the governing equations that result from these models. From this work, two computer programs were written to study reacting flows. Both programs were constructed to consider the multicomponent diffusion and convection of important chemical species, the finite rate reaction of these species, and the resulting interaction of the fluid mechanics and the chemistry. The first program employed a finite difference scheme for integrating the governing equations, whereas the second used a hybrid Chebyshev pseudospectral technique for improved accuracy.

Computational Fluid Dynamics–Discrete Element Method (CFD-DEM) Study of Mass-Transfer Mechanisms in Riser Flow

PubMed Central

2017-01-01

We report a computational fluid dynamics–discrete element method (CFD-DEM) simulation study on the interplay between mass transfer and a heterogeneous catalyzed chemical reaction in cocurrent gas-particle flows as encountered in risers. Slip velocity, axial gas dispersion, gas bypassing, and particle mixing phenomena have been evaluated under riser flow conditions to study the complex system behavior in detail. The most important factors are found to be directly related to particle cluster formation. Low air-to-solids flux ratios lead to more heterogeneous systems, where the cluster formation is more pronounced and mass transfer more influenced. Falling clusters can be partially circumvented by the gas phase, which therefore does not fully interact with the cluster particles, leading to poor gas–solid contact efficiencies. Cluster gas–solid contact efficiencies are quantified at several gas superficial velocities, reaction rates, and dilution factors in order to gain more insight regarding the influence of clustering phenomena on the performance of riser reactors. PMID:28553011

Computational Fluid Dynamics-Discrete Element Method (CFD-DEM) Study of Mass-Transfer Mechanisms in Riser Flow.

PubMed

Carlos Varas, Álvaro E; Peters, E A J F; Kuipers, J A M

2017-05-17

We report a computational fluid dynamics-discrete element method (CFD-DEM) simulation study on the interplay between mass transfer and a heterogeneous catalyzed chemical reaction in cocurrent gas-particle flows as encountered in risers. Slip velocity, axial gas dispersion, gas bypassing, and particle mixing phenomena have been evaluated under riser flow conditions to study the complex system behavior in detail. The most important factors are found to be directly related to particle cluster formation. Low air-to-solids flux ratios lead to more heterogeneous systems, where the cluster formation is more pronounced and mass transfer more influenced. Falling clusters can be partially circumvented by the gas phase, which therefore does not fully interact with the cluster particles, leading to poor gas-solid contact efficiencies. Cluster gas-solid contact efficiencies are quantified at several gas superficial velocities, reaction rates, and dilution factors in order to gain more insight regarding the influence of clustering phenomena on the performance of riser reactors.

ESM of ionic and electrochemical phenomena on the nanoscale

DOE PAGES

Kalinin, Sergei V.; Kumar, Amit; Balke, Nina; ...

2011-01-01

Operation of energy storage and conversion devices is ultimately controlled by series of intertwined ionic and electronic transport processes and electrochemical reactions at surfaces and interfaces, strongly mediated by strain and mechanical processes. In a typical fuel cell, these include chemical species transport in porous cathode and anode materials, gas-solid electrochemical reactions at grains and triple-phase boundaries (TPBs), ionic and electronic flows in multicomponent electrodes, and chemical and electronic potential drops at internal interfaces in electrodes and electrolytes. Furthermore, all these phenomena are sensitively affected by the microstructure of materials from device level to the atomic scales. Similar spectrum ofmore » length scales and phenomena underpin operation of other energy systems including primary and secondary batteries, as well as hybrid systems such flow and metal-air/water batteries.« less

Nonequilibrium thermodynamics and boundary conditions for reaction and transport in heterogeneous media

NASA Astrophysics Data System (ADS)

Gaspard, Pierre; Kapral, Raymond

2018-05-01

Nonequilibrium interfacial thermodynamics is formulated in the presence of surface reactions for the study of diffusiophoresis in isothermal systems. As a consequence of microreversibility and Onsager-Casimir reciprocal relations, diffusiophoresis, i.e., the coupling of the tangential components of the pressure tensor to the concentration gradients of solute species, has a reciprocal effect where the interfacial currents of solutes are coupled to the slip velocity. The presence of surface reactions is shown to modify the diffusiophoretic and reciprocal effects at the fluid-solid interface. The thin-layer approximation is used to describe the solution flowing near a reactive solid interface. Analytic formulas describing the diffusiophoretic and reciprocal effects are deduced in the thin-layer approximation and tested numerically for the Poiseuille flow of a solution between catalytic planar surfaces.

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

NASA Technical Reports Server (NTRS)

Goldstein, D.; Magnotti, F.; Chinitz, W.

1983-01-01

Reaction rates in turbulent, reacting flows are reviewed. Assumed probability density functions (pdf) modeling of reaction rates is being investigated in relation to a three variable pdf employing a 'most likely pdf' model. Chemical kinetic mechanisms treating hydrogen air combustion is studied. Perfectly stirred reactor modeling of flame stabilizing recirculation regions was used to investigate the stable flame regions for silane, hydrogen, methane, and propane, and for certain mixtures thereof. It is concluded that in general, silane can be counted upon to stabilize flames only when the overall fuel air ratio is close to or greater than unity. For lean flames, silane may tend to destabilize the flame. Other factors favoring stable flames are high initial reactant temperatures and system pressure.

"Batch" kinetics in flow: online IR analysis and continuous control.

PubMed

Moore, Jason S; Jensen, Klavs F

2014-01-07

Currently, kinetic data is either collected under steady-state conditions in flow or by generating time-series data in batch. Batch experiments are generally considered to be more suitable for the generation of kinetic data because of the ability to collect data from many time points in a single experiment. Now, a method that rapidly generates time-series reaction data from flow reactors by continuously manipulating the flow rate and reaction temperature has been developed. This approach makes use of inline IR analysis and an automated microreactor system, which allowed for rapid and tight control of the operating conditions. The conversion/residence time profiles at several temperatures were used to fit parameters to a kinetic model. This method requires significantly less time and a smaller amount of starting material compared to one-at-a-time flow experiments, and thus allows for the rapid generation of kinetic data. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Development of Visible-Light Photoredox Catalysis in Flow.

PubMed

Garlets, Zachary J; Nguyen, John D; Stephenson, Corey R J

2014-04-01

Visible-light photoredox catalysis has recently emerged as a viable alternative for radical reactions otherwise carried out with tin and boron reagents. It has been recognized that by merging photoredox catalysis with flow chemistry, slow reaction times, lower yields, and safety concerns may be obviated. While flow reactors have been successfully applied to reactions carried out with UV light, only recent developments have demonstrated the same potential of flow reactors for the improvement of visible-light-mediated reactions. This review examines the initial and continuing development of visible-light-mediated photoredox flow chemistry by exemplifying the benefits of flow chemistry compared with conventional batch techniques.

The Development of Visible-Light Photoredox Catalysis in Flow

PubMed Central

Garlets, Zachary J.; Nguyen, John D.

2014-01-01

Visible-light photoredox catalysis has recently emerged as a viable alternative for radical reactions otherwise carried out with tin and boron reagents. It has been recognized that by merging photoredox catalysis with flow chemistry, slow reaction times, lower yields, and safety concerns may be obviated. While flow reactors have been successfully applied to reactions carried out with UV light, only recent developments have demonstrated the same potential of flow reactors for the improvement of visible-light-mediated reactions. This review examines the initial and continuing development of visible-light-mediated photoredox flow chemistry by exemplifying the benefits of flow chemistry compared with conventional batch techniques. PMID:25484447

Online monitoring of a photocatalytic reaction by real-time high resolution FlowNMR spectroscopy.

PubMed

Hall, Andrew M R; Broomfield-Tagg, Rachael; Camilleri, Matthew; Carbery, David R; Codina, Anna; Whittaker, David T E; Coombes, Steven; Lowe, John P; Hintermair, Ulrich

2017-12-19

We demonstrate how FlowNMR spectroscopy can readily be applied to investigate photochemical reactions that require sustained input of light and air to yield mechanistic insight under realistic conditions. The Eosin Y mediated photo-oxidation of N-allylbenzylamine is shown to produce imines as primary reaction products from which undesired aldehydes form after longer reaction times. Facile variation of reaction conditions during the reaction in flow allows for probe experiments that give information about the mode of action of the photocatalyst.

In-situ diagnostic tools for hydrogen transfer leak characterization in PEM fuel cell stacks part II: Operational applications

NASA Astrophysics Data System (ADS)

Niroumand, Amir M.; Homayouni, Hooman; DeVaal, Jake; Golnaraghi, Farid; Kjeang, Erik

2016-08-01

This paper describes a diagnostic tool for in-situ characterization of the rate and distribution of hydrogen transfer leaks in Polymer Electrolyte Membrane (PEM) fuel cell stacks. The method is based on reducing the air flow rate from a high to low value at a fixed current, while maintaining an anode overpressure. At high air flow rates, the reduction in air flow results in lower oxygen concentration in the cathode and therefore reduction in cell voltages. Once the air flow rate in each cell reaches a low value at which the cell oxygen-starves, the voltage of the corresponding cell drops to zero. However, oxygen starvation results from two processes: 1) the electrochemical oxygen reduction reaction which produces current; and 2) the chemical reaction between oxygen and the crossed over hydrogen. In this work, a diagnostic technique has been developed that accounts for the effect of the electrochemical reaction on cell voltage to identify the hydrogen leak rate and number of leaky cells in a fuel cell stack. This technique is suitable for leak characterization during fuel cell operation, as it only requires stack air flow and voltage measurements, which are readily available in an operational fuel cell system.

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

NASA Technical Reports Server (NTRS)

Radhakrishnan, Krishnan; Bittker, David A.

1993-01-01

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

Research and development of a luminol-carbon monoxide flow system

NASA Technical Reports Server (NTRS)

Thomas, R. R.

1977-01-01

Adaption of the luminol-carbon monoxide injection system to a flowing type system is reported. Analysis of actual wastewater samples was carried out and revealed that bacteria can be associated with particles greater than 10 microns in size in samples such as mixed liquor. Research into the luminol reactive oxidation state indicates that oxidized iron porphyrins, cytochrome-c in particular, produce more luminol chemiluminescence than the reduced form. Correlation exists between the extent of porphyrin oxidation and relative chemiluminescence. In addition, the porphyrin nucleus is apparently destroyed under the current chemiluminescent reaction conditions.

Continuous real-time measurement of aqueous cyanide

DOEpatents

Rosentreter, Jeffrey J.; Gering, Kevin L.

2007-03-06

This invention provides a method and system capable of the continuous, real-time measurement of low concentrations of aqueous free cyanide (CN) using an on-line, flow through system. The system is based on the selective reactivity of cyanide anions and the characteristically nonreactive nature of metallic gold films, wherein this selective reactivity is exploited as an indirect measurement for aqueous cyanide. In the present invention the dissolution of gold, due to the solubilization reaction with the analyte cyanide anion, is monitored using a piezoelectric microbalance contained within a flow cell.

Development and validation of chemistry agnostic flow battery cost performance model and application to nonaqueous electrolyte systems: Chemistry agnostic flow battery cost performance model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crawford, Alasdair; Thomsen, Edwin; Reed, David

2016-04-20

A chemistry agnostic cost performance model is described for a nonaqueous flow battery. The model predicts flow battery performance by estimating the active reaction zone thickness at each electrode as a function of current density, state of charge, and flow rate using measured data for electrode kinetics, electrolyte conductivity, and electrode-specific surface area. Validation of the model is conducted using a 4kW stack data at various current densities and flow rates. This model is used to estimate the performance of a nonaqueous flow battery with electrode and electrolyte properties used from the literature. The optimized cost for this system ismore » estimated for various power and energy levels using component costs provided by vendors. The model allows optimization of design parameters such as electrode thickness, area, flow path design, and operating parameters such as power density, flow rate, and operating SOC range for various application duty cycles. A parametric analysis is done to identify components and electrode/electrolyte properties with the highest impact on system cost for various application durations. A pathway to 100$kWh -1 for the storage system is identified.« less

Space shuttle orbiter reaction control system jet interaction study

NASA Technical Reports Server (NTRS)

Rausch, J. R.

1975-01-01

The space shuttle orbiter has forward mounted and rear mounted Reaction Control Systems (RCS) which are used for orbital maneuvering and also provide control during entry and abort maneuvers in the atmosphere. The effects of interaction between the RCS jets and the flow over the vehicle in the atmosphere are studied. Test data obtained in the NASA Langley Research Center 31 inch continuous flow hypersonic tunnel at a nominal Mach number of 10.3 is analyzed. The data were obtained with a 0.01 scale force model with aft mounted RCS nozzles mounted on the sting off of the force model balance. The plume simulations were accomplished primarily using air in a cold gas simulation through scaled nozzles, however, various cold gas mixtures of Helium and Argon were also tested. The effect of number of nozzles was tested as were limited tests of combined controls. The data show that RCS nozzle exit momentum ratio is the primary correlating parameter for effects where the plume impinges on an adjacent surface and mass flow ratio is the parameter where the plume interaction is primarily with the external stream. An analytic model of aft mounted RCS units was developed in which the total reaction control moments are the sum of thrust, impingement, interaction, and cross-coupling terms.

Flow injection chemiluminescence determination of vitamin B12 using on-line UV-persulfate photooxidation and charge coupled device detection.

PubMed

Murillo Pulgarín, José A; García Bermejo, Luisa F; Sánchez García, M Nieves

2011-01-01

A sensitive chemiluminescence method for vitamin B(12) using a charge-coupled device (CCD) photodetector combined with on-line UV-persulfate oxidation in a simple continuous flow system has been developed. The principle for the determination of vitamin B(12) is based on the enhancive effect of cobalt (II) on the chemiluminescence reaction between luminol and percarbonate in alkaline medium. In addition, percarbonate has been investigated and proposed as a powerful source of hydrogen peroxide as oxidant agent in this chemiluminescence reaction. The digestion of vitamin B(12) to release the cobalt (II) is reached by UV irradiation treatment in a persulfate medium. The CCD detector, directly connected to the flow cell, is used with the continuous flow manifold to obtain the full spectral characteristics of cobalt (II) catalyzed luminol-percarbonate reaction. The vitamin B(12) oxidation process and chemical conditions for the chemiluminescence reaction were investigated and optimized. The increment of the emission intensity was proportional to the concentration of vitamin B(12) , giving a second-order calibration graph over the cobalt (II) concentration range from 10 to 5000 μg L(-1)(r(2) = 0.9985) with a detection limit of 9.3 μg L(-1). The proposed method was applied to the determination of vitamin B(12) in different kinds of pharmaceuticals. Copyright © 2011 John Wiley & Sons, Ltd.

Initiation structure of oblique detonation waves behind conical shocks

NASA Astrophysics Data System (ADS)

Yang, Pengfei; Ng, Hoi Dick; Teng, Honghui; Jiang, Zonglin

2017-08-01

The understanding of oblique detonation dynamics has both inherent basic research value for high-speed compressible reacting flow and propulsion application in hypersonic aerospace systems. In this study, the oblique detonation structures formed by semi-infinite cones are investigated numerically by solving the unsteady, two-dimensional axisymmetric Euler equations with a one-step irreversible Arrhenius reaction model. The present simulation results show that a novel wave structure, featured by two distinct points where there is close-coupling between the shock and combustion front, is depicted when either the cone angle or incident Mach number is reduced. This structure is analyzed by examining the variation of the reaction length scale and comparing the flow field with that of planar, wedge-induced oblique detonations. Further simulations are performed to study the effects of chemical length scale and activation energy, which are both found to influence the formation of this novel structure. The initiation mechanism behind the conical shock is discussed to investigate the interplay between the effect of the Taylor-Maccoll flow, front curvature, and energy releases from the chemical reaction in conical oblique detonations. The observed flow fields are interpreted by means of the energetic limit as in the critical regime for initiation of detonation.

Synthesis of Donor/Acceptor-Substituted Diazo Compounds in Flow and Their Application in Enantioselective Dirhodium-Catalyzed Cyclopropanation and C-H Functionalization.

PubMed

Rackl, Daniel; Yoo, Chun-Jae; Jones, Christopher W; Davies, Huw M L

2017-06-16

A tandem reaction system has been developed for the preparation of donor/acceptor-substituted diazo compounds in continuous flow coupled to dirhodium-catalyzed C-H functionalization or cyclopropanation. Hydrazones were oxidized in flow by solid-supported N-iodo-p-toluenesulfonamide potassium salt (PS-SO 2 NIK) to generate the diazo compounds, which were then purified by passing through a column of molecular sieves/sodium thiosulfate.

3D-printed devices for continuous-flow organic chemistry.

PubMed

Dragone, Vincenza; Sans, Victor; Rosnes, Mali H; Kitson, Philip J; Cronin, Leroy

2013-01-01

We present a study in which the versatility of 3D-printing is combined with the processing advantages of flow chemistry for the synthesis of organic compounds. Robust and inexpensive 3D-printed reactionware devices are easily connected using standard fittings resulting in complex, custom-made flow systems, including multiple reactors in a series with in-line, real-time analysis using an ATR-IR flow cell. As a proof of concept, we utilized two types of organic reactions, imine syntheses and imine reductions, to show how different reactor configurations and substrates give different products.

3D-printed and CNC milled flow-cells for chemiluminescence detection.

PubMed

Spilstead, Kara B; Learey, Jessica J; Doeven, Egan H; Barbante, Gregory J; Mohr, Stephan; Barnett, Neil W; Terry, Jessica M; Hall, Robynne M; Francis, Paul S

2014-08-01

Herein we explore modern fabrication techniques for the development of chemiluminescence detection flow-cells with features not attainable using the traditional coiled tubing approach. This includes the first 3D-printed chemiluminescence flow-cells, and a milled flow-cell designed to split the analyte stream into two separate detection zones within the same polymer chip. The flow-cells are compared to conventional detection systems using flow injection analysis (FIA) and high performance liquid chromatography (HPLC), with the fast chemiluminescence reactions of an acidic potassium permanganate reagent with morphine and a series of adrenergic phenolic amines. Copyright © 2014 Elsevier B.V. All rights reserved.

Solute transport with multiple equilibrium-controlled or kinetically controlled chemical reactions

USGS Publications Warehouse

Friedly, John C.; Rubin, Jacob

1992-01-01

A new approach is applied to the problem of modeling solute transport accompanied by many chemical reactions. The approach, based on concepts of the concentration space and its stoichiometric subspaces, uses elements of the subspaces as primary dependent variables. It is shown that the resulting model equations are compact in form, isolate the chemical reaction expressions from flow expressions, and can be used for either equilibrium or kinetically controlled reactions. The implications of the results on numerical algorithms for solving the equations are discussed. The application of the theory is illustrated throughout with examples involving a simple but broadly representative set of reactions previously considered in the literature. Numerical results are presented for four interconnected reactions: a homogeneous complexation reaction, two sorption reactions, and a dissolution/precipitation reaction. Three cases are considered: (1) four kinetically controlled reactions, (2) four equilibrium-controlled reactions, and (3) a system with two kinetically controlled reactions and two equilibrium-controlled reactions.

The Hitchhiker's Guide to Flow Chemistry ∥.

PubMed

Plutschack, Matthew B; Pieber, Bartholomäus; Gilmore, Kerry; Seeberger, Peter H

2017-09-27

Flow chemistry involves the use of channels or tubing to conduct a reaction in a continuous stream rather than in a flask. Flow equipment provides chemists with unique control over reaction parameters enhancing reactivity or in some cases enabling new reactions. This relatively young technology has received a remarkable amount of attention in the past decade with many reports on what can be done in flow. Until recently, however, the question, "Should we do this in flow?" has merely been an afterthought. This review introduces readers to the basic principles and fundamentals of flow chemistry and critically discusses recent flow chemistry accounts.

A miniature and field-applicable multipumping flow analyzer for ammonium monitoring in seawater with fluorescence detection.

PubMed

Horstkotte, Burkhard; Duarte, Carlos M; Cerdà, Víctor

2011-07-15

In this article, a simple, economic, and miniature flow analyzer for ammonium in seawater based on the solenoid micropumps is presented. A single reagent of sodium tetraborate, ortho-phthaldialdehyde (OPA), and sodium sulfite was used and optimized applying the modified SIMPLEX method. A special-made detection cell for fluorescence detection of the reaction product isoindol-1-sulfonat was made and combined with a commercial photomultiplier tube, a long-pass optical filter, and an UV-LED as excitation light source. A LOD down to 13 nmol/L was achieved. The fabrication and application of a miniature reaction coil heating device for reaction rate enhancement is further described. The system featured an injection frequency of 32 h(-1) at average standard deviation of 3%. Copyright © 2011 Elsevier B.V. All rights reserved.

Attrition reactor system

DOEpatents

Scott, Charles D.; Davison, Brian H.

1993-01-01

A reactor vessel for reacting a solid particulate with a liquid reactant has a centrifugal pump in circulatory flow communication with the reactor vessel for providing particulate attrition, resulting in additional fresh surface where the reaction can occur.

CATALYTIC EFFECTS OF CARBON SORBENTS FOR MERCURY CAPTURE. (R827649C001)

EPA Science Inventory

Activated carbon sorbents have the potential to be an effective means of mercury control in combustion systems. Reactions of activated carbons in flow systems with mercury and gas stream components were investigated to determine the types of chemical interactions that occur on...

PLIF Study of Mars Science Laboratory Capsule Reaction Control System Jets

NASA Technical Reports Server (NTRS)

Johansen, C. T.; Danehy, P. M.; Ashcraft, S. W.; Bathel, B. F.; Inman, J. A.; Jones, S. B.

2011-01-01

Nitric-oxide planar laser-induced fluorescence (NO PLIF) was used to visualize the flow in the wake of a Mars Science Lab (MSL) entry capsule with activated reaction control system (RCS) jets in NASA Langley Research Center s 31-Inch Mach 10 Air Tunnel facility. Images were processed using the Virtual Diagnostics Interface (ViDI) method, which brings out the three-dimensional nature of the flow visualization data while showing the relative location of the data with respect to the model. Comparison of wind-on and wind-off results illustrates the effect that the hypersonic crossflow has on the trajectory and structure of individual RCS jets. The visualization and comparison of both single and multiple activated RCS jets indicate low levels of jet-jet interaction. Quantitative streamwise velocity was also obtained via NO PLIF molecular tagging velocimetry (MTV).

PLIF Study of Mars Science Laboratory Capsule Reaction Control System Jets

NASA Technical Reports Server (NTRS)

Johansen, C. T.; Danehy, P. M.; Ashcraft, S. W.; Bathel, B. F.; Inman, J. A.; Jones, S. B.

2011-01-01

Nitric-oxide planar laser-induced fluorescence (NO PLIF) was used to visualize the flow in the wake of a Mars Science Lab (MSL) entry capsule with activated reaction control system (RCS) jets in NASA Langley Research Center's 31-Inch Mach 10 Air Tunnel facility. Images were processed using the Virtual Diagnostics Interface (ViDI) method, which brings out the three-dimensional nature of the flow visualization data while showing the relative location of the data with respect to the model. Comparison of wind-on and wind-off results illustrates the effect that the hypersonic crossflow has on the trajectory and structure of individual RCS jets. The visualization and comparison of both single and multiple activated RCS jets indicate low levels of jet-jet interaction. Quantitative streamwise velocity was also obtained via NO PLIF molecular tagging velocimetry (MTV).

Using Multiscale Modeling to Study Coupled Flow, Transport, Reaction and Biofilm Growth Processes in Porous Media

NASA Astrophysics Data System (ADS)

Valocchi, A. J.; Laleian, A.; Werth, C. J.

2017-12-01

Perturbation of natural subsurface systems by fluid inputs may induce geochemical or microbiological reactions that change porosity and permeability, leading to complex coupled feedbacks between reaction and transport processes. Some examples are precipitation/dissolution processes associated with carbon capture and storage and biofilm growth associated with contaminant transport and remediation. We study biofilm growth due to mixing controlled reaction of multiple substrates. As biofilms grow, pore clogging occurs which alters pore-scale flow paths thus changing the mixing and reaction. These interactions are challenging to quantify using conventional continuum-scale porosity-permeability relations. Pore-scale models can accurately resolve coupled reaction, biofilm growth and transport processes, but modeling at this scale is not feasible for practical applications. There are two approaches to address this challenge. Results from pore-scale models in generic pore structures can be used to develop empirical relations between porosity and continuum-scale parameters, such as permeability and dispersion coefficients. The other approach is to develop a multiscale model of biofilm growth in which non-overlapping regions at pore and continuum spatial scales are coupled by a suitable method that ensures continuity of flux across the interface. Thus, regions of high reactivity where flow alteration occurs are resolved at the pore scale for accuracy while regions of low reactivity are resolved at the continuum scale for efficiency. This approach thus avoids the need for empirical upscaling relations in regions with strong feedbacks between reaction and porosity change. We explore and compare these approaches for several two-dimensional cases.

Space Shuttle third flight /STS-3/ entry RCS analysis. [Reaction Control System

NASA Technical Reports Server (NTRS)

Scallion, W. I.; Compton, H. R.; Suit, W. T.; Powell, R. W.; Blackstock, T. A.; Bates, B. L.

1983-01-01

Flight data obtained from three Space Transportation System orbiter entries (STS-1, 2, and 3) are processed and analyzed to determine the roll interactions caused by the firing of the entry reaction control system (RCS). Comparisons between the flight-derived parameters and the predicted derivatives without interaction effects are made. The flight-derived RCS Plume flow-field interaction effects are independently deduced by direct integration of the incremental changes in the wing upper surface pressures induced by RCS side thruster firings. The separately obtained interaction effects are compared to the predicted values and the differences are discussed.

Rational design of functional and tunable oscillating enzymatic networks

NASA Astrophysics Data System (ADS)

Semenov, Sergey N.; Wong, Albert S. Y.; van der Made, R. Martijn; Postma, Sjoerd G. J.; Groen, Joost; van Roekel, Hendrik W. H.; de Greef, Tom F. A.; Huck, Wilhelm T. S.

2015-02-01

Life is sustained by complex systems operating far from equilibrium and consisting of a multitude of enzymatic reaction networks. The operating principles of biology's regulatory networks are known, but the in vitro assembly of out-of-equilibrium enzymatic reaction networks has proved challenging, limiting the development of synthetic systems showing autonomous behaviour. Here, we present a strategy for the rational design of programmable functional reaction networks that exhibit dynamic behaviour. We demonstrate that a network built around autoactivation and delayed negative feedback of the enzyme trypsin is capable of producing sustained oscillating concentrations of active trypsin for over 65 h. Other functions, such as amplification, analog-to-digital conversion and periodic control over equilibrium systems, are obtained by linking multiple network modules in microfluidic flow reactors. The methodology developed here provides a general framework to construct dissipative, tunable and robust (bio)chemical reaction networks.

Mass Transfer from Gas Bubbles to Impinging Flow of Biological Fluids with Chemical Reaction

PubMed Central

Yang, Wen-Jei; Echigo, R.; Wotton, D. R.; Ou, J. W.; Hwang, J. B.

1972-01-01

The rates of mass transfer from a gas bubble to an impinging flow of a biological fluid such as whole blood and plasma are investigated analytically and experimentally. Gases commonly found dissolved in body fluids are included. Consideration is given to the effects of the chemical reaction between the dissolved gas and the liquid on the rate of mass transfer. Through the application of boundary layer theory the over-all transfer is found to be Sh/(Re)1/2 = 0.845 Sc1/3 in the absence of chemical reaction, and Sh/(Re) 1/2 = F′ (0) in the presence of chemical reaction, where Sh, Re, and Sc are the Sherwood, Reynolds, and Schmidt numbers, respectively, and F′ (0) is a function of Sc and the dimensionless reaction rate constant. Analytical results are also obtained for the bubble lifetime and the bubble radius-time history. These results, which are not incompatible with experimental results, can be applied to predict the dissolution of the entrapped gas emboli in the circulatory system of the human body. PMID:4642218

Study of dynamics of glucose-glucose oxidase-ferricyanide reaction

NASA Astrophysics Data System (ADS)

Nováková, A.; Schreiberová, L.; Schreiber, I.

2011-12-01

This work is focused on dynamics of the glucose-glucose oxidase-ferricyanide enzymatic reaction with or without sodium hydroxide in a continuous-flow stirred tank reactor (CSTR) and in a batch reactor. This reaction exhibits pH-variations having autocatalytic character and is reported to provide nonlinear dynamic behavior (bistability, excitability). The dynamical behavior of the reaction was examined within a wide range of inlet parameters. The main inlet parameters were the ratio of concentrations of sodium hydroxide and ferricyanide and the flow rate. In a batch reactor we observed an autocatalytic drop of pH from slightly basic to medium acidic values. In a CSTR our aim was to find bistability in the presence of sodium hydroxide. However, only a basic steady state was found. In order to reach an acidic steady state, we investigated the system in the absence of sodium hydroxide. Under these conditions the transition from the basic to the acidic steady state was observed when inlet glucose concentration was increased.

Numerical investigation of combustion field of hypervelocity scramjet engine

NASA Astrophysics Data System (ADS)

Zhang, Shikong; Li, Jiang; Qin, Fei; Huang, Zhiwei; Xue, Rui

2016-12-01

A numerical study of the ground testing of a hydrogen-fueled scramjet engine was undertaken using the commercial computational-fluid-dynamics code CFD++. The simulated Mach number was 12. A 7-species, 9-reaction-step hydrogen-air chemistry kinetics system was adopted for the Reynolds-averaged Navier-Stokes simulation. The two-equation SST turbulence model, which takes into account the wall functions, was used to handle the turbulence-chemistry interactions. The results were validated by experimentally measuring the wall pressure distribution, and the values obtained proved to be in good agreement. The flow pattern at non-reaction/reaction is presented, as are the results of analyzing the supersonic premix/non-premix flame structure, the reaction heat release distribution in different modes, and the change in the equivalence ratio. In this study, we realize the working mode of a hypervelocity engine and provide some suggestions for the combustion organization of the engine as well as offer insight into the potential for exploiting the processes of combustion and flow.

Redox flow cell energy storage systems

NASA Technical Reports Server (NTRS)

Thaller, L. H.

1979-01-01

The redox flow cell energy storage system being developed by NASA for use in remote power systems and distributed storage installations for electric utilities is presented. The system under consideration is an electrochemical storage device which utilizes the oxidation and reduction of two fully soluble redox couples (acidified chloride solutions of chromium and iron) as active electrode materials separated by a highly selective ion exchange membrane. The reactants are contained in large storage tanks and pumped through a stack of redox flow cells where the electrochemical reactions take place at porous carbon felt electrodes. Redox equipment has allowed the incorporation of state of charge readout, stack voltage control and system capacity maintenance (rebalance) devices to regulate cells in a stack jointly. A 200 W, 12 V system with a capacity of about 400 Wh has been constructed, and a 2 kW, 10kWh system is planned.

Emergent Chemical Behavior in Variable-Volume Protocells

PubMed Central

Shirt-Ediss, Ben; Solé, Ricard V.; Ruiz-Mirazo, Kepa

2015-01-01

Artificial protocellular compartments and lipid vesicles have been used as model systems to understand the origins and requirements for early cells, as well as to design encapsulated reactors for biotechnology. One prominent feature of vesicles is the semi-permeable nature of their membranes, able to support passive diffusion of individual solute species into/out of the compartment, in addition to an osmotic water flow in the opposite direction to the net solute concentration gradient. Crucially, this water flow affects the internal aqueous volume of the vesicle in response to osmotic imbalances, in particular those created by ongoing reactions within the system. In this theoretical study, we pay attention to this often overlooked aspect and show, via the use of a simple semi-spatial vesicle reactor model, that a changing solvent volume introduces interesting non-linearities into an encapsulated chemistry. Focusing on bistability, we demonstrate how a changing volume compartment can degenerate existing bistable reactions, but also promote emergent bistability from very simple reactions, which are not bistable in bulk conditions. One particularly remarkable effect is that two or more chemically-independent reactions, with mutually exclusive reaction kinetics, are able to couple their dynamics through the variation of solvent volume inside the vesicle. Our results suggest that other chemical innovations should be expected when more realistic and active properties of protocellular compartments are taken into account. PMID:25590570

Mass spectrometric directed system for the continuous-flow synthesis and purification of diphenhydramine† †Electronic supplementary information (ESI) available: NMR spectra of selected product, mass spectra of selected products, crystallization information, and experimental procedures are supplied. See DOI: 10.1039/c7sc00905d Click here for additional data file.

PubMed Central

Loren, Bradley P.; Wleklinski, Michael; Koswara, Andy; Yammine, Kathryn; Hu, Yanyang

2017-01-01

A highly integrated approach to the development of a process for the continuous synthesis and purification of diphenhydramine is reported. Mass spectrometry (MS) is utilized throughout the system for on-line reaction monitoring, off-line yield quantitation, and as a reaction screening module that exploits reaction acceleration in charged microdroplets for high throughput route screening. This effort has enabled the discovery and optimization of multiple routes to diphenhydramine in glass microreactors using MS as a process analytical tool (PAT). The ability to rapidly screen conditions in charged microdroplets was used to guide optimization of the process in a microfluidic reactor. A quantitative MS method was developed and used to measure the reaction kinetics. Integration of the continuous-flow reactor/on-line MS methodology with a miniaturized crystallization platform for continuous reaction monitoring and controlled crystallization of diphenhydramine was also achieved. Our findings suggest a robust approach for the continuous manufacture of pharmaceutical drug products, exemplified in the particular case of diphenhydramine, and optimized for efficiency and crystal size, and guided by real-time analytics to produce the agent in a form that is readily adapted to continuous synthesis. PMID:28979759

Pauson-Khand reactions in a photochemical flow microreactor.

PubMed

Asano, Keisuke; Uesugi, Yuki; Yoshida, Jun-ichi

2013-05-17

Pauson-Khand reactions were achieved at ambient temperature without any additive using a photochemical flow microreactor. The efficiency of the reaction was better than that in a conventional batch reactor, and the reaction could be operated continuously for 1 h.

RaPToRS Sample Delivery System

NASA Astrophysics Data System (ADS)

Henchen, Robert; Shibata, Kye; Krieger, Michael; Pogozelski, Edward; Padalino, Stephen; Glebov, Vladimir; Sangster, Craig

2010-11-01

At various labs (NIF, LLE, NRL), activated material samples are used to measure reaction properties. The Rapid Pneumatic Transport of Radioactive Samples (RaPToRS) system quickly and safely moves these radioactive samples through a closed PVC tube via airflow. The carrier travels from the reaction chamber to the control and analysis station, pneumatically braking at the outlet. A reversible multiplexer routes samples from various locations near the shot chamber to the analysis station. Also, the multiplexer allows users to remotely load unactivated samples without manually approaching the reaction chamber. All elements of the system (pneumatic drivers, flow control valves, optical position sensors, multiplexers, Geiger counters, and release gates at the analysis station) can be controlled manually or automatically using a custom LabVIEW interface. A prototype is currently operating at NRL in Washington DC. Prospective facilities for Raptors systems include LLE and NIF.

Effects of the fluid flows on enzymatic chemical oscillations

NASA Astrophysics Data System (ADS)

Shklyaev, Oleg; Yashin, Victor; Balazs, Anna

2017-11-01

Chemical oscillations are ubiquitous in nature and have a variety of promising applications. Usually, oscillating chemical systems are analyzed within the context of a reaction-diffusion framework. Here, we examine how fluid flows carrying the reactants can be utilized to modulate the negative feedback loops and time delays that promote chemical oscillations. We consider a model where a chemical reaction network involves two species, X and Y, which undergo transformations catalyzed by respective enzymes immobilized at the bottom wall of a fluid-filled microchamber. The reactions with the enzymes provide a negative feedback in the chemically oscillating system. In particular, the first enzyme, localized on the first patch, promotes production of chemical X, while the second enzyme, immobilized on the second patch, promotes production of chemical Y, which inhibits the production of chemical X. The separation distance between the enzyme-coated patches sets the time delay required for the transportation of X and Y. The chemical transport is significantly enhanced if convective fluxes accompany the diffusive ones. Therefore, the parameter region where oscillations are present is modified. The findings provide guidance to designing micro-scale chemical reactors with improved functionalities.

Chemistry with spatial control using particles and streams†

PubMed Central

Kalinin, Yevgeniy V.; Murali, Adithya

2012-01-01

Spatial control of chemical reactions, with micro- and nanometer scale resolution, has important consequences for one pot synthesis, engineering complex reactions, developmental biology, cellular biochemistry and emergent behavior. We review synthetic methods to engineer this spatial control using chemical diffusion from spherical particles, shells and polyhedra. We discuss systems that enable both isotropic and anisotropic chemical release from isolated and arrayed particles to create inhomogeneous and spatially patterned chemical fields. In addition to such finite chemical sources, we also discuss spatial control enabled with laminar flow in 2D and 3D microfluidic networks. Throughout the paper, we highlight applications of spatially controlled chemistry in chemical kinetics, reaction-diffusion systems, chemotaxis and morphogenesis. PMID:23145348

Mode-locking in advection-reaction-diffusion systems: An invariant manifold perspective

NASA Astrophysics Data System (ADS)

Locke, Rory A.; Mahoney, John R.; Mitchell, Kevin A.

2018-01-01

Fronts propagating in two-dimensional advection-reaction-diffusion systems exhibit a rich topological structure. When the underlying fluid flow is periodic in space and time, the reaction front can lock to the driving frequency. We explain this mode-locking phenomenon using the so-called burning invariant manifolds (BIMs). In fact, the mode-locked profile is delineated by a BIM attached to a relative periodic orbit (RPO) of the front element dynamics. Changes in the type (and loss) of mode-locking can be understood in terms of local and global bifurcations of the RPOs and their BIMs. We illustrate these concepts numerically using a chain of alternating vortices in a channel geometry.

Attrition reactor system

DOEpatents

Scott, C.D.; Davison, B.H.

1993-09-28

A reactor vessel for reacting a solid particulate with a liquid reactant has a centrifugal pump in circulatory flow communication with the reactor vessel for providing particulate attrition, resulting in additional fresh surface where the reaction can occur. 2 figures.

Subsurface conditions in hydrothermal vents inferred from diffuse flow composition, and models of reaction and transport

NASA Astrophysics Data System (ADS)

Larson, B. I.; Houghton, J. L.; Lowell, R. P.; Farough, A.; Meile, C. D.

2015-08-01

Chemical gradients in the subsurface of mid-ocean ridge hydrothermal systems create an environment where minerals precipitate and dissolve and where chemosynthetic organisms thrive. However, owing to the lack of easy access to the subsurface, robust knowledge of the nature and extent of chemical transformations remains elusive. Here, we combine measurements of vent fluid chemistry with geochemical and transport modeling to give new insights into the under-sampled subsurface. Temperature-composition relationships from a geochemical mixing model are superimposed on the subsurface temperature distribution determined using a heat flow model to estimate the spatial distribution of fluid composition. We then estimate the distribution of Gibb's free energies of reaction beneath mid oceanic ridges and by combining flow simulations with speciation calculations estimate anhydrite deposition rates. Applied to vent endmembers observed at the fast spreading ridge at the East Pacific Rise, our results suggest that sealing times due to anhydrite formation are longer than the typical time between tectonic and magmatic events. The chemical composition of the neighboring low temperature flow indicates relatively uniform energetically favorable conditions for commonly inferred microbial processes such as methanogenesis, sulfate reduction and numerous oxidation reactions, suggesting that factors other than energy availability may control subsurface microbial biomass distribution. Thus, these model simulations complement fluid-sample datasets from surface venting and help infer the chemical distribution and transformations in subsurface flow.

Sample Handling and Chemical Kinetics in an Acoustically Levitated Drop Microreactor

PubMed Central

2009-01-01

Accurate measurement of enzyme kinetics is an essential part of understanding the mechanisms of biochemical reactions. The typical means of studying such systems use stirred cuvettes, stopped-flow apparatus, microfluidic systems, or other small sample containers. These methods may prove to be problematic if reactants or products adsorb to or react with the container’s surface. As an alternative approach, we have developed an acoustically-levitated drop reactor eventually intended to study enzyme-catalyzed reaction kinetics related to free radical and oxidative stress chemistry. Microliter-scale droplet generation, reactant introduction, maintenance, and fluid removal are all important aspects in conducting reactions in a levitated drop. A three capillary bundle system has been developed to address these needs. We report kinetic measurements for both luminol chemiluminescence and the reaction of pyruvate with nicotinamide adenine dinucleotide, catalyzed by lactate dehydrogenase, to demonstrate the feasibility of using a levitated drop in conjunction with the developed capillary sample handling system as a microreactor. PMID:19769373

Flow Cytometry and Solid Organ Transplantation: A Perfect Match

PubMed Central

Maguire, Orla; Tario, Joseph D.; Shanahan, Thomas C.; Wallace, Paul K.; Minderman, Hans

2015-01-01

In the field of transplantation, flow cytometry serves a well-established role in pre-transplant crossmatching and monitoring immune reconstitution following hematopoietic stem cell transplantation. The capabilities of flow cytometers have continuously expanded and this combined with more detailed knowledge of the constituents of the immune system, their function and interaction and newly developed reagents to study these parameters have led to additional utility of flow cytometry-based analyses, particularly in the post-transplant setting. This review discusses the impact of flow cytometry on managing alloantigen reactions, monitoring opportunistic infections and graft rejection and gauging immunosuppression in the context of solid organ transplantation. PMID:25296232

Open Markov Processes and Reaction Networks

NASA Astrophysics Data System (ADS)

Swistock Pollard, Blake Stephen

We begin by defining the concept of `open' Markov processes, which are continuous-time Markov chains where probability can flow in and out through certain `boundary' states. We study open Markov processes which in the absence of such boundary flows admit equilibrium states satisfying detailed balance, meaning that the net flow of probability vanishes between all pairs of states. External couplings which fix the probabilities of boundary states can maintain such systems in non-equilibrium steady states in which non-zero probability currents flow. We show that these non-equilibrium steady states minimize a quadratic form which we call 'dissipation.' This is closely related to Prigogine's principle of minimum entropy production. We bound the rate of change of the entropy of a driven non-equilibrium steady state relative to the underlying equilibrium state in terms of the flow of probability through the boundary of the process. We then consider open Markov processes as morphisms in a symmetric monoidal category by splitting up their boundary states into certain sets of `inputs' and `outputs.' Composition corresponds to gluing the outputs of one such open Markov process onto the inputs of another so that the probability flowing out of the first process is equal to the probability flowing into the second. Tensoring in this category corresponds to placing two such systems side by side. We construct a `black-box' functor characterizing the behavior of an open Markov process in terms of the space of possible steady state probabilities and probability currents along the boundary. The fact that this is a functor means that the behavior of a composite open Markov process can be computed by composing the behaviors of the open Markov processes from which it is composed. We prove a similar black-boxing theorem for reaction networks whose dynamics are given by the non-linear rate equation. Along the way we describe a more general category of open dynamical systems where composition corresponds to gluing together open dynamical systems.

Reactions and reaction rates in the regional aquifer beneath the Pajarito Plateau, north-central New Mexico, USA

NASA Astrophysics Data System (ADS)

Hereford, Anne G.; Keating, Elizabeth H.; Guthrie, George D.; Zhu, Chen

2007-05-01

Reactions and reaction rates within aquifers are fundamental components of critical hydrological processes. However, reactions simulated in laboratory experiments typically demonstrate rates that are much faster than those observed in the field. Therefore, it is necessary to conduct more reaction rate analyses in natural settings. This study of geochemical reactions in the regional aquifer in the Pajarito Plateau near Los Alamos, New Mexico combines modeling with petrographic assessment to further knowledge and understanding of complex natural hydrologic systems. Groundwater geochemistry shows marked evolution along assumed flow paths. The flow path chosen for this study was evaluated using inverse mass balance modeling to calculate the mass transfer. X-ray diffraction and field emission gun scanning electron microscopy were used to identify possible reactants and products. Considering the mineralogy of the aquifer and saturation indices for the regional water refined initial interpretations. Calculations yielded dissolution rates for plagioclase on the order of 10-15 mol s-1 m-2 and for K-feldspar on the order of 10-17 mol s-1 m-2, orders of magnitude slower than laboratory rates. While these rates agree with other aquifer studies, they must be considered in the light of the uncertainty associated with geometric surface area estimates, 14C ages, and aquifer properties.

In Depth Analysis of AVCOAT TPS Response to a Reentry Flow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Titov, E. V.; Kumar, Rakesh; Levin, D. A.

2011-05-20

Modeling of the high altitude portion of reentry vehicle trajectories with DSMC or statistical BGK solvers requires accurate evaluation of the boundary conditions at the ablating TPS surface. Presented in this article is a model which takes into account the complex ablation physics including the production of pyrolysis gases, and chemistry at the TPS surface. Since the ablation process is time dependent the modeling of the material response to the high energy reentry flow starts with the solution of the rarefied flow over the vehicle and then loosely couples with the material response. The objective of the present work ismore » to carry out conjugate thermal analysis by weakly coupling a flow solver to a material thermal response model. The latter model solves the one dimensional heat conduction equation accounting for the pyrolysis process that takes place in the reaction zone of an ablative thermal protection system (TPS) material. An estimate of the temperature range within which the pyrolysis reaction (decomposition and volatilization) takes place is obtained from Ref. [1]. The pyrolysis reaction results in the formation of char and the release of gases through the porous charred material. These gases remove additional amount of heat as they pass through the material, thus cooling the material (the process known as transpiration cooling). In the present work, we incorporate the transpiration cooling model in the material thermal response code in addition to the pyrolysis model. The flow in the boundary layer and in the vicinity of the TPS material is in the transitional flow regime. Therefore, we use a previously validated statistical BGK method to model the flow physics in the vicinity of the micro-cracks, since the BGK method allows simulations of flow at pressures higher than can be computed using DSMC.« less

3D-printed devices for continuous-flow organic chemistry

PubMed Central

Dragone, Vincenza; Sans, Victor; Rosnes, Mali H; Kitson, Philip J

2013-01-01

Summary We present a study in which the versatility of 3D-printing is combined with the processing advantages of flow chemistry for the synthesis of organic compounds. Robust and inexpensive 3D-printed reactionware devices are easily connected using standard fittings resulting in complex, custom-made flow systems, including multiple reactors in a series with in-line, real-time analysis using an ATR-IR flow cell. As a proof of concept, we utilized two types of organic reactions, imine syntheses and imine reductions, to show how different reactor configurations and substrates give different products. PMID:23766811

A novel stopped flow injection-amperometric procedure for the determination of chlorate.

PubMed

Tue-Ngeun, Orawan; Jakmunee, Jaroon; Grudpan, Kate

2005-12-15

A novel stopped flow injection-amperometric (sFI-Amp) procedure for determination of chlorate has been developed. The reaction of chlorate with excess potassium iodide and hydrochloric acid, forming iodine/triiodide that is further electrochemically reduced at a glassy carbon electrode at +200mV versus Ag/AgCl electrode is employed. In order to increase sensitivity without using of too high acid concentration, promoting of the reaction by increasing reaction time and temperature can be carried out. This can be done without increase of dispersion of the product zone by stopping the flow while the injected zone is being in a mixing coil which is immersed in a water bath of 55+/-0.5 degrees C. In a closed system of FIA, a side reaction of oxygen with iodide is also minimized. Under a set of conditions, linear calibration graphs were in the ranges of 1.2x10(-6)-6.0x10(-5)moll(-1)and 6.0x10(-5)-6.0x10(-4)moll(-1). A sample throughput of 25h(-1) was accomplished. Relative standard deviation was 2% (n=21, 1.2x10(-4)moll(-1) chlorate). The proposed sFI-Amp procedure was successfully applied to the determination of chlorate in soil samples from longan plantation area.

Design, Integration, Certification and Testing of the Orion Crew Module Propulsion System

NASA Technical Reports Server (NTRS)

McKay, Heather; Freeman, Rich; Cain, George; Albright, John D.; Schoenberg, Rich; Delventhal, Rex

2014-01-01

The Orion Multipurpose Crew Vehicle (MPCV) is NASA's next generation spacecraft for human exploration of deep space. Lockheed Martin is the prime contractor for the design, development, qualification and integration of the vehicle. A key component of the Orion Crew Module (CM) is the Propulsion Reaction Control System, a high-flow hydrazine system used during re-entry to orient the vehicle for landing. The system consists of a completely redundant helium (GHe) pressurization system and hydrazine fuel system with monopropellant thrusters. The propulsion system has been designed, integrated, and qualification tested in support of the Orion program's first orbital flight test, Exploration Flight Test One (EFT-1), scheduled for 2014. A subset of the development challenges and lessons learned from this first flight test campaign will be discussed in this paper for consideration when designing future spacecraft propulsion systems. The CONOPS and human rating requirements of the CM propulsion system are unique when compared with a typical satellite propulsion reaction control system. The system requires a high maximum fuel flow rate. It must operate at both vacuum and sea level atmospheric pressure conditions. In order to meet Orion's human rating requirements, multiple parts of the system must be redundant, and capable of functioning after spacecraft system fault events.

Prediction of pressure and flow transients in a gaseous bipropellant reaction control rocket engine

NASA Technical Reports Server (NTRS)

Markowsky, J. J.; Mcmanus, H. N., Jr.

1974-01-01

An analytic model is developed to predict pressure and flow transients in a gaseous hydrogen-oxygen reaction control rocket engine feed system. The one-dimensional equations of momentum and continuity are reduced by the method of characteristics from partial derivatives to a set of total derivatives which describe the state properties along the feedline. System components, e.g., valves, manifolds, and injectors are represented by pseudo steady-state relations at discrete junctions in the system. Solutions were effected by a FORTRAN IV program on an IBM 360/65. The results indicate the relative effect of manifold volume, combustion lag time, feedline pressure fluctuations, propellant temperature, and feedline length on the chamber pressure transient. The analytical combustion model is verified by good correlation between predicted and observed chamber pressure transients. The developed model enables a rocket designer to vary the design parameters analytically to obtain stable combustion for a particular mode of operation which is prescribed by mission objectives.

Reactive Transport Modeling of Induced Calcite Precipitation Reaction Fronts in Porous Media Using A Parallel, Fully Coupled, Fully Implicit Approach

NASA Astrophysics Data System (ADS)

Guo, L.; Huang, H.; Gaston, D.; Redden, G. D.; Fox, D. T.; Fujita, Y.

2010-12-01

Inducing mineral precipitation in the subsurface is one potential strategy for immobilizing trace metal and radionuclide contaminants. Generating mineral precipitates in situ can be achieved by manipulating chemical conditions, typically through injection or in situ generation of reactants. How these reactants transport, mix and react within the medium controls the spatial distribution and composition of the resulting mineral phases. Multiple processes, including fluid flow, dispersive/diffusive transport of reactants, biogeochemical reactions and changes in porosity-permeability, are tightly coupled over a number of scales. Numerical modeling can be used to investigate the nonlinear coupling effects of these processes which are quite challenging to explore experimentally. Many subsurface reactive transport simulators employ a de-coupled or operator-splitting approach where transport equations and batch chemistry reactions are solved sequentially. However, such an approach has limited applicability for biogeochemical systems with fast kinetics and strong coupling between chemical reactions and medium properties. A massively parallel, fully coupled, fully implicit Reactive Transport simulator (referred to as “RAT”) based on a parallel multi-physics object-oriented simulation framework (MOOSE) has been developed at the Idaho National Laboratory. Within this simulator, systems of transport and reaction equations can be solved simultaneously in a fully coupled, fully implicit manner using the Jacobian Free Newton-Krylov (JFNK) method with additional advanced computing capabilities such as (1) physics-based preconditioning for solution convergence acceleration, (2) massively parallel computing and scalability, and (3) adaptive mesh refinements for 2D and 3D structured and unstructured mesh. The simulator was first tested against analytical solutions, then applied to simulating induced calcium carbonate mineral precipitation in 1D columns and 2D flow cells as analogs to homogeneous and heterogeneous porous media, respectively. In 1D columns, calcium carbonate mineral precipitation was driven by urea hydrolysis catalyzed by urease enzyme, and in 2D flow cells, calcium carbonate mineral forming reactants were injected sequentially, forming migrating reaction fronts that are typically highly nonuniform. The RAT simulation results for the spatial and temporal distributions of precipitates, reaction rates and major species in the system, and also for changes in porosity and permeability, were compared to both laboratory experimental data and computational results obtained using other reactive transport simulators. The comparisons demonstrate the ability of RAT to simulate complex nonlinear systems and the advantages of fully coupled approaches, over de-coupled methods, for accurate simulation of complex, dynamic processes such as engineered mineral precipitation in subsurface environments.

Numerical simulation of two-dimensional flow over a heated carbon surface with coupled heterogeneous and homogeneous reactions

NASA Astrophysics Data System (ADS)

Johnson, Ryan Federick; Chelliah, Harsha Kumar

2017-01-01

For a range of flow and chemical timescales, numerical simulations of two-dimensional laminar flow over a reacting carbon surface were performed to understand further the complex coupling between heterogeneous and homogeneous reactions. An open-source computational package (OpenFOAM®) was used with previously developed lumped heterogeneous reaction models for carbon surfaces and a detailed homogeneous reaction model for CO oxidation. The influence of finite-rate chemical kinetics was explored by varying the surface temperatures from 1800 to 2600 K, while flow residence time effects were explored by varying the free-stream velocity up to 50 m/s. The reacting boundary layer structure dependence on the residence time was analysed by extracting the ratio of chemical source and species diffusion terms. The important contributions of radical species reactions on overall carbon removal rate, which is often neglected in multi-dimensional simulations, are highlighted. The results provide a framework for future development and validation of lumped heterogeneous reaction models based on multi-dimensional reacting flow configurations.

Simple interface of high-performance liquid chromatography-atomic fluorescence spectrometry hyphenated system for speciation of mercury based on photo-induced chemical vapour generation with formic acid in mobile phase as reaction reagent.

PubMed

Yin, Yongguang; Liu, Jingfu; He, Bin; Shi, Jianbo; Jiang, Guibin

2008-02-15

Photo-induced chemical vapour generation (CVG) with formic acid in mobile phase as reaction reagent was developed as interface to on-line couple HPLC with atomic fluorescence spectrometry for the separation and determination of inorganic mercury, methylmercury (MeHg), ethylmercury (EtHg) and phenylmercury (PhHg). In the developed procedure, formic acid in mobile phase was used to decompose organomercuries and reduce Hg(2+) to mercury cold vapour under UV irradiation. Therefore, no post-column reagent was used and the flow injection system in traditional procedure is omitted. A number of operating parameters including pH of mobile phase, concentration of formate, flow rate of mobile phase, length of PTFE reaction coil, flow rate of carrier gas and Na(2)S(2)O(3) in sample matrix were optimized. The limits of detection at the optimized conditions were 0.085, 0.033, 0.029 and 0.038 microg L(-1) for inorganic mercury, MeHg, EtHg and PhHg, respectively. The developed method was validated by determination of certified reference material DORM-2 and was further applied in analyses of seafood samples from Yantai port, China. The UV-CVG with formic acid simplifies the instrumentation and reduces the analytical cost significantly.

Scaling Hydrologic Exchange Flows and Biogeochemical Reactions from Bedforms to Basins

NASA Astrophysics Data System (ADS)

Harvey, J. W.; Gomez-Velez, J. D.

2015-12-01

River water moves in and out of the main channel along pathways that are perpendicular to the channel's main axis that flow across or beneath the ground surface. These hydrologic exchange flows (HEFs) are difficult to measure, yet no less important than a river's downstream flow, or exchanges with the atmosphere and deeper groundwater (Harvey and Gooseff, 2015, WRR). There are very few comprehensive investigations of exchange fluxes to understand patterns with river size and relative importance of specific types of exchanges. We used the physically based model NEXSS to simulate multiple scales of hyporheic flow and their cumulative effects on solute reaction in large basins (on the order of Chesapeake Bay basin or larger). Our goal was to explain where and when particular types of hyporheic flow are important in enhancing key biogeochemical reactions, such as organic carbon respiration and denitrification. Results demonstrate that hyporheic flux (expressed per unit area of streambed) varies surprisingly little across the continuum of first-order streams to eighth-order rivers, and vertical exchange beneath small bedforms dominates in comparison with lateral flow beneath gravel bars and meanders. Also, the river's entire volume is exchanged many times with hyporheic flow within a basin, and the turnover length (after one entire river volume is exchanged) is strongly influenced by hydrogeomorphic differences between physiographic regions as well as by river size. The cumulative effects on biogeochemical reactions were assessed using a the reaction significance factor, RSF, which computes the cumulative potential for hyporheic reactions using a dimensionless index that balances reaction progress in a single hyporheic flow path against overall processing efficiency of river turnover through hyporheic flow paths of that type. Reaction significance appears to be strongly dominated by hydrologic factors rather than biogeochemical factors, and seems to be dominated by vertical exchange beneath small bedforms throughout river networks. Future implementations of NEXSS will expand the model to consider flow variation and to consider HEFs beyond hyporheic flow to include exchange with marginal surface waters such as riparian wetlands, floodplains, and ponded water.

A dynamic plug flow reactor model for a vanadium redox flow battery cell

NASA Astrophysics Data System (ADS)

Li, Yifeng; Skyllas-Kazacos, Maria; Bao, Jie

2016-04-01

A dynamic plug flow reactor model for a single cell VRB system is developed based on material balance, and the Nernst equation is employed to calculate cell voltage with consideration of activation and concentration overpotentials. Simulation studies were conducted under various conditions to investigate the effects of several key operation variables including electrolyte flow rate, upper SOC limit and input current magnitude on the cell charging performance. The results show that all three variables have a great impact on performance, particularly on the possibility of gassing during charging at high SOCs or inadequate flow rates. Simulations were also carried out to study the effects of electrolyte imbalance during long term charging and discharging cycling. The results show the minimum electrolyte flow rate needed for operation within a particular SOC range in order to avoid gassing side reactions during charging. The model also allows scheduling of partial electrolyte remixing operations to restore capacity and also avoid possible gassing side reactions during charging. Simulation results also suggest the proper placement for cell voltage monitoring and highlight potential problems associated with setting the upper charging cut-off limit based on the inlet SOC calculated from the open-circuit cell voltage measurement.

Fast fluid-flow events within a subduction-related vein system in oceanic eclogite: implications for pore fluid pressure at the plate interface

NASA Astrophysics Data System (ADS)

Taetz, Stephan; John, Timm; Bröcker, Michael; Spandler, Carl; Stracke, Andreas

2017-04-01

A better understanding of the subduction zone fluid cycle and its mechanical feedback requires in-depth knowledge of how fluids flow within and out of the descending slabs. In order to develop reliable quantitative models of fluid flow, the general relationship between dehydration reactions, fluid pathway formation, and the dimensions and timescales of distinct fluid flow events have to be explored. The high-pressure/low-temperature metamorphic rocks of the Pouébo Eclogite Mélange in New Caledonia provide an excellent opportunity to study the fluid flux in a subduction zone setting. Fluid dynamics are recorded by high-pressure veins that cross-cut eclogite facies mélange blocks from this occurrence. Two types of garnet-quartz-phengite veins can be distinguished. These veins record both synmetamorphic internal fluid release by mineral breakdown reactions (type I veins) as well as infiltration of an external fluid (type II veins) and the associated formation of a reaction halo. The overall dehydration, fluid accumulation and fluid migration documented by the type I veins occurred on a timescale of 10^5-106 years that is mainly given by the geometry and convergence rate of the subduction system. In order to quantify the timeframe of fluid-rock interaction between the external fluid and the wall-rock, we have applied Li-isotope chronology. A continuous profile was sampled perpendicular to a type II vein including material from the vein, the reaction selvage and the immediate host rock. Additional drill cores were taken from parts of the outcrop that most likely remained completely unaffected by fluid infiltration-induced alteration. Different Li concentrations in the internal and external fluid reservoirs produced a distinct diffusion profile of decreasing Li concentration and increasing δ7Li as the reaction front propagated into the host-rock. Li-chronometric constraints indicate that fluid-rock interaction related to the formation of the type II veins and had been completed within ca. 3 years. The short-lived, pulse-like character of this process is in accordance with the notion that fluid flow related to oceanic crust dehydration at the blueschist-to-eclogite transition contributes to or even dominates episodic pore fluid pressure increases at the plate interface which may trigger slip events reported from many subduction zones.

Applying flow chemistry: methods, materials, and multistep synthesis.

PubMed

McQuade, D Tyler; Seeberger, Peter H

2013-07-05

The synthesis of complex molecules requires control over both chemical reactivity and reaction conditions. While reactivity drives the majority of chemical discovery, advances in reaction condition control have accelerated method development/discovery. Recent tools include automated synthesizers and flow reactors. In this Synopsis, we describe how flow reactors have enabled chemical advances in our groups in the areas of single-stage reactions, materials synthesis, and multistep reactions. In each section, we detail the lessons learned and propose future directions.

Numerical Simulation of Desulfurization Behavior in Gas-Stirred Systems Based on Computation Fluid Dynamics-Simultaneous Reaction Model (CFD-SRM) Coupled Model

NASA Astrophysics Data System (ADS)

Lou, Wentao; Zhu, Miaoyong

2014-10-01

A computation fluid dynamics-simultaneous reaction model (CFD-SRM) coupled model has been proposed to describe the desulfurization behavior in a gas-stirred ladle. For the desulfurization thermodynamics, different models were investigated to determine sulfide capacity and oxygen activity. For the desulfurization kinetic, the effect of bubbly plume flow, as well as oxygen absorption and oxidation reactions in slag eyes are considered. The thermodynamic and kinetic modification coefficients are proposed to fit the measured data, respectively. Finally, the effects of slag basicity and gas flow rate on the desulfurization efficiency are investigated. The results show that as the interfacial reactions (Al2O3)-(FeO)-(SiO2)-(MnO)-[S]-[O] simultaneous kinetic equilibrium is adopted to determine the oxygen activity, and the Young's model with the modification coefficient R th of 1.5 is adopted to determine slag sulfide capacity, the predicted sulfur distribution ratio LS agrees well with the measured data. With an increase of the gas blowing time, the predicted desulfurization rate gradually decreased, and when the modification parameter R k is 0.8, the predicted sulfur content changing with time in ladle agrees well with the measured data. If the oxygen absorption and oxidation reactions in slag eyes are not considered in this model, then the sulfur removal rate in the ladle would be overestimated, and this trend would become more obvious with an increase of the gas flow rate and decrease of the slag layer height. With the slag basicity increasing, the total desulfurization ratio increases; however, the total desulfurization ratio changes weakly as the slag basicity exceeds 7. With the increase of the gas flow rate, the desulfurization ratio first increases and then decreases. When the gas flow rate is 200 NL/min, the desulfurization ratio reaches a maximum value in an 80-ton gas-stirred ladle.

Smouldering (thermal) remediation of soil contaminated with industrial organic liquids: novel insights into heat transfer and kinetics uncovered by integrating experiments and modelling

NASA Astrophysics Data System (ADS)

Gerhard, J.; Zanoni, M. A. B.; Torero, J. L.

2017-12-01

Smouldering (i.e., flameless combustion) underpins the technology Self-sustaining Treatment for Active Remediation (STAR). STAR achieves the in situ destruction of nonaqueous phase liquids (NAPLs) by generating a self-sustained smouldering reaction that propagates through the source zone. This research explores the nature of the travelling reaction and the influence of key in situ and engineered characteristics. A novel one-dimensional numerical model was developed (in COMSOL) to simulate the smouldering remediation of bitumen-contaminated sand. This model was validated against laboratory column experiments. Achieving model validation depended on correctly simulating the energy balance at the reaction front, including properly accounting for heat transfer, smouldering kinetics, and heat losses. Heat transfer between soil and air was demonstrated to be generally not at equilibrium. Moreover, existing heat transfer correlations were found to be inappropriate for the low air flow Reynold's numbers (Re < 30) relevant in this and similar thermal remediation systems. Therefore, a suite of experiments were conducted to generate a new heat transfer correlation, which generated correct simulations of convective heat flow through soil. Moreover, it was found that, for most cases of interest, a simple two-step pyrolysis/oxidation set of kinetic reactions was sufficient. Arrhenius parameters, calculated independently from thermogravimetric experiments, allowed the reaction kinetics to be validated in the smouldering model. Furthermore, a simple heat loss term sufficiently accounted for radial heat losses from the column. Altogether, these advances allow this simple model to reasonably predict the self-sustaining process including the peak reaction temperature, the reaction velocity, and the complete destruction of bitumen behind the front. Simulations with the validated model revealed numerous unique insights, including how the system inherently recycles energy, how air flow rate and NAPL saturation dictate contaminant destruction rates, and the extremes that lead to extinction. Overall, this research provides unique insights into the complex interplay of thermochemical processes that govern the success of smouldering as well as other thermal remediation approaches.

High pressure stopped-flow apparatus for the rapid mixing and subsequent study of two fluids under high hydrostatic pressures

NASA Astrophysics Data System (ADS)

Karan, Daniel M.; Macey, Robert I.

1980-08-01

A stopped-flow apparatus is described for the rapid mixing and subsequent study of two dissimilar fluids under pressures up to 1200 bar. The device consists of two identical pressure chambers which contain the two fluids, a third pressure chamber which contains gas to maintain the pressure in the system, an optical port for photometric observation, and various connections. The device has been used to measure reaction times on the order of a hundred milliseconds to tens of seconds, using a maximum of 2 ml of each reagent per experimental determination. The dead time is found to be 5-25 ms with minium average flow velocities of 2.0 m/s. The construction and operation of the device are described and examples of water transport data in red blood cells and the bromophenolblue indicated chemical reaction of NaHCO3 and HCl under pressure are presented.

A Computer Model for Analyzing Volatile Removal Assembly

NASA Technical Reports Server (NTRS)

Guo, Boyun

2010-01-01

A computer model simulates reactional gas/liquid two-phase flow processes in porous media. A typical process is the oxygen/wastewater flow in the Volatile Removal Assembly (VRA) in the Closed Environment Life Support System (CELSS) installed in the International Space Station (ISS). The volatile organics in the wastewater are combusted by oxygen gas to form clean water and carbon dioxide, which is solved in the water phase. The model predicts the oxygen gas concentration profile in the reactor, which is an indicator of reactor performance. In this innovation, a mathematical model is included in the computer model for calculating the mass transfer from the gas phase to the liquid phase. The amount of mass transfer depends on several factors, including gas-phase concentration, distribution, and reaction rate. For a given reactor dimension, these factors depend on pressure and temperature in the reactor and composition and flow rate of the influent.

Development of a PCR/LDR/flow-through hybridization assay using a capillary tube, probe DNA-immobilized magnetic beads and chemiluminescence detection.

PubMed

Hommatsu, Manami; Okahashi, Hisamitsu; Ohta, Keisuke; Tamai, Yusuke; Tsukagoshi, Kazuhiko; Hashimoto, Masahiko

2013-01-01

A polymerase chain reaction (PCR)/ligase detection reaction (LDR)/flow-through hybridization assay using chemiluminescence (CL) detection was developed for analyzing point mutations in gene fragments with high diagnostic value for colorectal cancers. A flow-through hybridization format using a capillary tube, in which probe DNA-immobilized magnetic beads were packed, provided accelerated hybridization kinetics of target DNA (i.e. LDR product) to the probe DNA. Simple fluid manipulations enabled both allele-specific hybridization and the removal of non-specifically bound DNA in the wash step. Furthermore, the use of CL detection greatly simplified the detection scheme, since CL does not require a light source for excitation of the fluorescent dye tags on the LDR products. Preliminary results demonstrated that this analytical system could detect both homozygous and heterozygous mutations, without the expensive instrumentation and cumbersome procedures required by conventional DNA microarray-based methods.

Dispersion relation in oscillatory reaction-diffusion systems with self-consistent flow in true slime mold.

PubMed

Yamada, H; Nakagaki, T; Baker, R E; Maini, P K

2007-06-01

In the large amoeboid organism Physarum, biochemical oscillators are spatially distributed throughout the organism and their collective motion exhibits phase waves, which carry physiological signals. The basic nature of this wave behaviour is not well-understood because, to date, an important effect has been neglected, namely, the shuttle streaming of protoplasm which accompanies the biochemical rhythms. Here we study the effects of self-consistent flow on the wave behaviour of oscillatory reaction-diffusion models proposed for the Physarum plasmodium, by means of numerical simulation for the dispersion relation and weakly nonlinear analysis for derivation of the phase equation. We conclude that the flow term is able to increase the speed of phase waves (similar to elongation of wave length). We compare the theoretical consequences with real waves observed in the organism and also point out the physiological roles of these effects on control mechanisms of intracellular communication.

Chemiluminescence detection of peroxynitrite with flow injection

NASA Astrophysics Data System (ADS)

Kang, Dai; Evmiridis, Nick P.; Vlessidis, Athanasios; Zhou, Yikai

2001-09-01

Peroxynitrite is an important derivative made by nitric oxide in vivo. It can make damages in many kinds of tissue and cells. Its research value in heart disease and cancer is a very high. A sensitive, specific method for analysis of peroxynitrite is described. In this method, chemiluminescence reaction between perodynitrite and luminol was used to detect with flow injection system. The assay has a detection limit of 2 by 10-8 mol L-1, and linear range of 5 by 10-8 mol L-1 to 5 by 10-5 mol L-1. The application o f flow injection system offers the possibility to establish biosensor for real-time detection of perodynitrite.

Influence of chemical reactions on the nonlinear dynamics of dissipative flows

NASA Astrophysics Data System (ADS)

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

2015-08-01

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

Catalytic reaction in confined flow channel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Hassel, Bart A.

A chemical reactor comprises a flow channel, a source, and a destination. The flow channel is configured to house at least one catalytic reaction converting at least a portion of a first nanofluid entering the channel into a second nanofluid exiting the channel. The flow channel includes at least one turbulating flow channel element disposed axially along at least a portion of the flow channel. A plurality of catalytic nanoparticles is dispersed in the first nanofluid and configured to catalytically react the at least one first chemical reactant into the at least one second chemical reaction product in the flowmore » channel.« less

Fuels Combustion Research.

DTIC Science & Technology

1985-12-09

benzene and toluene have been greatly improved and show even better corre- spondence with flow reactor results. The studies of alkylated aromatics have...of the flow reactor ; the use of a unique high temperature sampling system; and an automated gas chromatographic apparatus , and the presence of the gas...In these studies a clear analogy between the reactions of the alkylated aromatics and those of the, corresponding alkanes wqs observed [7,8,93. This

Desktop Systems for Manufacturing Carbon Nanotube Films by Chemical Vapor Deposition

DTIC Science & Technology

2007-06-01

existing low cost tube furnace designs limit the researcher’s ability to fully separate critical reaction parameters such as temperature and flow...Often heated using an external resistive heater coil, a typical configuration, shown in Figure 4, might place a tube made of a non- reactive ...researcher’s ability to fully separate critical parameters such as temperature and flow profiles. Additionally, the use of heating elements external to

Computational reacting gas dynamics

NASA Technical Reports Server (NTRS)

Lam, S. H.

1993-01-01

In the study of high speed flows at high altitudes, such as that encountered by re-entry spacecrafts, the interaction of chemical reactions and other non-equilibrium processes in the flow field with the gas dynamics is crucial. Generally speaking, problems of this level of complexity must resort to numerical methods for solutions, using sophisticated computational fluid dynamics (CFD) codes. The difficulties introduced by reacting gas dynamics can be classified into three distinct headings: (1) the usually inadequate knowledge of the reaction rate coefficients in the non-equilibrium reaction system; (2) the vastly larger number of unknowns involved in the computation and the expected stiffness of the equations; and (3) the interpretation of the detailed reacting CFD numerical results. The research performed accepts the premise that reacting flows of practical interest in the future will in general be too complex or 'untractable' for traditional analytical developments. The power of modern computers must be exploited. However, instead of focusing solely on the construction of numerical solutions of full-model equations, attention is also directed to the 'derivation' of the simplified model from the given full-model. In other words, the present research aims to utilize computations to do tasks which have traditionally been done by skilled theoreticians: to reduce an originally complex full-model system into an approximate but otherwise equivalent simplified model system. The tacit assumption is that once the appropriate simplified model is derived, the interpretation of the detailed numerical reacting CFD numerical results will become much easier. The approach of the research is called computational singular perturbation (CSP).

Effect of the SiCl₄ Flow Rate on SiBN Deposition Kinetics in SiCl₄-BCl₃-NH₃-H₂-Ar Environment.

PubMed

Li, Jianping; Qin, Hailong; Liu, Yongsheng; Ye, Fang; Li, Zan; Cheng, Laifei; Zhang, Litong

2017-06-07

To improve the thermal and mechanical stability of SiC f /SiC or C/SiC composites with SiBN interphase, SiBN coating was deposited by low pressure chemical vapor deposition (LPCVD) using SiCl₄-BCl₃-NH₃-H₂-Ar gas system. The effect of the SiCl₄ flow rate on deposition kinetics was investigated. Results show that deposition rate increases at first and then decreases with the increase of the SiCl₄ flow rate. The surface of the coating is a uniform cauliflower-like structure at the SiCl₄ flow rate of 10 mL/min and 20 mL/min. The surface is covered with small spherical particles when the flow rate is 30 mL/min. The coatings deposited at various SiCl₄ flow rates are all X-ray amorphous and contain Si, B, N, and O elements. The main bonding states are B-N, Si-N, and N-O. B element and B-N bonding decrease with the increase of SiCl₄ flow rate, while Si element and Si-N bonding increase. The main deposition mechanism refers to two parallel reactions of BCl₃+NH₃ and SiCl₄+NH₃. The deposition process is mainly controlled by the reaction of BCl₃+NH₃.

Investigation of supersonic chemically reacting and radiating channel flow

NASA Technical Reports Server (NTRS)

Mani, Mortaza; Tiwari, Surendra N.

1988-01-01

The 2-D time-dependent Navier-Stokes equations are used to investigate supersonic flows undergoing finite rate chemical reaction and radiation interaction for a hydrogen-air system. The explicit multistage finite volume technique of Jameson is used to advance the governing equations in time until convergence is achieved. The chemistry source term in the species equation is treated implicitly to alleviate the stiffness associated with fast reactions. The multidimensional radiative transfer equations for a nongray model are provided for a general configuration and then reduced for a planar geometry. Both pseudo-gray and nongray models are used to represent the absorption-emission characteristics of the participating species. The supersonic inviscid and viscous, nonreacting flows are solved by employing the finite volume technique of Jameson and the unsplit finite difference scheme of MacCormack. The specified problem considered is of the flow in a channel with a 10 deg compression-expansion ramp. The calculated results are compared with those of an upwind scheme. The problem of chemically reacting and radiating flows are solved for the flow of premixed hydrogen-air through a channel with parallel boundaries, and a channel with a compression corner. Results obtained for specific conditions indicate that the radiative interaction can have a significant influence on the entire flow field.

3D CFD Modeling of the LMF System: Desulfurization Kinetics

NASA Astrophysics Data System (ADS)

Cao, Qing; Pitts, April; Zhang, Daojie; Nastac, Laurentiu; Williams, Robert

A fully transient 3D CFD modeling approach capable of predicting the three phase (gas, slag and steel) fluid flow characteristics and behavior of the slag/steel interface in the argon gas bottom stirred ladle with two off-centered porous plugs (Ladle Metallurgical Furnace or LMF) has been recently developed. The model predicts reasonably well the fluid flow characteristics in the LMF system and the observed size of the slag eyes for both the high-stirring and low-stirring conditions. A desulfurization reaction kinetics model considering metal/slag interface characteristics is developed in conjunction with the CFD modeling approach. The model is applied in this study to determine the effects of processing time, and gas flow rate on the efficiency of desulfurization in the studied LMF system.

Cascade redox flow battery systems

DOEpatents

Horne, Craig R.; Kinoshita, Kim; Hickey, Darren B.; Sha, Jay E.; Bose, Deepak

2014-07-22

A reduction/oxidation ("redox") flow battery system includes a series of electrochemical cells arranged in a cascade, whereby liquid electrolyte reacts in a first electrochemical cell (or group of cells) before being directed into a second cell (or group of cells) where it reacts before being directed to subsequent cells. The cascade includes 2 to n stages, each stage having one or more electrochemical cells. During a charge reaction, electrolyte entering a first stage will have a lower state-of-charge than electrolyte entering the nth stage. In some embodiments, cell components and/or characteristics may be configured based on a state-of-charge of electrolytes expected at each cascade stage. Such engineered cascades provide redox flow battery systems with higher energy efficiency over a broader range of current density than prior art arrangements.

Continuous flow chemistry: a discovery tool for new chemical reactivity patterns.

PubMed

Hartwig, Jan; Metternich, Jan B; Nikbin, Nikzad; Kirschning, Andreas; Ley, Steven V

2014-06-14

Continuous flow chemistry as a process intensification tool is well known. However, its ability to enable chemists to perform reactions which are not possible in batch is less well studied or understood. Here we present an example, where a new reactivity pattern and extended reaction scope has been achieved by transferring a reaction from batch mode to flow. This new reactivity can be explained by suppressing back mixing and precise control of temperature in a flow reactor set up.

Hypothetical Modeling of Redox Conditions Within a Complex Ground-Water Flow Field in a Glacial Setting

USGS Publications Warehouse

Feinstein, Daniel T.; Thomas, Mary Ann

2009-01-01

This report describes a modeling approach for studying how redox conditions evolve under the influence of a complex ground-water flow field. The distribution of redox conditions within a flow system is of interest because of the intrinsic susceptibility of an aquifer to redox-sensitive, naturally occurring contaminants - such as arsenic - as well as anthropogenic contaminants - such as chlorinated solvents. The MODFLOW-MT3D-RT3D suite of code was applied to a glacial valley-fill aquifer to demonstrate a method for testing the interaction of flow patterns, sources of reactive organic carbon, and availability of electron acceptors in controlling redox conditions. Modeling results show how three hypothetical distributions of organic carbon influence the development of redox conditions in a water-supply aquifer. The distribution of strongly reduced water depends on the balance between the rate of redox reactions and the capability of different parts of the flow system to transmit oxygenated water. The method can take account of changes in the flow system induced by pumping that result in a new distribution of reduced water.

A thermal biosensor based on enzyme reaction.

PubMed

Zheng, Yi-Hua; Hua, Tse-Chao; Xu, Fei

2005-01-01

Application of the thermal biosensor as analytical tool is promising due to advantages as universal, simplicity and quick response. A novel thermal biosensor based on enzyme reaction has been developed. This biosensor is a flow injection analysis system and consists of two channels with enzyme reaction column and reference column. The reference column, which is set for eliminating the unspecific heat, is inactived on special enzyme reaction of the ingredient to be detected. The special enzyme reaction takes places in the enzyme reaction column at a constant temperature realizing by a thermoelectric thermostat. Thermal sensor based on the thermoelectric module containing 127 serial BiTe-thermocouples is used to monitor the temperature difference between two streams from the enzyme reaction column and the reference column. The analytical example for dichlorvos shows that this biosensor can be used as analytical tool in medicine and biology.

Numerical Simulation of Pulse Detonation Rocket-Induced MHD Ejector (PDRIME) Concepts for Advanced Propulsion Systems

DTIC Science & Technology

2012-02-28

Coupling in Detonation Waves: 1D Dynamics”, Paper 89, 23rd International Colloquium on the Dynamics of Explosions and Reactive ...and temperature, and can be modeled as a constant volume reaction , which is more efficient than a constant pressure reaction . After the detonation ... kinetics , and flow processes using high order numerical methods. A fifth-order WENO (weighted essentially non -oscillatory12,13) scheme was used

Emergent structures in reaction-advection-diffusion systems on a sphere.

PubMed

Krause, Andrew L; Burton, Abigail M; Fadai, Nabil T; Van Gorder, Robert A

2018-04-01

We demonstrate unusual effects due to the addition of advection into a two-species reaction-diffusion system on the sphere. We find that advection introduces emergent behavior due to an interplay of the traditional Turing patterning mechanisms with the compact geometry of the sphere. Unidirectional advection within the Turing space of the reaction-diffusion system causes patterns to be generated at one point of the sphere, and transported to the antipodal point where they are destroyed. We illustrate these effects numerically and deduce conditions for Turing instabilities on local projections to understand the mechanisms behind these behaviors. We compare this behavior to planar advection which is shown to only transport patterns across the domain. Analogous transport results seem to hold for the sphere under azimuthal transport or away from the antipodal points in unidirectional flow regimes.

Emergent structures in reaction-advection-diffusion systems on a sphere

NASA Astrophysics Data System (ADS)

Krause, Andrew L.; Burton, Abigail M.; Fadai, Nabil T.; Van Gorder, Robert A.

2018-04-01

We demonstrate unusual effects due to the addition of advection into a two-species reaction-diffusion system on the sphere. We find that advection introduces emergent behavior due to an interplay of the traditional Turing patterning mechanisms with the compact geometry of the sphere. Unidirectional advection within the Turing space of the reaction-diffusion system causes patterns to be generated at one point of the sphere, and transported to the antipodal point where they are destroyed. We illustrate these effects numerically and deduce conditions for Turing instabilities on local projections to understand the mechanisms behind these behaviors. We compare this behavior to planar advection which is shown to only transport patterns across the domain. Analogous transport results seem to hold for the sphere under azimuthal transport or away from the antipodal points in unidirectional flow regimes.

PDF calculation of scalar mixing layer with simple chemical reactions

NASA Astrophysics Data System (ADS)

Kanzaki, Takao; Pope, Stephen B.

1999-11-01

A joint velocity-composition-turbulent frequency PDF(JPDF) model is used to simulate reactive mixing layer in a grid-generated turbulence with the influence of second-order irreversible chemical reactions. To investigate the effects of molecular mixing, a gas flow and a liquid flow are simulated. For a gas flow, the oxidation reaction (NO+ O3 arrow NO2 +O2 ) between nitricoxide (NO) and ozone (O3 ) is used. For a liquid flow, the saponification reaction(NaOH+HCOOCH3 arrow HCOONa+CH_3OH) between sodiumhydroxide(NaOH) and methylformate(HCOOCH_3) is used. The both cases are moderately fast reactions. Therefore, reactive scalar statistics are affected by turbulent mixing. The results of caliculation are compared with experimental data of Komori et al.(1994) and Bilger et al.(1991)

Automatic flow system for simultaneous determination of iron and chromium in steel alloys employing photometers based on LEDs as radiation source

PubMed Central

Fernandes, Ridvan N.; Campos, Luís Fernando P.

2003-01-01

A multicommutated flow system for simultaneous determination of iron and chromium in steel alloys by photometry is described. The flow network consisted of an automatic injector and four solenoid valves assembled to form two independent analytical pathways, each one comprising reaction coils and a flow cell. The light source (LED) and detector (photodiode) were attached to the flow cells to form a compact unit. The flow system was microcomputer controlled by Quick BASIC 4.5 software, which carried out all steps of the analytical procedure. The feasibility of the system was proved by the determination of iron and chromium in steel alloys and its accuracy was accessed by comparing results with those obtained by plasma atomic emission spectrometry (ICP-AES). No significant difference at the 95% confidence level was observed. Other profitable features such as low reagent consumption (0.33 mg 1,10-phenantroline and 0.03 mg 1,5-diphenylcarbazide per determination); relative standard deviations (n = 5) of 0.4% for iron and 1.2% for chromium; and an analytical throughput of 160 determinations per h were also achieved. PMID:18924884

Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass balance

USGS Publications Warehouse

Harvey, Judson W.; Fuller, Christopher C.

1998-01-01

We determined the role of the hyporheic zone (the subsurface zone where stream water and shallow groundwater mix) in enhancing microbially mediated oxidation of dissolved manganese (to form manganese precipitates) in a drainage basin contaminated by copper mining. The fate of manganese is of overall importance to water quality in Pinal Creek Basin, Arizona, because manganese reactions affect the transport of trace metals. The basin-scale role of the hyporheic zone is difficult to quantify because stream-tracer studies do not always reliably characterize the cumulative effects of the hyporheic zone. This study determined cumulative effects of hyporheic reactions in Pinal Creek basin by characterizing manganese uptake at several spatial scales (stream-reach scale, hyporheic-flow-path scale, and sediment-grain scale). At the stream-reach scale a one-dimensional stream-transport model (including storage zones to represent hyporheic flow paths) was used to determine a reach-averaged time constant for manganese uptake in hyporheic zones, 1/λs, of 1.3 hours, which was somewhat faster but still similar to manganese uptake time constants that were measured directly in centimeter-scale hyporheic flow paths (1/λh= 2.6 hours), and in laboratory batch experiments using streambed sediment (1/λ = 2.7 hours). The modeled depths of subsurface storage zones (ds = 4–17 cm) and modeled residence times of water in storage zones (ts = 3–12 min) were both consistent with direct measurements in hyporheic flow paths (dh = 0–15 cm, th = 1–25 min). There was also good agreement between reach-scale modeling and direct measurements of the percentage removal of dissolved manganese in hyporheic flow paths (fs = 8.9%, andfh = 9.3%rpar;. Manganese uptake experiments in the laboratory using sediment from Pinal Creek demonstrated (through comparison of poisoned and unpoisoned treatments) that the manganese removal process was enhanced by microbially mediated oxidation. The cumulative effect of hyporheic exchange in Pinal Creek basin was to remove approximately 20% of the dissolved manganese flowing out of the drainage basin. Our results illustrate that the cumulative significance of reactive uptake in the hyporheic zone depends on the balance between chemical reaction rates, hyporheic porewater residence time, and turnover of streamflow through hyporheic flow paths. The similarity between the hyporheic reaction timescale (1/λs ≈ 1.3 hours), and the hyporheic porewater residence timescale (ts ≈ 8 min) ensured that there was adequate time for the reaction to progress. Furthermore, it was the similarity between the turnover length for stream water flow through hyporheic flow paths (Ls = stream velocity/storage-zone exchange coefficient ≈ 1.3 km) and the length of Pinal Creek (L ≈ 7 km), which ensured that all stream water passed through hyporheic flow paths several times. As a means to generalize our findings to other sites where similar types of hydrologic and chemical information are available, we suggest a cumulative significance index for hyporheic reactions, Rs = λstsL/Ls (dimensionless); higher values indicate a greater potential for hyporheic reactions to influence geochemical mass balance. Our experience in Pinal Creek basin suggests that values of Rs > 0.2 characterize systems where hyporheic reactions are likely to influence geochemical mass balance at the drainage-basin scale.

Boosting the value of biodiesel byproduct by the non-catalytic transesterification of dimethyl carbonate via a continuous flow system under ambient pressure.

PubMed

Kwon, Eilhann E; Yi, Haakrho; Jeon, Young Jae

2014-10-01

Transformation of coconut oil into biodiesel by using dimethyl carbonate (DMC) via a non-catalytic transesterification reaction under ambient pressure was investigated in this study. The non-catalytic transformation to biodiesel was achieved by means of a heterogeneous reaction between liquid triglycerides and gas phase DMC. The reaction was enhanced in the presence of porous material due to its intrinsic physical properties such as tortuosity and absorption/adsorption. The numerous pores in the material served as micro reaction chambers and ensured that there was enough contact time between the liquid triglycerides and the gaseous DMC, which enabled the completion of the transesterification. The highest fatty acid methyl esters (FAMEs) yield achieved was 98±0.5% within 1-2min at a temperature of 360-450°C under ambient pressure. The fast reaction rates made it possible to convert the lipid feedstock into biodiesel via a continuous flow system without the application of increased pressure. This suggested that the commonly used supercritical conditions could be avoided, resulting in huge cost benefits for biodiesel production. In addition, the high value of the byproduct from the transesterification of the lipid feedstock with DMC suggested that the production biodiesel using this method could be more economically competitive. Finally, the basic properties of biodiesel derived from the non-catalytic conversion of rapeseed oil with DMC were summarised. Copyright © 2014 Elsevier Ltd. All rights reserved.

Probing fast ribozyme reactions under biological conditions with rapid quench-flow kinetics.

PubMed

Bingaman, Jamie L; Messina, Kyle J; Bevilacqua, Philip C

2017-05-01

Reaction kinetics on the millisecond timescale pervade the protein and RNA fields. To study such reactions, investigators often perturb the system with abiological solution conditions or substrates in order to slow the rate to timescales accessible by hand mixing; however, such perturbations can change the rate-limiting step and obscure key folding and chemical steps that are found under biological conditions. Mechanical methods for collecting data on the millisecond timescale, which allow these perturbations to be avoided, have been developed over the last few decades. These methods are relatively simple and can be conducted on affordable and commercially available instruments. Here, we focus on using the rapid quench-flow technique to study the fast reaction kinetics of RNA enzymes, or ribozymes, which often react on the millisecond timescale under biological conditions. Rapid quench of ribozymes is completely parallel to the familiar hand-mixing approach, including the use of radiolabeled RNAs and fractionation of reactions on polyacrylamide gels. We provide tips on addressing and preventing common problems that can arise with the rapid-quench technique. Guidance is also offered on ensuring the ribozyme is properly folded and fast-reacting. We hope that this article will facilitate the broader use of rapid-quench instrumentation to study fast-reacting ribozymes under biological reaction conditions. Copyright © 2017 Elsevier Inc. All rights reserved.

Probing fast ribozyme reactions under biological conditions with rapid quench-flow kinetics

PubMed Central

Bingaman, Jamie L.; Messina, Kyle J.; Bevilacqua, Philip C.

2017-01-01

Reaction kinetics on the millisecond timescale pervade the protein and RNA fields. To study such reactions, investigators often perturb the system with abiological solution conditions or substrates in order to slow the rate to timescales accessible by hand-mixing; however, such perturbations can change the rate-limiting step and obscure key folding and chemical steps that are found under biological conditions. Mechanical methods for collecting data on the millisecond timescale, which allow these perturbations to be avoided, have been developed over the last few decades. These methods are relatively simple and can be conducted on affordable and commercially available instruments. Here, we focus on using the rapid quench-flow technique to study the fast reaction kinetics of RNA enzymes, or ribozymes, which often react on the millisecond timescale under biological conditions. Rapid quench of ribozymes is completely parallel to the familiar hand-mixing approach, including the use of radiolabeled RNAs and fractionation of reactions on polyacrylamide gels. We provide tips on addressing and preventing common problems that can arise with the rapid-quench technique. Guidance is also offered on ensuring the ribozyme is properly folded and fast-reacting. We hope that this article will facilitate the broader use of rapid-quench instrumentation to study fast-reacting ribozymes under biological reaction conditions. PMID:28315484

Single-drop reactive extraction/extractive reaction with forced convective diffusion and interphase mass transfer

NASA Technical Reports Server (NTRS)

Kleinman, Leonid S.; Red, X. B., Jr.

1995-01-01

An algorithm has been developed for time-dependent forced convective diffusion-reaction having convection by a recirculating flow field within the drop that is hydrodynamically coupled at the interface with a convective external flow field that at infinity becomes a uniform free-streaming flow. The concentration field inside the droplet is likewise coupled with that outside by boundary conditions at the interface. A chemical reaction can take place either inside or outside the droplet, or reactions can take place in both phases. The algorithm has been implemented, and for comparison results are shown here for the case of no reaction in either phase and for the case of an external first order reaction, both for unsteady behavior. For pure interphase mass transfer, concentration isocontours, local and average Sherwood numbers, and average droplet concentrations have been obtained as a function of the physical properties and external flow field. For mass transfer enhanced by an external reaction, in addition to the above forms of results, we present the enhancement factor, with the results now also depending upon the (dimensionless) rate of reaction.

Single-drop reactive extraction/extractive reaction with forced convective diffusion and interphase mass transfer

NASA Technical Reports Server (NTRS)

Kleinman, Leonid S.; Reed, X. B., Jr.

1995-01-01

An algorithm has been developed for the forced convective diffusion-reaction problem for convection inside and outside a droplet by a recirculating flow field hydrodynamically coupled at the droplet interface with an external flow field that at infinity becomes a uniform streaming flow. The concentration field inside the droplet is likewise coupled with that outside by boundary conditions at the interface. A chemical reaction can take place either inside or outside the droplet or reactions can take place in both phases. The algorithm has been implemented and results are shown here for the case of no reaction and for the case of an external first order reaction, both for unsteady behavior. For pure interphase mass transfer, concentration isocontours, local and average Sherwood numbers, and average droplet concentrations have been obtained as a function of the physical properties and external flow field. For mass transfer enhanced by an external reaction, in addition to the above forms of results, we present the enhancement factor, with the results now also depending upon the (dimensionless) rate of reaction.

Computed potential energy surfaces for chemical reactions

NASA Technical Reports Server (NTRS)

Walch, Stephen P.

1990-01-01

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

Magnetohydrodynamic pump with a system for promoting flow of fluid in one direction

DOEpatents

Lemoff, Asuncion V [Union City, CA; Lee, Abraham P [Irvine, CA

2010-07-13

A magnetohydrodynamic pump for pumping a fluid. The pump includes a microfluidic channel for channeling the fluid, a MHD electrode/magnet system operatively connected to the microfluidic channel, and a system for promoting flow of the fluid in one direction in the microfluidic channel. The pump has uses in the medical and biotechnology industries for blood-cell-separation equipment, biochemical assays, chemical synthesis, genetic analysis, drug screening, an array of antigen-antibody reactions, combinatorial chemistry, drug testing, medical and biological diagnostics, and combinatorial chemistry. The pump also has uses in electrochromatography, surface micromachining, laser ablation, inkjet printers, and mechanical micromilling.

Flow-Driven Waves and Phase-Locked Self-Organization in Quasi-One-Dimensional Colonies of Dictyostelium discoideum

NASA Astrophysics Data System (ADS)

Gholami, A.; Steinbock, O.; Zykov, V.; Bodenschatz, E.

2015-01-01

We report experiments on flow-driven waves in a microfluidic channel containing the signaling slime mold Dictyostelium discoideum. The observed cyclic adenosine monophosphate (cAMP) wave trains developed spontaneously in the presence of flow and propagated with the velocity proportional to the imposed flow velocity. The period of the wave trains was independent of the flow velocity. Perturbations of flow-driven waves via external periodic pulses of the signaling agent cAMP induced 1 ∶1 , 2 ∶1 , 3 ∶1 , and 1 ∶2 frequency responses, reminiscent of Arnold tongues in forced oscillatory systems. We expect our observations to be generic to active media governed by reaction-diffusion-advection dynamics, where spatially bound autocatalytic processes occur under flow conditions.

In situ IR and X-ray high spatial-resolution microspectroscopy measurements of multistep organic transformation in flow microreactor catalyzed by Au nanoclusters.

PubMed

Gross, Elad; Shu, Xing-Zhong; Alayoglu, Selim; Bechtel, Hans A; Martin, Michael C; Toste, F Dean; Somorjai, Gabor A

2014-03-05

Analysis of catalytic organic transformations in flow reactors and detection of short-lived intermediates are essential for optimization of these complex reactions. In this study, spectral mapping of a multistep catalytic reaction in a flow microreactor was performed with a spatial resolution of 15 μm, employing micrometer-sized synchrotron-based IR and X-ray beams. Two nanometer sized Au nanoclusters were supported on mesoporous SiO2, packed in a flow microreactor, and activated toward the cascade reaction of pyran formation. High catalytic conversion and tunable products selectivity were achieved under continuous flow conditions. In situ synchrotron-sourced IR microspectroscopy detected the evolution of the reactant, vinyl ether, into the primary product, allenic aldehyde, which then catalytically transformed into acetal, the secondary product. By tuning the residence time of the reactants in a flow microreactor a detailed analysis of the reaction kinetics was performed. An in situ micrometer X-ray absorption spectroscopy scan along the flow reactor correlated locally enhanced catalytic conversion, as detected by IR microspectroscopy, to areas with high concentration of Au(III), the catalytically active species. These results demonstrate the fundamental understanding of the mechanism of catalytic reactions which can be achieved by the detailed mapping of organic transformations in flow reactors.

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

NASA Astrophysics Data System (ADS)

Davis, Jeffery Jon

1998-09-01

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.

Cumulative Significance of Hyporheic Exchange and Biogeochemical Processing in River Networks

NASA Astrophysics Data System (ADS)

Harvey, J. W.; Gomez-Velez, J. D.

2014-12-01

Biogeochemical reactions in rivers that decrease excessive loads of nutrients, metals, organic compounds, etc. are enhanced by hydrologic interactions with microbially and geochemically active sediments of the hyporheic zone. The significance of reactions in individual hyporheic flow paths has been shown to be controlled by the contact time between river water and sediment and the intrinsic reaction rate in the sediment. However, little is known about how the cumulative effects of hyporheic processing in large river basins. We used the river network model NEXSS (Gomez-Velez and Harvey, submitted) to simulate hyporheic exchange through synthetic river networks based on the best available models of network topology, hydraulic geometry and scaling of geomorphic features, grain size, hydraulic conductivity, and intrinsic reaction rates of nutrients and metals in river sediment. The dimensionless reaction significance factor, RSF (Harvey et al., 2013) was used to quantify the cumulative removal fraction of a reactive solute by hyporheic processing. SF scales reaction progress in a single pass through the hyporheic zone with the proportion of stream discharge passing through the hyporheic zone for a specified distance. Reaction progress is optimal where the intrinsic reaction timescale in sediment matches the residence time of hyporheic flow and is less efficient in longer residence time hyporheic flow as a result of the decreasing proportion of river flow that is processed by longer residence time hyporheic flow paths. In contrast, higher fluxes through short residence time hyporheic flow paths may be inefficient because of the repeated surface-subsurface exchanges required to complete the reaction. Using NEXSS we found that reaction efficiency may be high in both small streams and large rivers, although for different reasons. In small streams reaction progress generally is dominated by faster pathways of vertical exchange beneath submerged bedforms. Slower exchange beneath meandering river banks mainly has importance only in large rivers. For solutes entering networks in proportion to water inputs it is the lower order streams that tend to dominate cumulative reaction progress.

Detection of Neisseria meningitidis in cerebrospinal fluid using a multiplex PCR and the Luminex detection technology.

PubMed

Møller, Jens Kjølseth

2012-01-01

Rapid clinical and laboratory diagnoses are the foundation for a successful management of serious infections with Neisseria meningitidis. A species-specific multiplex polymerase chain reaction (PCR) coupled with fluidic microarrays using microbeads (the Luminex xMAP™ Technology) can detect pathogens most frequently found in the cerebrospinal fluid of patients. The Luminex suspension array system uniquely combines flow cytometry, microspheres, laser technology, digital signal processing, and traditional chemistry. In this method, the reaction is carried out in one vessel, in which distinctly color-coded bead sets, each conjugated with a different specific nucleic acid reactant, are hybridized with the PCR products, and a reporter molecule is used to quantify the interaction. The flow-based Luminex array reader identifies each reaction (bead set) after excitation by a red classification laser. Reporter signals from each reaction are simultaneously quantified by fluorescence generated by a green reporter laser. This nonculture, multiplex assay may prove to be an important tool for optimal laboratory diagnosis, not only of meningococcal meningitis, but also of meningitis caused by other bacterial or viral pathogens.

Exploring the Cattaneo-Christov heat flux phenomenon on a Maxwell-type nanofluid coexisting with homogeneous/heterogeneous reactions

NASA Astrophysics Data System (ADS)

Sarkar, Amit; Kundu, Prabir Kumar

2017-12-01

This specific article unfolds the efficacy of Cattaneo-Christov heat flux on the heat and mass transport of Maxwell nanofluid flow over a stretched sheet with changeable thickness. Homogeneous/heterogeneous reactions in the fluid are additionally considered. The Cattaneo-Christov heat flux model is initiated in the energy equation. Appropriate similarity transformations are taken up to form a system of nonlinear ODEs. The impact of related parameters on the nanoparticle concentration and temperature is inspected through tables and diagrams. It is renowned that temperature distribution increases for lower values of the thermal relaxation parameter. The rate of mass transfer is enhanced for increasing in the heterogeneous reaction parameter but the reverse tendency is ensued for the homogeneous reaction parameter. On the other side, the rate of heat transfer is getting enhanced for the Cattaneo-Christov model compared to the classical Fourier's model for some flow factors. Thus the implication of the current study is to delve its unique effort towards the generalized version of traditional Fourier's law at nano level.

A numerical study of mixing enhancement in supersonic reacting flow fields. [in scramjets

NASA Technical Reports Server (NTRS)

Drummond, J. Philip; Mukunda, H. S.

1988-01-01

NASA Langley has intensively investigated the components of ramjet and scramjet systems for endoatmospheric, airbreathing hypersonic propulsion; attention is presently given to the optimization of scramjet combustor fuel-air mixing and reaction characteristics. A supersonic, spatially developing and reacting mixing layer has been found to serve as an excellent physical model for the mixing and reaction process. Attention is presently given to techniques that have been applied to the enhancement of the mixing processes and the overall combustion efficiency of the mixing layer. A fuel injector configuration has been computationally designed which significantly increases mixing and reaction rates.

Silane-Pyrolysis Reactor With Nonuniform Heating

NASA Technical Reports Server (NTRS)

Iya, Sridhar K.

1991-01-01

Improved reactor serves as last stage in system processing metallurgical-grade silicon feedstock into silicon powder of ultrahigh purity. Silane pyrolized to silicon powder and hydrogen gas via homogeneous decomposition reaction in free space. Features set of individually adjustable electrical heaters and purge flow of hydrogen to improve control of pyrolysis conditions. Power supplied to each heater set in conjunction with flow in reactor to obtain desired distribution of temperature as function of position along reactor.

Buoyancy effects on the radiative magneto Micropolar nanofluid flow with double stratification, activation energy and binary chemical reaction.

PubMed

Ramzan, M; Ullah, Naeem; Chung, Jae Dong; Lu, Dianchen; Farooq, Umer

2017-10-10

A mathematical model has been developed to examine the magneto hydrodynamic micropolar nanofluid flow with buoyancy effects. Flow analysis is carried out in the presence of nonlinear thermal radiation and dual stratification. The impact of binary chemical reaction with Arrhenius activation energy is also considered. Apposite transformations are engaged to transform nonlinear partial differential equations to differential equations with high nonlinearity. Resulting nonlinear system of differential equations is solved by differential solver method in Maple software which uses Runge-Kutta fourth and fifth order technique (RK45). To authenticate the obtained results, a comparison with the preceding article is also made. The evaluations are executed graphically for numerous prominent parameters versus velocity, micro rotation component, temperature, and concentration distributions. Tabulated numerical calculations of Nusselt and Sherwood numbers with respective well-argued discussions are also presented. Our findings illustrate that the angular velocity component declines for opposing buoyancy forces and enhances for aiding buoyancy forces by changing the micropolar parameter. It is also found that concentration profile increases for higher values of chemical reaction parameter, whereas it diminishes for growing values of solutal stratification parameter.

Numerical Simulations of High-Speed Chemically Reacting Flow

NASA Technical Reports Server (NTRS)

Ton, V. T.; Karagozian, A. R.; Marble, F. E.; Osher, S. J.; Engquist, B. E.

1994-01-01

The essentially nonoscillatory (ENO) shock-capturing scheme for the solution of hyperbolic equations is extended to solve a system of coupled conservation equations governing two-dimensional, time-dependent, compressible chemically reacting flow with full chemistry. The thermodynamic properties of the mixture are modeled accurately, and stiff kinetic terms are separated from the fluid motion by a fractional step algorithm. The methodology is used to study the concept of shock-induced mixing and combustion, a process by which the interaction of a shock wave with a jet of low-density hydrogen fuel enhances mixing through streamwise vorticity generation. Test cases with and without chemical reaction are explored here. Our results indicate that, in the temperature range examined, vorticity generation as well as the distribution of atomic species do not change significantly with the introduction of a chemical reaction and subsequent heat release. The actual diffusion of hydrogen is also relatively unaffected by the reaction process. This suggests that the fluid mechanics of this problem may be successfully decoupled from the combustion processes, and that computation of the mixing problem (without combustion chemistry) can elucidate much of the important physical features of the flow.

Numerical Simulations of High-Speed Chemically Reacting Flow

NASA Technical Reports Server (NTRS)

Ton, V. T.; Karagozin, A. R.; Marble, F. E.; Osher, S. J.; Engquist, B. E.

1994-01-01

The Essentially NonOscillatory (ENO) shock-capturing scheme for the solution of hyperbolic equations is extended to solve a system of coupled conservation equations governing two-dimensional, time-dependent, compressible chemically reacting flow with full chemistry. The thermodynamic properties of the mixture are modeled accurately, and stiff kinetic terms are separated from the fluid motion by a fractional step algorithm. The methodology is used to study the concept of shock-induced mixing and combustion, a process by which the interaction of a shock wave with a jet of low-density hydrogen fuel enhances mixing through streamwise vorticity generation. Test cases with and without chemical reaction are explored here. Our results indicate that, in the temperature range examined, vorticity generation as well as the distribution of atomic species do not change significantly with the introduction of a chemical reaction and subsequent heat release. The actual diffusion of hydrogen is also relatively unaffected by the reaction process. This suggests that the fluid mechanics of this problem may be successfully decoupled from the combustion processes, and that computation of the mixing problem (without combustion chemistry) can elucidate much of the important physical features of the flow.

Numerical modeling study on the epitaxial growth of silicon from dichlorosilane

NASA Astrophysics Data System (ADS)

Zaidi, Imama; Jang, Yeon-Ho; Ko, Dong Guk; Im, Ik-Tae

2018-02-01

Computer simulations play an important role in determining the optimal design parameters for chemical vapor deposition (CVD) reactors, such as flow rates, positions of the inlet and outlet orifices, and rotational rates, etc. Reliability of the results of these simulations depends on the set of chemical reaction used to represent the process of deposition in the reactor. Aim of the present work is to validate the simple empirical reaction to model the epitaxial growth of silicon for a Dichlorosilane-H2 (DCS)-H2 system. Governing equations for continuity, momentum, energy, and reacting species are solved numerically using the finite volume method. The agreement between experimental and predicted growth rates for various DCS flow rates is shown to be satisfactory. The increase in growth rate with the increase in pressure is in accordance with the available data. Based on the validated chemical reaction model, a study was carried out to analyze the uniformity of the silicon layer thickness for two different flow rates in a planetary reactor. It was concluded that, based on the operating conditions, the uniformity of the silicon layer over the wafer is independent of the satellite rotational rate in the reactor.

Investigating the air oxidation of V(II) ions in a vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Ngamsai, Kittima; Arpornwichanop, Amornchai

2015-11-01

The air oxidation of vanadium (V(II)) ions in a negative electrolyte reservoir is a major side reaction in a vanadium redox flow battery (VRB), which leads to electrolyte imbalance and self-discharge of the system during long-term operation. In this study, an 80% charged negative electrolyte solution is employed to investigate the mechanism and influential factors of the reaction in a negative-electrolyte reservoir. The results show that the air oxidation of V(II) ions occurs at the air-electrolyte solution interface area and leads to a concentration gradient of vanadium ions in the electrolyte solution and to the diffusion of V(II) and V(III) ions. The effect of the ratio of the electrolyte volume to the air-electrolyte solution interface area and the concentrations of vanadium and sulfuric acid in an electrolyte solution is investigated. A higher ratio of electrolyte volume to the air-electrolyte solution interface area results in a slower oxidation reaction rate. The high concentrations of vanadium and sulfuric acid solution also retard the air oxidation of V(II) ions. This information can be utilized to design an appropriate electrolyte reservoir for the VRB system and to prepare suitable ingredients for the electrolyte solution.

Modeling mass transfer and reaction of dilute solutes in a ternary phase system by the lattice Boltzmann method

NASA Astrophysics Data System (ADS)

Fu, Yu-Hang; Bai, Lin; Luo, Kai-Hong; Jin, Yong; Cheng, Yi

2017-04-01

In this work, we propose a general approach for modeling mass transfer and reaction of dilute solute(s) in incompressible three-phase flows by introducing a collision operator in lattice Boltzmann (LB) method. An LB equation was used to simulate the solute dynamics among three different fluids, in which the newly expanded collision operator was used to depict the interface behavior of dilute solute(s). The multiscale analysis showed that the presented model can recover the macroscopic transport equations derived from the Maxwell-Stefan equation for dilute solutes in three-phase systems. Compared with the analytical equation of state of solute and dynamic behavior, these results are proven to constitute a generalized framework to simulate solute distributions in three-phase flows, including compound soluble in one phase, compound adsorbed on single-interface, compound in two phases, and solute soluble in three phases. Moreover, numerical simulations of benchmark cases, such as phase decomposition, multilayered planar interfaces, and liquid lens, were performed to test the stability and efficiency of the model. Finally, the multiphase mass transfer and reaction in Janus droplet transport in a straight microchannel were well reproduced.

Continuous Flow Science in an Undergraduate Teaching Laboratory: Photocatalytic Thiol-Ene Reaction Using Visible Light

ERIC Educational Resources Information Center

Santandrea, Jeffrey; Kairouz, Vanessa; Collins, Shawn K.

2018-01-01

An undergraduate teaching laboratory experiment involving a continuous flow, photocatalytic thiol-ene reaction using visible-light irradiation is described that allows students to explore concepts of green chemistry, photochemistry, photocatalysis, and continuous flow chemistry.

Barriers to front propagation in laminar, three-dimensional fluid flows

NASA Astrophysics Data System (ADS)

Doan, Minh; Simons, J. J.; Lilienthal, Katherine; Solomon, Tom; Mitchell, Kevin A.

2018-03-01

We present experiments on one-way barriers that block reaction fronts in a fully three-dimensional (3D) fluid flow. Fluorescent Belousov-Zhabotinsky reaction fronts are imaged with laser-scanning in a laminar, overlapping vortex flow. The barriers are analyzed with a 3D extension to burning invariant manifold (BIM) theory that was previously applied to two-dimensional advection-reaction-diffusion processes. We discover tube and sheet barriers that guide the front evolution. The experimentally determined barriers are explained by BIMs calculated from a model of the flow.

Method and apparatus for measuring coupled flow, transport, and reaction processes under liquid unsaturated flow conditions

DOEpatents

McGrail, Bernard P.; Martin, Paul F.; Lindenmeier, Clark W.

1999-01-01

The present invention is a method and apparatus for measuring coupled flow, transport and reaction processes under liquid unsaturated flow conditions. The method and apparatus of the present invention permit distinguishing individual precipitation events and their effect on dissolution behavior isolated to the specific event. The present invention is especially useful for dynamically measuring hydraulic parameters when a chemical reaction occurs between a particulate material and either liquid or gas (e.g. air) or both, causing precipitation that changes the pore structure of the test material.

An atmospheric pressure flow reactor: Gas phase kinetics and mechanism in tropospheric conditions without wall effects

NASA Technical Reports Server (NTRS)

Koontz, Steven L.; Davis, Dennis D.; Hansen, Merrill

1988-01-01

A new type of gas phase flow reactor, designed to permit the study of gas phase reactions near 1 atm of pressure, is described. A general solution to the flow/diffusion/reaction equations describing reactor performance under pseudo-first-order kinetic conditions is presented along with a discussion of critical reactor parameters and reactor limitations. The results of numerical simulations of the reactions of ozone with monomethylhydrazine and hydrazine are discussed, and performance data from a prototype flow reactor are presented.

Droplet-based microfluidic flow injection system with large-scale concentration gradient by a single nanoliter-scale injection for enzyme inhibition assay.

PubMed

Cai, Long-Fei; Zhu, Ying; Du, Guan-Sheng; Fang, Qun

2012-01-03

We described a microfluidic chip-based system capable of generating droplet array with a large scale concentration gradient by coupling flow injection gradient technique with droplet-based microfluidics. Multiple modules including sample injection, sample dispersion, gradient generation, droplet formation, mixing of sample and reagents, and online reaction within the droplets were integrated into the microchip. In the system, nanoliter-scale sample solution was automatically injected into the chip under valveless flow injection analysis mode. The sample zone was first dispersed in the microchannel to form a concentration gradient along the axial direction of the microchannel and then segmented into a linear array of droplets by immiscible oil phase. With the segmentation and protection of the oil phase, the concentration gradient profile of the sample was preserved in the droplet array with high fidelity. With a single injection of 16 nL of sample solution, an array of droplets with concentration gradient spanning 3-4 orders of magnitude could be generated. The present system was applied in the enzyme inhibition assay of β-galactosidase to preliminarily demonstrate its potential in high throughput drug screening. With a single injection of 16 nL of inhibitor solution, more than 240 in-droplet enzyme inhibition reactions with different inhibitor concentrations could be performed with an analysis time of 2.5 min. Compared with multiwell plate-based screening systems, the inhibitor consumption was reduced 1000-fold. © 2011 American Chemical Society

High-yield synthesis of vaterite microparticles in gypsum suspension system via ultrasonic probe vibration/magnetic stirring

NASA Astrophysics Data System (ADS)

Wang, Bo; Pan, Zihe; Cheng, Huaigang; Chen, Zuliang; Cheng, Fangqin

2018-06-01

Vaterite-type calcium carbonate particles have some unique properties such as high hydrophilicity, large surface areas, and hierarchical structures consisting of primary vaterite particles in comparison with calcite or aragonite-type polymorphs. In this paper, gypsum (CaSO4·2H2O) suspension is used to synthesize micro-sized vaterite CaCO3 through magnetic stirring (MS) and ultrasonic probe vibration (UPV) methods. The effects of ammonia concentration, CO2 flow rate, solid-liquid ratio on the gypsum carbonation process, mineral phase composition, morphology and particle size distribution of CaCO3 are investigated. The results show that the carbonation process is significantly influenced by ammonia concentration, CO2 flow rate and ultrasound. Comparing with magnetic stirring, ultrasonic probe vibration take less time to reach the complete carbonate reaction. Gypsum is transformed to vaterite with the conversion rate about ∼95% when the mole ratio of NH4+/Ca2+ is 2.4 otherwise the carbonation reaction was uncompleted with gypsum residues left. Comparing with MS method, the UPV method resulted in smaller size and narrower size distribution of as-prepared microparticles and approximately 80% reduction of the particle size was achieved. It is established that increasing the solid-liquid ratio resulted in larger particle size in MS system and smaller particle size in UPV system. Increasing CO2 flow rate caused the particle size decreased in MS system and increased in UPV system.

Gold-nanoparticle-catalyzed synthesis of propargylamines: the traditional A3-multicomponent reaction performed as a two-step flow process.

PubMed

Abahmane, Lahbib; Köhler, J Michael; Gross, G Alexander

2011-03-01

The alkyne, aldehyde, amine A(3)-coupling reaction, a traditional multicomponent reaction (MCR), has been investigated as a two-step flow process. The implicated aminoalkylation reaction of phenylacetylene with appropriate aldimine intermediates was catalyzed by gold nanoparticles impregnated on alumina. The aldimine formation was catalyzed by Montmorillonite K10 beforehand. The performance of the process has been investigated with respect to different reaction regimes. Usually, the A(3)-multicomponent reaction is performed as a "one-pot" process. Diversity-oriented syntheses using MCRs often have the shortcoming that only low selectivity and low yields are achieved. We have used a flow-chemistry approach to perform the A(3)-MCR in a sequential manner. In this way, the reaction performance was significantly enhanced in terms of shortened reaction time, and the desired propargylamines were obtained in high yields. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Commodity-Free Calibration

NASA Technical Reports Server (NTRS)

2008-01-01

Commodity-free calibration is a reaction rate calibration technique that does not require the addition of any commodities. This technique is a specific form of the reaction rate technique, where all of the necessary reactants, other than the sample being analyzed, are either inherent in the analyzing system or specifically added or provided to the system for a reason other than calibration. After introduction, the component of interest is exposed to other reactants or flow paths already present in the system. The instrument detector records one of the following to determine the rate of reaction: the increase in the response of the reaction product, a decrease in the signal of the analyte response, or a decrease in the signal from the inherent reactant. With this data, the initial concentration of the analyte is calculated. This type of system can analyze and calibrate simultaneously, reduce the risk of false positives and exposure to toxic vapors, and improve accuracy. Moreover, having an excess of the reactant already present in the system eliminates the need to add commodities, which further reduces cost, logistic problems, and potential contamination. Also, the calculations involved can be simplified by comparison to those of the reaction rate technique. We conducted tests with hypergols as an initial investigation into the feasiblility of the technique.

Comparison of online reporting systems and their compatibility check with respective adverse drug reaction reporting forms.

PubMed

Maharshi, Vikas; Nagar, Pravesh

2017-01-01

Different forms and online tools are available in different countries for spontaneous reporting, one of the most widely used methods of pharmacovigilance. Capturing sufficient information and adequate compatibility of online systems with respective reporting form is highly desirable for appropriate reporting of adverse drug reactions (ADRs). This study was aimed to compare three major online reporting systems (US, UK, and WHO) of the world and also to check their compatibility with the respective ADR reporting form. A total of 89 data elements to provide relevant information were found out from above three online reporting systems. All three online systems were compared regarding magnitude of information captured by each of them and scoring was done by providing a score of "1" to each element. Compatibility of ADR reporting forms of India (Red form), US (Form 3500), and UK (Yellow card form) was assessed by comparing the information gathered by them with that can be entered into their respective online reporting systems, namely, "VigiFlow," "US online reporting," and "Yellow card online reporting." Each unmatching item was given a score of "-1". VigiFlow scored "74" points, whereas online reporting systems of the US and UK scored "56" and "49," respectively, regarding magnitude of the information gathered by them. Compatibility score was found to be "0," "-9," and "-26" in case of ADR reporting systems of US, UK, and India, respectively. Our study reveals that "VigiFlow" is capable of capturing the maximum amount of information but "Form 3500" and "Online reporting system of US" are maximally compatible to each other among ADR reporting systems of all three countries.

Assessing hydrodynamic effects on jarosite dissolution rates, reaction products, and preservation on Mars

NASA Astrophysics Data System (ADS)

Dixon, Emily M.; Elwood Madden, Andrew S.; Hausrath, Elisabeth M.; Elwood Madden, Megan E.

2015-04-01

Jarosite flow-through dissolution experiments were conducted in ultrapure water (UPW), pH 2 sulfuric acid, and saturated NaCl and CaCl2 brines at 295-298 K to investigate how hydrologic variables may affect jarosite preservation and reaction products on Mars. K+-based dissolution rates in flowing UPW did not vary significantly with flow rate, indicating that mineral surface reactions control dissolution rates over the range of flow rates investigated. In all of the solutions tested, hydrologic variables do not significantly affect extent of jarosite alteration; therefore, jarosite is equally likely to be preserved in flowing or stagnant waters on Mars. However, increasing flow rate did affect the mineralogy and accumulation of secondary reaction products. Iron release rates in dilute solutions increased as the flow rate increased, likely due to nanoscale iron (hydr)oxide transport in flowing water. Anhydrite formed in CaCl2 brine flow-through experiments despite low temperatures, while metastable gypsum and bassanite were observed in batch experiments. Therefore, observations of the hydration state of calcium sulfate minerals on Mars may provide clues to unravel past salinity and hydrologic conditions as well as temperatures and vapor pressures.

The Phase Behavior Effect on the Reaction Engineering of Transesterification Reactions and Reactor Design for Continuous Biodiesel Production

NASA Astrophysics Data System (ADS)

Csernica, Stephen N.

The demand for renewable forms of energy has increased tremendously over the past two decades. Of all the different forms of renewable energy, biodiesel, a liquid fuel, has emerged as one of the more viable possibilities. This is in large part due to the fact that biodiesel can readily be used in modern day diesel engines with nearly no engine modifications. It is commonly blended with conventional petroleum-derived diesel but it can also be used neat. As a result of the continued growth of the industry, there has been a correspondingly large increase in the scientific and technical research conducted on the subject. Much of the research has been conducted on the feasibility of using different types of feedstocks, which generally vary with respect to geographic locale, as well as different types of catalysts. Much of the work of the present study was involved with the investigation of the binary liquid-liquid nature of the system and its effects on the reaction kinetics. Initially, the development of an analytical method for the analysis of the compounds present in transesterification reaction mixtures using high performance liquid chromatography (HPLC) was developed. The use of UV(205 nm) as well as refractive index detection (RID) were shown capable to detect the various different types of components associated with transesterification reactions. Reversed-phase chromatography with isocratic elution was primarily used. Using a unique experimental apparatus enabling the simultaneous analysis of both liquid phases throughout the reaction, an experimental method was developed for measuring the reaction rate under both mass transfer control and reaction control. The transesterification reaction rate under each controlling mechanism was subsequently evaluated and compared. It was determined that the reaction rate is directly proportional to the concentration of triglycerides in the methanol phase. Furthermore, the reaction rate accelerates rapidly as the system transitions from two phases to a single phase, or pseudo-single phase. The transition to a single phase or pseudo-single phase is a function of the methanol content. Regardless, the maximum observed reaction rate occurs at the point of the phase transition, when the concentration of triglycerides in the methanol phase is largest. The phase transition occurs due to the accumulation of the primary product, biodiesel methyl esters. Through various experiments, it was determined that the rate of the triglyceride mass transfer into the methanol phase, as well as the solubility of triglycerides in methanol, increases with increasing methyl ester concentration. Thus, there exists some critical methyl ester concentration which favors the formation of a single or pseudo-single phase system. The effect of the by-product glycerol on the reaction kinetics was also investigated. It was determined that at low methanol to triglyceride molar ratios, glycerol acts to inhibit the reaction rate and limit the overall triglyceride conversion. This occurs because glycerol accumulates in the methanol phase, i.e. the primary reaction volume. When glycerol is at relatively high concentrations within the methanol phase, triglycerides become excluded from the reaction volume. This greatly reduces the reaction rate and limits the overall conversion. As the concentration of methanol is increased, glycerol becomes diluted and the inhibitory effects become dampened. Assuming pseudo-homogeneous phase behavior, a simple kinetic model incorporating the inhibitory effects of glycerol was proposed based on batch reactor data. The kinetic model was primarily used to theoretically compare the performance of different types of continuous flow reactors for continuous biodiesel production. It was determined that the inhibitory effects of glycerol result in the requirement of very large reactor volumes when using continuous stirred tank reactors (CSTR). The reactor volume can be greatly reduced using tubular style plug flow reactors (PFR). Despite this fact, the use of CSTRs is more common than the use of PFRs. This is mostly due to the fact that the two initial reactant phases are relatively immiscible and significant agitation is generally supplied to initiate the reaction. Based on the theoretical results, however, the use of a packed-bed tubular flow reactor was investigated experimentally. A series of two tubular flow reactors was built in the laboratory. The first reactor was of the shell and tube variety and also functioned as a preheater. The second reactor was larger and contained a packed-bed. Two different flow configurations were invested, upflow-upflow and downflow-downflow. It was determined that the downflow-downflow configuration provided significantly better triglyceride conversions that the upflow-upflow configuration.

Kinetics of ozone-initiated oxidation of textile dye, Amaranth in aqueous systems.

PubMed

Dachipally, Purnachandar; Jonnalagadda, Sreekanth B

2011-01-01

The ozone facilitated oxidation mechanism of water soluble azo anionic dye, amaranth (Am) was investigated monitoring the depletion kinetics of the dye spectrometrically at 521 nm. The oxidation kinetics of the dye by ozone was studied under semi-batch conditions, by bubbling ozone enriched oxygen through the aqueous reaction mixture of dye, as function of flow rate, ionic strength, [O(3)] and pH variations. With excess concentration of ozone and other reagents and low [amaranth], reaction followed pseudo-first-order kinetics with respect to the dye. Added neutral salts had marginal effect on the reaction rate and the variation of pH from 7 to 2 and 7 to 12 exerted only small increases in the reaction rate suggesting molecular ozone possibly is the principle reactive species in oxidation of dye. The reaction order with respect ozone was near unity and it varied slightly with pH and flow rate variations. The overall second-order rate constant for the reaction was (105 ± 4) M(-1) min(-1). The main oxidation products immediately after amaranth decolorization were identified. The reaction mechanism and overall rate law were proposed. After spiking the seawater, river water and wastewaters with Amaranth dye, the reaction rates and trends in BOD and COD under control and natural conditions were investigated. The rate of depletion of the dye in natural waters was relatively lower, but the ozonation process significantly decreased both the BOD and COD levels.

On site experiments of the slanted soil treatment systems for domestic gray water.

PubMed

Itayama, Tomoaki; Kiji, Masato; Suetsugu, Aya; Tanaka, Nobuyuki; Saito, Takeshi; Iwami, Norio; Mizuochi, Motoyuki; Inamori, Yuhei

2006-01-01

In order to make a breakthrough for the acute problem of water shortage in the world, the key words "decentralization and re-use" are very important for new sustainable sanitation systems that will be developed. Therefore, we focused on a new treatments system called "a slanted soil treatment system" which combines a biotoilet system with a domestic grey water treatment system. Because this system is a low cost and compact system, the system can be easily introduced to homes in urban areas or in the suburbs of cities in many developing countries. In this study, we performed on site experiments carried out on Shikoku Island, Japan, for several years. We obtained the following results. The slanted soil treatment system could remove organic pollutants and total nitrogen and total phosphorus in grey water effectively. Furthermore, the system performance became high in the case of the high concentration of the influent water. The nitrification reaction and denitrification reaction were speculated to exist due to aerobic zones and anaerobic zones present in the slanted soil treatment system. The slanted soil treatment system could perform for approximately 3 years with zero maintenance. The plug flow model of 1st order reaction kinetics could describe the reaction in the slanted soil treatment system. However, it is necessary to improve the system to maintain the performance in all seasons.

Impact of microstructure evolution on the difference between geometric and reactive surface areas in natural chalk

NASA Astrophysics Data System (ADS)

Yang, Y.; Bruns, S.; Stipp, S. L. S.; Sørensen, H. O.

2018-05-01

The coupling between flow and mineral dissolution drives the evolution of many natural and engineered flow systems. Pore surface changes as microstructure evolves but this transient behaviour has traditionally been difficult to model. We combined a reactor network model with experimental, greyscale tomography data to establish the morphological grounds for differences among geometric, reactive and apparent surface areas in dissolving chalk. This approach allowed us to study the effects of initial geometry and macroscopic flow rate independently. The simulations showed that geometric surface, which represents a form of local transport heterogeneity, increases in an imposed flow field, even when the porous structure is chemically homogeneous. Hence, the fluid-reaction coupling leads to solid channelisation, which further results in fluid focusing and an increase in geometric surface area. Fluid focusing decreases the area of reactive surface and the residence time of reactant, both contribute to the over-normalisation of reaction rate. In addition, the growing and merging of microchannels, near the fluid entrance, contribute to the macroscopic, fast initial dissolution rate of rocks.

Simultaneous destraction and desulfurization of Illinois coals with supercritical ethanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, B.C.

1983-01-01

Various Illinois coals (with Illinois number6 being the main one) are liquefied with various supercritical solvents (ethanol being the main solvent) at 543-598 K, system pressures of 6.99-24.23 MPa, flow rates of 3.0-7.5 ml/min, reaction time of 0-180 minutes, and coal particle sizes of 0.36-0.85 mm to 1.00-2.36 mm to systematically investigate the effects of flow rates, reaction time, coal particle size, temperature, pressure, coal characteristics (by using different Illinois coals), supercritical medium (by using different solvents), and the addition of potassium hydroxide. The % weight loss of coal and the % sulfur removal during destraction and desulfurization of coalmore » are functions of the flow rate, the reaction time, the coal particle size, temperature, pressure and the supercritical solvent. Temperature, pressure and the supercritical medium are the most important parameters in controlling the % weight loss of coal and the % sulfur removal. The % weight loss of coal can be related to a power law and fits quite nicely into a second order kinetic model. The % sulfur removal also follows a second order kinetic model. A secondary reaction is observed during the destraction process, which implies that destraction, and possibly desulfurization, of coal is a multistep reaction including a physical extraction step where the major portion of the coal and sulfur was removed and then followed by a chemical reaction. Supercritical ethanol definitely enhances the removal of sulfur compounds from coal. The enhanced selectivity by supercritical ethanol is greatest at a pressure just above the critical pressure of ethanol. Finally, addition of a base such as potassium hydroxide enhances both % weight loss of coal and the % sulfur removal.« less

Heterogeneous Pd catalysts as emulsifiers in Pickering emulsions for integrated multistep synthesis in flow chemistry.

PubMed

Hiebler, Katharina; Lichtenegger, Georg J; Maier, Manuel C; Park, Eun Sung; Gonzales-Groom, Renie; Binks, Bernard P; Gruber-Woelfler, Heidrun

2018-01-01

Within the "compartmentalised smart factory" approach of the ONE-FLOW project the implementation of different catalysts in "compartments" provided by Pickering emulsions and their application in continuous flow is targeted. We present here the development of heterogeneous Pd catalysts that are ready to be used in combination with biocatalysts for catalytic cascade synthesis of active pharmaceutical ingredients (APIs). In particular, we focus on the application of the catalytic systems for Suzuki-Miyaura cross-coupling reactions, which is the key step in the synthesis of the targeted APIs valsartan and sacubitril. An immobilised enzyme will accomplish the final product formation via hydrolysis. In order to create a large interfacial area for the catalytic reactions and to keep the reagents separated until required, the catalyst particles are used to stabilise Pickering emulsions of oil and water. A set of Ce-Sn-Pd oxides with the molecular formula Ce 0.99- x Sn x Pd 0.01 O 2-δ ( x = 0-0.99) has been prepared utilising a simple single-step solution combustion method. The high applicability of the catalysts for different functional groups and their minimal leaching behaviour is demonstrated with various Suzuki-Miyaura cross-coupling reactions in batch as well as in continuous flow employing the so-called "plug & play reactor". Finally, we demonstrate the use of these particles as the sole emulsifier of oil-water emulsions for a range of oils.

Micromixer-based time-resolved NMR: applications to ubiquitin protein conformation.

PubMed

Kakuta, Masaya; Jayawickrama, Dimuthu A; Wolters, Andrew M; Manz, Andreas; Sweedler, Jonathan V

2003-02-15

Time-resolved NMR spectroscopy is used to studychanges in protein conformation based on the elapsed time after a change in the solvent composition of a protein solution. The use of a micromixer and a continuous-flow method is described where the contents of two capillary flows are mixed rapidly, and then the NMR spectra of the combined flow are recorded at precise time points. The distance after mixing the two fluids and flow rates define the solvent-protein interaction time; this method allows the measurement of NMR spectra at precise mixing time points independent of spectral acquisition time. Integration of a micromixer and a microcoil NMR probe enables low-microliter volumes to be used without losing significant sensitivity in the NMR measurement. Ubiquitin, the model compound, changes its conformation from native to A-state at low pH and in 40% or higher methanol/water solvents. Proton NMR resonances of the His-68 and the Tyr-59 of ubiquitin are used to probe the conformational changes. Mixing ubiquitin and methanol solutions under low pH at microliter per minute flow rates yields both native and A-states. As the flow rate decreases, yielding longer reaction times, the population of the A-state increases. The micromixer-NMR system can probe reaction kinetics on a time scale of seconds.

Frozen reaction fronts in steady flows: A burning-invariant-manifold perspective

NASA Astrophysics Data System (ADS)

Mahoney, John R.; Li, John; Boyer, Carleen; Solomon, Tom; Mitchell, Kevin A.

2015-12-01

The dynamics of fronts, such as chemical reaction fronts, propagating in two-dimensional fluid flows can be remarkably rich and varied. For time-invariant flows, the front dynamics may simplify, settling in to a steady state in which the reacted domain is static, and the front appears "frozen." Our central result is that these frozen fronts in the two-dimensional fluid are composed of segments of burning invariant manifolds, invariant manifolds of front-element dynamics in x y θ space, where θ is the front orientation. Burning invariant manifolds (BIMs) have been identified previously as important local barriers to front propagation in fluid flows. The relevance of BIMs for frozen fronts rests in their ability, under appropriate conditions, to form global barriers, separating reacted domains from nonreacted domains for all time. The second main result of this paper is an understanding of bifurcations that lead from a nonfrozen state to a frozen state, as well as bifurcations that change the topological structure of the frozen front. Although the primary results of this study apply to general fluid flows, our analysis focuses on a chain of vortices in a channel flow with an imposed wind. For this system, we present both experimental and numerical studies that support the theoretical analysis developed here.

Viscous dissipation and Joule heating effects in MHD 3D flow with heat and mass fluxes

NASA Astrophysics Data System (ADS)

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

2018-03-01

The present research explores the three-dimensional stretched flow of viscous fluid in the presence of prescribed heat (PHF) and concentration (PCF) fluxes. Mathematical formulation is developed in the presence of chemical reaction, viscous dissipation and Joule heating effects. Fluid is electrically conducting in the presence of an applied magnetic field. Appropriate transformations yield the nonlinear ordinary differential systems. The resulting nonlinear system has been solved. Graphs are plotted to examine the impacts of physical parameters on the temperature and concentration distributions. Skin friction coefficients and local Nusselt and Sherwood numbers are computed and analyzed.

Discontinuous Galerkin method for multicomponent chemically reacting flows and combustion

NASA Astrophysics Data System (ADS)

Lv, Yu; Ihme, Matthias

2014-08-01

This paper presents the development of a discontinuous Galerkin (DG) method for application to chemically reacting flows in subsonic and supersonic regimes under the consideration of variable thermo-viscous-diffusive transport properties, detailed and stiff reaction chemistry, and shock capturing. A hybrid-flux formulation is developed for treatment of the convective fluxes, combining a conservative Riemann-solver and an extended double-flux scheme. A computationally efficient splitting scheme is proposed, in which advection and diffusion operators are solved in the weak form, and the chemically stiff substep is advanced in the strong form using a time-implicit scheme. The discretization of the viscous-diffusive transport terms follows the second form of Bassi and Rebay, and the WENO-based limiter due to Zhong and Shu is extended to multicomponent systems. Boundary conditions are developed for subsonic and supersonic flow conditions, and the algorithm is coupled to thermochemical libraries to account for detailed reaction chemistry and complex transport. The resulting DG method is applied to a series of test cases of increasing physico-chemical complexity. Beginning with one- and two-dimensional multispecies advection and shock-fluid interaction problems, computational efficiency, convergence, and conservation properties are demonstrated. This study is followed by considering a series of detonation and supersonic combustion problems to investigate the convergence-rate and the shock-capturing capability in the presence of one- and multistep reaction chemistry. The DG algorithm is then applied to diffusion-controlled deflagration problems. By examining convergence properties for polynomial order and spatial resolution, and comparing these with second-order finite-volume solutions, it is shown that optimal convergence is achieved and that polynomial refinement provides advantages in better resolving the localized flame structure and complex flow-field features associated with multidimensional and hydrodynamic/thermo-diffusive instabilities in deflagration and detonation systems. Comparisons with standard third- and fifth-order WENO schemes are presented to illustrate the benefit of the DG scheme for application to detonation and multispecies flow/shock-interaction problems.

Modeling convection-diffusion-reaction systems for microfluidic molecular communications with surface-based receivers in Internet of Bio-Nano Things

PubMed Central

Akan, Ozgur B.

2018-01-01

We consider a microfluidic molecular communication (MC) system, where the concentration-encoded molecular messages are transported via fluid flow-induced convection and diffusion, and detected by a surface-based MC receiver with ligand receptors placed at the bottom of the microfluidic channel. The overall system is a convection-diffusion-reaction system that can only be solved by numerical methods, e.g., finite element analysis (FEA). However, analytical models are key for the information and communication technology (ICT), as they enable an optimisation framework to develop advanced communication techniques, such as optimum detection methods and reliable transmission schemes. In this direction, we develop an analytical model to approximate the expected time course of bound receptor concentration, i.e., the received signal used to decode the transmitted messages. The model obviates the need for computationally expensive numerical methods by capturing the nonlinearities caused by laminar flow resulting in parabolic velocity profile, and finite number of ligand receptors leading to receiver saturation. The model also captures the effects of reactive surface depletion layer resulting from the mass transport limitations and moving reaction boundary originated from the passage of finite-duration molecular concentration pulse over the receiver surface. Based on the proposed model, we derive closed form analytical expressions that approximate the received pulse width, pulse delay and pulse amplitude, which can be used to optimize the system from an ICT perspective. We evaluate the accuracy of the proposed model by comparing model-based analytical results to the numerical results obtained by solving the exact system model with COMSOL Multiphysics. PMID:29415019

Modeling convection-diffusion-reaction systems for microfluidic molecular communications with surface-based receivers in Internet of Bio-Nano Things.

PubMed

Kuscu, Murat; Akan, Ozgur B

2018-01-01

We consider a microfluidic molecular communication (MC) system, where the concentration-encoded molecular messages are transported via fluid flow-induced convection and diffusion, and detected by a surface-based MC receiver with ligand receptors placed at the bottom of the microfluidic channel. The overall system is a convection-diffusion-reaction system that can only be solved by numerical methods, e.g., finite element analysis (FEA). However, analytical models are key for the information and communication technology (ICT), as they enable an optimisation framework to develop advanced communication techniques, such as optimum detection methods and reliable transmission schemes. In this direction, we develop an analytical model to approximate the expected time course of bound receptor concentration, i.e., the received signal used to decode the transmitted messages. The model obviates the need for computationally expensive numerical methods by capturing the nonlinearities caused by laminar flow resulting in parabolic velocity profile, and finite number of ligand receptors leading to receiver saturation. The model also captures the effects of reactive surface depletion layer resulting from the mass transport limitations and moving reaction boundary originated from the passage of finite-duration molecular concentration pulse over the receiver surface. Based on the proposed model, we derive closed form analytical expressions that approximate the received pulse width, pulse delay and pulse amplitude, which can be used to optimize the system from an ICT perspective. We evaluate the accuracy of the proposed model by comparing model-based analytical results to the numerical results obtained by solving the exact system model with COMSOL Multiphysics.

The crystallization kinetic model of nano-CaCO3 in CO2-ammonia-phosphogypsum three-phase reaction system

NASA Astrophysics Data System (ADS)

Liu, Hao; Lan, Peiqiang; Lu, Shangqing; Wu, Sufang

2018-06-01

Phosphogypsum (PG) as a low-cost calcium resource was used to prepare nano-CaCO3 in a three-phase system by reactions. Based on the population balance equation, nano-CaCO3 crystal nucleation and growth model in the gas (CO2)-liquid (NH3·H2O)-solid (CaSO4) three-phase system was established. The crystallization kinetic model of nano-CaCO3 in CO2-NH3·H2O-CaSO4 reactions system was experimental developed over an optimized temperature range of 20-40 °C and CO2 flow rate range of 138-251 ml/min as rCaCO3 =kn 32 πM2γ3/3R3ρ2T3 (C -C∗)0.8/[ ln (C /C∗) ]3 + πρ/3M kg3 kn(C -C∗) 2t3 , where nano-CaCO3 nucleation rate constant was kn = 6.24 ×1019 exp(-15940/RT) and nano-CaCO3 growth rate constant was kg = 0.79 exp(-47650/RT) respectively. Research indicated that nucleation rates and growth rates both increased with the increasing of temperature and CO32- ion concentration. And crystal growth was dependent on temperature more than that of nucleation process because the activation energy of CaCO3 growth was bigger than that of CaCO3 nucleation. Decreasing the reaction temperature and CO2 flow rate was more beneficial for producing nano-size CaCO3 because of the lower CaCO3 growth rates. The deduced kinetic equation could briefly predict the average particle sizes of nano-CaCO3.

Moving from Batch to Field Using the RT3D Reactive Transport Modeling System

NASA Astrophysics Data System (ADS)

Clement, T. P.; Gautam, T. R.

2002-12-01

The public domain reactive transport code RT3D (Clement, 1997) is a general-purpose numerical code for solving coupled, multi-species reactive transport in saturated groundwater systems. The code uses MODFLOW to simulate flow and several modules of MT3DMS to simulate the advection and dispersion processes. RT3D employs the operator-split strategy which allows the code solve the coupled reactive transport problem in a modular fashion. The coupling between reaction and transport is defined through a separate module where the reaction equations are specified. The code supports a versatile user-defined reaction option that allows users to define their own reaction system through a Fortran-90 subroutine, known as the RT3D-reaction package. Further a utility code, known as BATCHRXN, allows the users to independently test and debug their reaction package. To analyze a new reaction system at a batch scale, users should first run BATCHRXN to test the ability of their reaction package to model the batch data. After testing, the reaction package can simply be ported to the RT3D environment to study the model response under 1-, 2-, or 3-dimensional transport conditions. This paper presents example problems that demonstrate the methods for moving from batch to field-scale simulations using BATCHRXN and RT3D codes. The first example describes a simple first-order reaction system for simulating the sequential degradation of Tetrachloroethene (PCE) and its daughter products. The second example uses a relatively complex reaction system for describing the multiple degradation pathways of Tetrachloroethane (PCA) and its daughter products. References 1) Clement, T.P, RT3D - A modular computer code for simulating reactive multi-species transport in 3-Dimensional groundwater aquifers, Battelle Pacific Northwest National Laboratory Research Report, PNNL-SA-28967, September, 1997. Available at: http://bioprocess.pnl.gov/rt3d.htm.

[THE STATE OF HEPATIC AND SPLANCHNIC BLOOD FLOW IN VARIOUS TYPES OF COMPLICATED PANCREATIC PSEUDOCYSTS].

PubMed

Kryvoruchko, I A; Goncharova, N M; Andreyeshchev, S A; Yavorska, T P

2015-05-01

Investigations were conducted in 37 patients, suffering complicated pancreatic pseudocysts. In accordance to data of ultrasound Doppler flowmetry for the blood flow along portal vein, a. hepatis communis, a. mesenterica superior in complicated pancreatic pseudocysts compensatory--adaptive reactions on level of hepatic--spanchnic blood flow are directed towards restriction of the blood inflow through the portal vein system. This is accompanied by the common peripheral vascular resistence raising in basin of a. mesenterica superior, which have depended upon the patients' state severity, caused by reduction of the volume blood flow in a certan vascular collector. The oxygen debt of the liver in these patients is compensated by the volume blood flow enhancement along a. hepatis communis.

Simultaneous removal of SO2 and NOx from flue gas by wet scrubbing using a urea solution.

PubMed

Li, Ge; Wang, Baodong; Xu, Wayne Qiang; Li, Yonglong; Han, Yifan; Sun, Qi

2018-03-27

Nitrogen oxides (NO x ) and sulfur dioxide (SO 2 ) are major air pollutants, so simultaneously removing them from gases emitted during fossil fuel combustion in stationary systems is important. Wet denitrification using urea is used for a wide range of systems. Additives have strong effects on wet denitrification using urea, and different mechanisms are involved and different effects found using different additives. In this study, the effects of different additives, initial urea concentrations, reaction temperatures, initial pH values, gas flow rates, and reaction times on the simultaneous desulfurization and denitrification efficiencies achieved using wet denitrification using urea were studied in single factor experiment. The optimum reaction conditions for desulfurization and denitrification were found. Desulfurization and denitrification efficiencies of 97.5% and 96.3%, respectively, were achieved at a KMnO 4 concentration 5 mmol/L, a reaction temperature of 70°C, initial urea solution pH 8, a urea concentration of 9%, and a gas flow rate of 40 L/h. The concentrations of the desulfurization and denitrification reaction products in the solution were determined. NO x was mainly transformed into N 2 , and the [Formula: see text] and [Formula: see text] concentrations in the solution became very low. The reactions involved in SO 2 and NO x removal using urea were analyzed from the thermodynamic viewpoint. Increasing the temperature was not conducive to the reactions but increased the rate constant, so an optimum temperature was determined. The simultaneous desulfurization and denitrification kinetics were calculated. The urea consumption and [Formula: see text], [Formula: see text], and [Formula: see text] generation reactions were all zero order. The [Formula: see text] generation rate was greater than the [Formula: see text] generation rate. The simultaneous desulfurization and denitrification process and mechanism were studied. The results provide reference data for performing flue gas desulfurization and denitrification in factories.

Numerical investigation of flow and heat transfer in a novel configuration multi-tubular fixed bed reactor for propylene to acrolein process

NASA Astrophysics Data System (ADS)

Jiang, Bin; Hao, Li; Zhang, Luhong; Sun, Yongli; Xiao, Xiaoming

2015-01-01

In the present contribution, a numerical study of fluid flow and heat transfer performance in a pilot-scale multi-tubular fixed bed reactor for propylene to acrolein oxidation reaction is presented using computational fluid dynamics (CFD) method. Firstly, a two-dimensional CFD model is developed to simulate flow behaviors, catalytic oxidation reaction, heat and mass transfer adopting porous medium model on tube side to achieve the temperature distribution and investigate the effect of operation parameters on hot spot temperature. Secondly, based on the conclusions of tube-side, a novel configuration multi-tubular fixed-bed reactor comprising 790 tubes design with disk-and-doughnut baffles is proposed by comparing with segmental baffles reactor and their performance of fluid flow and heat transfer is analyzed to ensure the uniformity condition using molten salt as heat carrier medium on shell-side by three-dimensional CFD method. The results reveal that comprehensive performance of the reactor with disk-and-doughnut baffles is better than that of with segmental baffles. Finally, the effects of operating conditions to control the hot spots are investigated. The results show that the flow velocity range about 0.65 m/s is applicable and the co-current cooling system flow direction is better than counter-current flow to control the hottest temperature.

Effect of the SiCl4 Flow Rate on SiBN Deposition Kinetics in SiCl4-BCl3-NH3-H2-Ar Environment

PubMed Central

Li, Jianping; Qin, Hailong; Liu, Yongsheng; Ye, Fang; Li, Zan; Cheng, Laifei; Zhang, Litong

2017-01-01

To improve the thermal and mechanical stability of SiCf/SiC or C/SiC composites with SiBN interphase, SiBN coating was deposited by low pressure chemical vapor deposition (LPCVD) using SiCl4-BCl3-NH3-H2-Ar gas system. The effect of the SiCl4 flow rate on deposition kinetics was investigated. Results show that deposition rate increases at first and then decreases with the increase of the SiCl4 flow rate. The surface of the coating is a uniform cauliflower-like structure at the SiCl4 flow rate of 10 mL/min and 20 mL/min. The surface is covered with small spherical particles when the flow rate is 30 mL/min. The coatings deposited at various SiCl4 flow rates are all X-ray amorphous and contain Si, B, N, and O elements. The main bonding states are B-N, Si-N, and N-O. B element and B-N bonding decrease with the increase of SiCl4 flow rate, while Si element and Si-N bonding increase. The main deposition mechanism refers to two parallel reactions of BCl3+NH3 and SiCl4+NH3. The deposition process is mainly controlled by the reaction of BCl3+NH3. PMID:28772986

Coupling desalination and energy storage with redox flow electrodes.

PubMed

Hou, Xianhua; Liang, Qian; Hu, Xiaoqiao; Zhou, Yu; Ru, Qiang; Chen, Fuming; Hu, Shejun

2018-06-26

Both freshwater shortage and energy crisis are global issues. Herein, we present a double-function system of faradaic desalination and a redox flow battery consisting of VCl3|NaI redox flow electrodes and a feed stream. The system has a nominal cell potential (E0 = +0.79 V). During the discharge process, the salt ions in the feed are extracted by the redox reaction of the flow electrodes, which is indicated by salt removal. Stable and reversible salt removal capacity and electricity can be achieved up to 30 cycles. The energy consumption is as low as 10.27 kJ mol-1 salt. The energy efficiency is as high as 50% in the current aqueous redox flow battery. With energy recovery, the desalination energy consumption decreases greatly to 5.38 kJ mol-1; this is the lowest reported value to date. This "redox flow battery desalination generator" can be operated in a voltage range of 0.3-1.1 V. Our research provides a novel method for obtaining energy-saving desalination and redox flow batteries.

A pilot study of a simple screening technique for estimation of salivary flow.

PubMed

Kanehira, Takashi; Yamaguchi, Tomotaka; Takehara, Junji; Kashiwazaki, Haruhiko; Abe, Takae; Morita, Manabu; Asano, Kouzo; Fujii, Yoshinori; Sakamoto, Wataru

2009-09-01

The purpose of this study was to develop a simple screening technique for estimation of salivary flow and to test the usefulness of the method for determining decreased salivary flow. A novel assay system comprising 3 spots containing 30 microg starch and 49.6 microg potassium iodide per spot on filter paper and a coloring reagent, based on the color reaction of iodine-starch and theory of paper chromatography, was designed. We investigated the relationship between resting whole salivary rates and the number of colored spots on the filter produced by 41 hospitalized subjects. A significant negative correlation was observed between the number of colored spots and the resting salivary flow rate (n = 41; r = -0.803; P < .01). For all complaints of decreased salivary flow (n = 9) having cutoff values <100 microL/min for the salivary flow rate, 3 colored spots appeared on the paper, whereas for healthy subjects there was < or =1 colored spot. This novel assay system might be effective for estimation of salivary flow not only in healthy but also in bedridden and disabled elderly people.

A comprehensive model to determine the effects of temperature and species fluctuations on reactions in turbulent reacting flows

NASA Technical Reports Server (NTRS)

Antaki, P. J.

1981-01-01

The joint probability distribution function (pdf), which is a modification of the bivariate Gaussian pdf, is discussed and results are presented for a global reaction model using the joint pdf. An alternative joint pdf is discussed. A criterion which permits the selection of temperature pdf's in different regions of turbulent, reacting flow fields is developed. Two principal approaches to the determination of reaction rates in computer programs containing detailed chemical kinetics are outlined. These models represent a practical solution to the modeling of species reaction rates in turbulent, reacting flows.

Stopped-in-loop flow analysis of trace vanadium in water.

PubMed

Teshima, Norio; Ohno, Shinsuke; Sakai, Tadao

2007-01-01

The new concept of stopped-in-loop flow analysis (SIL-FA) is proposed, and an SIL-FA method for the catalytic determination of vanadium is demonstrated. In an SIL format, a sample solution merges with reagent(s), and the well-mixed solution is loaded into a loop. The solution in the loop is separated by a six-way switching valve from the main stream. While the reaction proceeds in the stationary loop, the SIL-FA system does not need to establish a baseline continuously. This leads to a reduction in reagent consumption and waste generation compared with traditional flow injection analysis.

Conductivity detection for monitoring mixing reactions in microfluidic devices.

PubMed

Liu, Y; Wipf, D O; Henry, C S

2001-08-01

A conductivity detector was coupled to poly(dimethylsiloxane)-glass capillary electrophoresis microchips to monitor microfluidic flow. Electroosmotic flow was investigated with both conductivity detection (CD) and the current monitoring method. No significant variation was observed between these methods, but CD showed a lower relative standard deviation. Gradient mixing experiments were employed to investigate the relationship between the electrolyte conductivity and the electrolyte concentration. A good linear response of conductivity to concentration was obtained for solutions whose difference in concentrations were less than 27 mM. The new system holds great promise for precision mixing in microfluidic devices using electrically driven flows.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bohner, Bíborka; Endrődi, Balázs; Tóth, Ágota, E-mail: atoth@chem.u-szeged.hu

The precipitation reaction of calcium oxalate is studied experimentally in the presence of spatial gradients by controlled flow of calcium into oxalate solution. The density difference between the reactants leads to strong convection in the form of a gravity current that drives the spatiotemporal pattern formation. The phase diagram of the system is constructed, the evolving precipitate patterns are analyzed and quantitatively characterized by their diameters and the average height of the gravity flow. The compact structures of calcium oxalate monohydrate produced at low flow rates are replaced by the thermodynamically unstable calcium oxalate dihydrate favored in the presence ofmore » a strong gravity current.« less

Large enhancement of oscillating chemiluminescence with [Ru(bpy)3 ](2+) -catalyzed Belousov-Zhabotinsky reaction in the presence of tri-n-propylamine.

PubMed

Lan, Xiaolan; Zheng, Baozhan; Zhao, Yan; Yuan, Hongyan; Du, Juan; Xiao, Dan

2013-01-01

Oscillating chemiluminescence enhanced by the addition of tri-n-propylamine (TPrA) to the typical Belousov-Zhabotinsky (BZ) reaction system catalyzed by ruthenium(II)tris(2.2'-bipyridine)(Ru(bpy)3 (2+) ) was investigated using a luminometry method. The [Ru(bpy)3 ](2+) /TPrA system was first used as the catalyst for a BZ oscillator in a closed system, which exhibited a shorter induction period, higher amplitude and much more stable chemiluminescence (CL) oscillation. The effects of various concentrations of TPrA, oxygen and nitrogen flow rate on the oscillating behavior of this system were examined. In addition, the CL intensity of the [Ru(bpy)3 ](2+) /TPrA-BZ system was found to be inhibited by phenol, thus providing a way for use of the BZ system in the determination of phenolic compounds. Moreover, the possible mechanism of the oscillating CL reaction catalyzed by [Ru(bpy)3 ](2+) /TPrA and the inhibition effects of oxygen and phenol on this oscillating CL system were considered. Copyright © 2012 John Wiley & Sons, Ltd.

Computational manipulation of a radiative MHD flow with Hall current and chemical reaction in the presence of rotating fluid

NASA Astrophysics Data System (ADS)

Alias Suba, Subbu; Muthucumaraswamy, R.

2018-04-01

A numerical analysis of transient radiative MHD(MagnetoHydroDynamic) natural convective flow of a viscous, incompressible, electrically conducting and rotating fluid along a semi-infinite isothermal vertical plate is carried out taking into consideration Hall current, rotation and first order chemical reaction.The coupled non-linear partial differential equations are expressed in difference form using implicit finite difference scheme. The difference equations are then reduced to a system of linear algebraic equations with a tri-diagonal structure which is solved by Thomas Algorithm. The primary and secondary velocity profiles, temperature profile, concentration profile, skin friction, Nusselt number and Sherwood Number are depicted graphically for a range of values of rotation parameter, Hall parameter,magnetic parameter, chemical reaction parameter, radiation parameter, Prandtl number and Schmidt number.It is recognized that rate of heat transfer and rate of mass transfer decrease with increase in time but they increase with increasing values of radiation parameter and Schmidt number respectively.

Controlling transient chaos in deterministic flows with applications to electrical power systems and ecology

NASA Astrophysics Data System (ADS)

Dhamala, Mukeshwar; Lai, Ying-Cheng

1999-02-01

Transient chaos is a common phenomenon in nonlinear dynamics of many physical, biological, and engineering systems. In applications it is often desirable to maintain sustained chaos even in parameter regimes of transient chaos. We address how to sustain transient chaos in deterministic flows. We utilize a simple and practical method, based on extracting the fundamental dynamics from time series, to maintain chaos. The method can result in control of trajectories from almost all initial conditions in the original basin of the chaotic attractor from which transient chaos is created. We apply our method to three problems: (1) voltage collapse in electrical power systems, (2) species preservation in ecology, and (3) elimination of undesirable bursting behavior in a chemical reaction system.

Methodology for extracting local constants from petroleum cracking flows

DOEpatents

Chang, Shen-Lin; Lottes, Steven A.; Zhou, Chenn Q.

2000-01-01

A methodology provides for the extraction of local chemical kinetic model constants for use in a reacting flow computational fluid dynamics (CFD) computer code with chemical kinetic computations to optimize the operating conditions or design of the system, including retrofit design improvements to existing systems. The coupled CFD and kinetic computer code are used in combination with data obtained from a matrix of experimental tests to extract the kinetic constants. Local fluid dynamic effects are implicitly included in the extracted local kinetic constants for each particular application system to which the methodology is applied. The extracted local kinetic model constants work well over a fairly broad range of operating conditions for specific and complex reaction sets in specific and complex reactor systems. While disclosed in terms of use in a Fluid Catalytic Cracking (FCC) riser, the inventive methodology has application in virtually any reaction set to extract constants for any particular application and reaction set formulation. The methodology includes the step of: (1) selecting the test data sets for various conditions; (2) establishing the general trend of the parametric effect on the measured product yields; (3) calculating product yields for the selected test conditions using coupled computational fluid dynamics and chemical kinetics; (4) adjusting the local kinetic constants to match calculated product yields with experimental data; and (5) validating the determined set of local kinetic constants by comparing the calculated results with experimental data from additional test runs at different operating conditions.

Highly sensitive silicon microreactor for catalyst testing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henriksen, Toke R.; Hansen, Ole; Department of Physics, Danish National Research Foundation's Center for Individual Nanoparticle Functionality

2009-12-15

A novel microfabricated chemical reactor for highly sensitive measurements of catalytic activity and surface kinetics is presented. The reactor is fabricated in a silicon chip and is intended for gas-phase reactions at pressures ranging from 0.1 to 5.0 bar. A high sensitivity is obtained by directing the entire gas flow through the catalyst bed to a mass spectrometer, thus ensuring that nearly all reaction products are present in the analyzed gas flow. Although the device can be employed for testing a wide range of catalysts, the primary aim of the design is to allow characterization of model catalysts which canmore » only be obtained in small quantities. Such measurements are of significant fundamental interest but are challenging because of the low surface areas involved. The relationship between the reaction zone gas flow and the pressure in the reaction zone is investigated experimentally. A corresponding theoretical model is presented, and the gas flow through an on-chip flow-limiting capillary is predicted to be in the intermediate regime. The experimental data for the gas flow are found to be in good agreement with the theoretical model. At typical experimental conditions, the total gas flow through the reaction zone is around 3x10{sup 14} molecules s{sup -1}, corresponding to a gas residence time in the reaction zone of about 11 s. To demonstrate the operation of the microreactor, CO oxidation on low-area platinum thin film circles is employed as a test reaction. Using temperature ramping, it is found that platinum catalysts with areas as small as 15 {mu}m{sup 2} are conveniently characterized with the device.« less

Local thermodynamic equilibrium for globally disequilibrium open systems under stress

NASA Astrophysics Data System (ADS)

Podladchikov, Yury

2016-04-01

Predictive modeling of far and near equilibrium processes is essential for understanding of patterns formation and for quantifying of natural processes that are never in global equilibrium. Methods of both equilibrium and non-equilibrium thermodynamics are needed and have to be combined. For example, predicting temperature evolution due to heat conduction requires simultaneous use of equilibrium relationship between internal energy and temperature via heat capacity (the caloric equation of state) and disequilibrium relationship between heat flux and temperature gradient. Similarly, modeling of rocks deforming under stress, reactions in system open for the porous fluid flow, or kinetic overstepping of the equilibrium reaction boundary necessarily needs both equilibrium and disequilibrium material properties measured under fundamentally different laboratory conditions. Classical irreversible thermodynamics (CIT) is the well-developed discipline providing the working recipes for the combined application of mutually exclusive experimental data such as density and chemical potential at rest under constant pressure and temperature and viscosity of the flow under stress. Several examples will be presented.

Determination of fast ozone oxidation rate for textile dyes by using a continuous quench-flow system.

PubMed

Gomes, Arlindo C; Nunes, José C; Simões, Rogério M S

2010-06-15

To study the fast kinetic decolourisation of textile dyes by ozone a continuous quench-flow system was used. This system has not been used before for these purposes. Reaction times in the range of 7-3000 ms were explored. The reaction was quenched with potassium iodide, which proved to be very effective, and the indigo method was used to follow the ozone concentration. Dyes from the most representative chemical classes currently used in the textile industry, i.e. azo and anthraquinone, were selected. Using the initial slope method, the effect of dye and ozone concentrations was researched and the kinetic equations thus established. Using tert-butyl alcohol, as radical scavenger, and pH close to 2.5, the second-order rate constant of the reactant dyes at 280 K varies in the range of 1.20x10(4)-7.09x10(5)M(-1)s(-1); the Acid Orange 7 exhibiting thus its lowest value, the Acid Blue 45 its highest value and the Acid Green 25 and 27 and Direct Yellow 4 intermediate values (approximately 1.6x10(5)M(-1)s(-1)). Without radical scavenger and the pH close to 4, the reaction rate increases one order of magnitude, but, on the reverse, the efficiency of ozone to decolourisation decreases. Copyright 2010 Elsevier B.V. All rights reserved.

Flow chemistry vs. flow analysis.

PubMed

Trojanowicz, Marek

2016-01-01

The flow mode of conducting chemical syntheses facilitates chemical processes through the use of on-line analytical monitoring of occurring reactions, the application of solid-supported reagents to minimize downstream processing and computerized control systems to perform multi-step sequences. They are exactly the same attributes as those of flow analysis, which has solid place in modern analytical chemistry in several last decades. The following review paper, based on 131 references to original papers as well as pre-selected reviews, presents basic aspects, selected instrumental achievements and developmental directions of a rapidly growing field of continuous flow chemical synthesis. Interestingly, many of them might be potentially employed in the development of new methods in flow analysis too. In this paper, examples of application of flow analytical measurements for on-line monitoring of flow syntheses have been indicated and perspectives for a wider application of real-time analytical measurements have been discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

CHARACTERIZATION OF SUB-MICRON AQUEOUS IRON(III) COLLOIDS FORMED IN THE PRESENCE OF PHOSPHATE BY SEDIMENTATION FIELD FLOW FRACTIONATION WITH MULTI-ANGLE LASER LIGHT SCATTERING DETECTION

EPA Science Inventory

Iron colloids play a major role in the water chemistry of natural watersheds and of engineered drinking water distribution systems. Phosphate is frequently added to distribution systems to control corrosion problems, so iron-phosphate colloids may form through reaction of iron in...

Towards a new method for modeling multicomponent, multiphase flow and transport in porous media

NASA Astrophysics Data System (ADS)

Kong, X. Z.; Schaedle, P.; Leal, A. M. M.; Saar, M. O.

2016-12-01

The ability to computationally simulate multiphase-multicomponent fluid flow, coupled with geochemical reactions between fluid species and rock minerals, in porous and/or fractured subsurface systems is of major importance to a vast number of applications. These include (1) carbon dioxide storage in geologic formations, (2) geothermal energy extraction, (3) combinations of the latter two applications during CO2-Plume Geothermal energy extraction, (4) waste fluid and waste storage, as well as (5) groundwater and contaminant transport. Modeling these systems with such a wide variety of coupled physical and chemical processes is both challenging and computationally expensive. In this work we present a new approach to develop a simulator for multicomponent-multiphase flow and reactive transport in porous media by using state of the art numerical tools, namely FEniCS (fenicsproject.org) and Reaktoro (reaktoro.org). The governing partial differential equations for fluid flow and transport are solved using FEniCS, which enables fast and efficient implementation of computer codes for the simulation of complex physical phenomena using finite element methods on unstructured meshes. FEniCS supports a wide range of finite element schemes of special interest to porous media flow. In addition, FEniCS interfaces with many sparse linear solvers and provides convenient tools for adaptive mesh refinement and the capability of massively parallel calculations. A fundamental component of our contribution is the coupling of our FEniCS based flow and transport solver with our chemical reaction simulator, Reaktoro, which implements efficient, robust, and accurate methods for chemical equilibrium and kinetics calculations at every node of the mesh, at every time step. These numerical methods for reaction modeling have been especially developed for performance-critical applications such as reactive transport modeling. Furthermore, Reaktoro is also used for the calculation of thermodynamic properties of rock minerals and fluids. The proposed simulator can, however, be coupled with other back-ends for the calculation of both thermodynamic and thermophysical properties of rock minerals and fluids. We present several example applications of our new approach, demonstrating its capabilities and computation speed.

Ionic Attachment as a Feasible Approach to Heterogenizing Anionic Solution Catalysts. The Carbonylation of Methanol,

DTIC Science & Technology

1980-08-01

carbonylation of methanol to acetic acid reaction is well suited for a demonstration of the feasibility and value of ionically binding a catalyst to a...approximate doubling of the reaction rate. This result suggests that a liquid flow system design in which there is a large catalyst to methanol ratio could...Heterogenizing Anionic Solution Catalysts . The Carbonylation of Methanol by Russell S. Drago, Eric D. Nyberg, Anton El A’mma and Alan Zombeck ABSTRACT -’Few

High-rate synthesis of Cu-BTC metal-organic frameworks.

PubMed

Kim, Ki-Joong; Li, Yong Jun; Kreider, Peter B; Chang, Chih-Hung; Wannenmacher, Nick; Thallapally, Praveen K; Ahn, Ho-Geun

2013-12-21

The reaction conditions for the synthesis of Cu-BTC (BTC = benzene-1,3,5-tricarboxylic acid) were elucidated using a continuous-flow microreactor-assisted solvothermal system to achieve crystal size and phase control. A high-rate synthesis of Cu-BTC metal-organic frameworks with a BET surface area of more than 1600 m(2) g(-1) (Langmuir surface area of more than 2000 m(2) g(-1)) and with a 97% production yield could be achieved with a total reaction time of 5 minutes.

Minimization of a free-energy-like potential for non-equilibrium flow systems at steady state

PubMed Central

Niven, Robert K.

2010-01-01

This study examines a new formulation of non-equilibrium thermodynamics, which gives a conditional derivation of the ‘maximum entropy production’ (MEP) principle for flow and/or chemical reaction systems at steady state. The analysis uses a dimensionless potential function ϕst for non-equilibrium systems, analogous to the free energy concept of equilibrium thermodynamics. Spontaneous reductions in ϕst arise from increases in the ‘flux entropy’ of the system—a measure of the variability of the fluxes—or in the local entropy production; conditionally, depending on the behaviour of the flux entropy, the formulation reduces to the MEP principle. The inferred steady state is also shown to exhibit high variability in its instantaneous fluxes and rates, consistent with the observed behaviour of turbulent fluid flow, heat convection and biological systems; one consequence is the coexistence of energy producers and consumers in ecological systems. The different paths for attaining steady state are also classified. PMID:20368250

Turbidimetric and photometric determination of total tannins in tea using a micro-flow-batch analyzer.

PubMed

Lima, Marcelo B; Andrade, Stéfani I E; Harding, David P; Pistonesi, Marcelo F; Band, Beatriz S F; Araújo, Mário C U

2012-01-15

Both turbidimetric and photometric determinations of total tannins in samples of green and black tea, using a micro-flow-batch analyzer (μFBA) were studied. The miniaturized system was formed using photocurable urethane-acrylate resin and ultraviolet lithography technique. The turbidimetric method was based on the precipitation reaction of Cu (II) with tannins in acetate medium at a pH of 4.5. The photometric method was based on the complexation reaction of tannins with ferrous tartrate. The turbidimetric μFBA was able to test 200 samples per hour. The photometric μFBA allowed 300 analyses per hour, generating 136μL of residue per analysis. The paired t test, at a 95% confidence level, showed no statistically significant differences between results obtained by both methods and the reference method. The urethane-acrylate μFBA maintained satisfactory physical and chemical properties, and represents an improvement over conventional flow-batch analyzer. Copyright © 2011 Elsevier B.V. All rights reserved.

A numerical treatment of radiative nanofluid 3D flow containing gyrotactic microorganism with anisotropic slip, binary chemical reaction and activation energy.

PubMed

Lu, Dianchen; Ramzan, M; Ullah, Naeem; Chung, Jae Dong; Farooq, Umer

2017-12-05

A numerical investigation of steady three dimensional nanofluid flow carrying effects of gyrotactic microorganism with anisotropic slip condition along a moving plate near a stagnation point is conducted. Additionally, influences of Arrhenius activation energy, joule heating accompanying binary chemical reaction and viscous dissipation are also taken into account. A system of nonlinear differential equations obtained from boundary layer partial differential equations is found by utilization of apposite transformations. RK fourth and fifth order technique of Maple software is engaged to acquire the solution of the mathematical model governing the presented fluid flow. A Comparison with previously done study is also made and a good agreement is achieved with existing results; hence reliable results are being presented. Evaluations are carried out for involved parameters graphically against velocity, temperature, concentration fields, microorganism distribution, density number, local Nusselt and Sherwood numbers. It is detected that microorganism distribution exhibit diminishing behavior for rising values of bio-convection Lewis and Peclet numbers.

Rapid detection of Bacillus anthracis spores using a super-paramagnetic lateral-flow immunological detection system.

PubMed

Wang, Dian-Bing; Tian, Bo; Zhang, Zhi-Ping; Deng, Jiao-Yu; Cui, Zong-Qiang; Yang, Rui-Fu; Wang, Xu-Ying; Wei, Hong-Ping; Zhang, Xian-En

2013-04-15

There is an urgent need for convenient, sensitive, and specific methods to detect the spores of Bacillus anthracis, the causative agent of anthrax, because of the bioterrorism threat posed by this bacterium. In this study, we firstly develop a super-paramagnetic lateral-flow immunological detection system for B. anthracis spores. This system involves the use of a portable magnetic assay reader, super-paramagnetic iron oxide particles, lateral-flow strips and two different monoclonal antibodies directed against B. anthracis spores. This detection system specifically recognises as few as 400 pure B. anthracis spores in 30 min. This system has a linear range of 4×10³-10⁶ CFU ml⁻¹ and reproducible detection limits of 200 spores mg⁻¹ milk powder and 130 spores mg⁻¹ soil for simulated samples. In addition, this approach shows no obvious cross-reaction with other related Bacillus spores, even at high concentrations, and has no significant dependence on the duration of the storage of the immunological strips. Therefore, this super-paramagnetic lateral-flow immunological detection system is a promising tool for the rapid and sensitive detection of Bacillus anthracis spores under field conditions. Copyright © 2012 Elsevier B.V. All rights reserved.

Transient Macroscopic Chemistry in the DSMC Method

NASA Astrophysics Data System (ADS)

Goldsworthy, M. J.; Macrossan, M. N.; Abdel-Jawad, M.

2008-12-01

In the Direct Simulation Monte Carlo method, a combination of statistical and deterministic procedures applied to a finite number of `simulator' particles are used to model rarefied gas-kinetic processes. Traditionally, chemical reactions are modelled using information from specific colliding particle pairs. In the Macroscopic Chemistry Method (MCM), the reactions are decoupled from the specific particle pairs selected for collisions. Information from all of the particles within a cell is used to determine a reaction rate coefficient for that cell. MCM has previously been applied to steady flow DSMC simulations. Here we show how MCM can be used to model chemical kinetics in DSMC simulations of unsteady flow. Results are compared with a collision-based chemistry procedure for two binary reactions in a 1-D unsteady shock-expansion tube simulation and during the unsteady development of 2-D flow through a cavity. For the shock tube simulation, close agreement is demonstrated between the two methods for instantaneous, ensemble-averaged profiles of temperature and species mole fractions. For the cavity flow, a high degree of thermal non-equilibrium is present and non-equilibrium reaction rate correction factors are employed in MCM. Very close agreement is demonstrated for ensemble averaged mole fraction contours predicted by the particle and macroscopic methods at three different flow-times. A comparison of the accumulated number of net reactions per cell shows that both methods compute identical numbers of reaction events. For the 2-D flow, MCM required similar CPU and memory resources to the particle chemistry method. The Macroscopic Chemistry Method is applicable to any general DSMC code using any viscosity or non-reacting collision models and any non-reacting energy exchange models. MCM can be used to implement any reaction rate formulations, whether these be from experimental or theoretical studies.

Gas Exchange Models for a Flexible Insect Tracheal System.

PubMed

Simelane, S M; Abelman, S; Duncan, F D

2016-06-01

In this paper two models for movement of respiratory gases in the insect trachea are presented. One model considers the tracheal system as a single flexible compartment while the other model considers the trachea as a single flexible compartment with gas exchange. This work represents an extension of Ben-Tal's work on compartmental gas exchange in human lungs and is applied to the insect tracheal system. The purpose of the work is to study nonlinear phenomena seen in the insect respiratory system. It is assumed that the flow inside the trachea is laminar, and that the air inside the chamber behaves as an ideal gas. Further, with the isothermal assumption, the expressions for the tracheal partial pressures of oxygen and carbon dioxide, rate of volume change, and the rates of change of oxygen concentration and carbon dioxide concentration are derived. The effects of some flow parameters such as diffusion capacities, reaction rates and air concentrations on net flow are studied. Numerical simulations of the tracheal flow characteristics are performed. The models developed provide a mathematical framework to further investigate gas exchange in insects.

Synthesis of α-amino-1,3-dicarbonyl compounds via Ugi flow chemistry reaction: access to functionalized 1,2,3-triazoles.

PubMed

Vasconcelos, Stanley N S; Fornari, Evelin; Caracelli, Ignez; Stefani, Hélio A

2017-11-01

The Ugi multicomponent reaction has been used as an important synthetic route to obtain compounds with potential biological activity. We present the rapid and efficient synthesis of [Formula: see text]-amino-1,3-dicarbonyl compounds in moderate to good yields via Ugi flow chemistry reactions performed with a continuous flow reactor. Such [Formula: see text]-amino-1,3-dicarbonyl compounds can act as precursors for the production of [Formula: see text]-amino acids via hydrolysis of the ethyl ester group as well as building blocks for the synthesis of novel compounds with the 1,2,3-triazole ring. The [Formula: see text]-amino acid derivatives of the Ugi flow chemistry reaction products were then used for dipeptide synthesis.

FAD C(4a)-hydroxide stabilized in a naturally fused styrene monooxygenase

PubMed Central

Schlömann, Michael; van Berkel, Willem J.H.; Gassner, George T.

2013-01-01

StyA2B represents a new class of styrene monooxygenases that integrates flavin-reductase and styrene-epoxidase activities into a single polypeptide. This naturally-occurring fusion protein offers new avenues for studying and engineering biotechnologically relevant enantioselective biochemical epoxidation reactions. Stopped-flow kinetic studies of StyA2B reported here identify reaction intermediates similar to those reported for the separate reductase and epoxidase components of related two-component systems. Our studies identify substrate epoxidation and elimination of water from the FAD C(4a)-hydroxide as rate-limiting steps in the styrene epoxidation reaction. Efforts directed at accelerating these reaction steps are expected to greatly increase catalytic efficiency and the value of StyA2B as biocatalyst. PMID:24157359

Link between alginate reaction front propagation and general reaction diffusion theory.

PubMed

Braschler, Thomas; Valero, Ana; Colella, Ludovica; Pataky, Kristopher; Brugger, Jürgen; Renaud, Philippe

2011-03-15

We provide a common theoretical framework reuniting specific models for the Ca(2+)-alginate system and general reaction diffusion theory along with experimental validation on a microfluidic chip. As a starting point, we use a set of nonlinear, partial differential equations that are traditionally solved numerically: the Mikkelsen-Elgsaeter model. Applying the traveling-wave hypothesis as a major simplification, we obtain an analytical solution. The solution indicates that the fundamental properties of the alginate reaction front are governed by a single dimensionless parameter λ. For small λ values, a large depletion zone accompanies the reaction front. For large λ values, the alginate reacts before having the time to diffuse significantly. We show that the λ parameter is of general importance beyond the alginate model system, as it can be used to classify known solutions for second-order reaction diffusion schemes, along with the novel solution presented here. For experimental validation, we develop a microchip model system, in which the alginate gel formation can be carried out in a highly controlled, essentially 1D environment. The use of a filter barrier enables us to rapidly renew the CaCl(2) solution, while maintaining flow speeds lower than 1 μm/s for the alginate compartment. This allows one to impose an exactly known bulk CaCl(2) concentration and diffusion resistance. This experimental model system, taken together with the theoretical development, enables the determination of the entire set of physicochemical parameters governing the alginate reaction front in a single experiment.

Space and time-resolved probing of heterogeneous catalysis reactions using lab-on-a-chip

NASA Astrophysics Data System (ADS)

Navin, Chelliah V.; Krishna, Katla Sai; Theegala, Chandra S.; Kumar, Challa S. S. R.

2016-03-01

Probing catalytic reactions on a catalyst surface in real time is a major challenge. Herein, we demonstrate the utility of a continuous flow millifluidic chip reactor coated with a nanostructured gold catalyst as an effective platform for in situ investigation of the kinetics of catalytic reactions by taking 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) conversion as a model reaction. The idea conceptualized in this paper can not only dramatically change the ability to probe the time-resolved kinetics of heterogeneous catalysis reactions but also used for investigating other chemical and biological catalytic processes, thereby making this a broad platform for probing reactions as they occur within continuous flow reactors.Probing catalytic reactions on a catalyst surface in real time is a major challenge. Herein, we demonstrate the utility of a continuous flow millifluidic chip reactor coated with a nanostructured gold catalyst as an effective platform for in situ investigation of the kinetics of catalytic reactions by taking 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) conversion as a model reaction. The idea conceptualized in this paper can not only dramatically change the ability to probe the time-resolved kinetics of heterogeneous catalysis reactions but also used for investigating other chemical and biological catalytic processes, thereby making this a broad platform for probing reactions as they occur within continuous flow reactors. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06752a

Continuous-flow Heck synthesis of 4-methoxybiphenyl and methyl 4-methoxycinnamate in supercritical carbon dioxide expanded solvent solutions

PubMed Central

Lau, Phei Li; Allen, Ray W K

2013-01-01

Summary The palladium metal catalysed Heck reaction of 4-iodoanisole with styrene or methyl acrylate has been studied in a continuous plug flow reactor (PFR) using supercritical carbon dioxide (scCO2) as the solvent, with THF and methanol as modifiers. The catalyst was 2% palladium on silica and the base was diisopropylethylamine due to its solubility in the reaction solvent. No phosphine co-catalysts were used so the work-up procedure was simplified and the green credentials of the reaction were enhanced. The reactions were studied as a function of temperature, pressure and flow rate and in the case of the reaction with styrene compared against a standard, stirred autoclave reaction. Conversion was determined and, in the case of the reaction with styrene, the isomeric product distribution was monitored by GC. In the case of the reaction with methyl acrylate the reactor was scaled from a 1.0 mm to 3.9 mm internal diameter and the conversion and turnover frequency determined. The results show that the Heck reaction can be effectively performed in scCO2 under continuous flow conditions with a palladium metal, phosphine-free catalyst, but care must be taken when selecting the reaction temperature in order to ensure the appropriate isomer distribution is achieved. Higher reaction temperatures were found to enhance formation of the branched terminal alkene isomer as opposed to the linear trans-isomer. PMID:24367454

[Function of alveoles as a result of evolutionary development of respiratory system in mammals].

PubMed

Ivanov, K P

2013-01-01

Reaction of hemoglobin oxygenation is known to occur for 40 femtoseconds (40 x 10(-15) s). However, the process of oxygen diffusion to hemoglobin under physiologic conditions decelerated this reaction approximately billion times. In mammalian lungs, blood is moving at a high rate and in a relatively high amount. The human lung mass is as low as 600 g, but the complete cardiac output approaches 6 1/min. In rat, from 20 to 40 ml of blood is passed for q min through the lung whose mass is about 1.5 g. Such blood flow rate is possible, as in lungs of high animals there exists a dense network of relatively large microvessels with diameter from 20 to 40 microm and more. In spite of a large volume and a high blood flow rate hampering oxygen diffusion, the complete blood oxygenation occurs in lung alveoli. This is due to peculiar mechanisms that facilitate markedly the oxygen diffusion and that developed in alveoli of mammals in the course of many million years of evolution of their respiratory system. Thus, alveolus is not a bubble with air, but a complex tool of fight with inertness of diffusion. It is interesting that in lungs of the low vertebrates, neither such system of blood vessels nor alveoli exist, and their blood flow rate is much lower than in mammals.

High pressure gas flow, storage, and displacement in fractured rock—Experimental setup development and application

NASA Astrophysics Data System (ADS)

Hadi Mosleh, M.; Turner, M.; Sedighi, M.; Vardon, P. J.

2017-01-01

This paper presents the design, development, and application of a laboratory setup for the experimental investigations of gas flow and reactions in a fractured rock. The laboratory facility comprises (i) a high pressure manometric sorption apparatus, where equilibrium and kinetic phenomena of adsorption and desorption can be examined, (ii) a high pressure triaxial core flooding system where the chemical reactive transport properties or processes can be explored, and (iii) an ancillary system including pure and mixed gas supply and analysis units. Underground conditions, in terms of pore pressure, confining pressure, and temperature, can be replicated using the triaxial core flooding system developed for depths up to 2 km. Core flooding experiments can be conducted under a range of gas injection pressures up to 20 MPa and temperatures up to 338 K. Details of the design considerations and the specification for the critical measuring instruments are described. The newly developed laboratory facility has been applied to study the adsorption of N2, CH4, and CO2 relevant to applications in carbon sequestration in coal and enhanced coalbed methane recovery. Under a wide range of pressures, the flow of helium in a core sample was studied and the evolution of absolute permeability at different effective stress conditions has been investigated. A comprehensive set of high resolution data has been produced on anthracite coal samples from the South Wales coalfield, using the developed apparatus. The results of the applications provide improved insight into the high pressure flow and reaction of various gas species in the coal samples from the South Wales coalfield.

On-line Analysis of Catalytic Reaction Products Using a High-Pressure Tandem Micro-reactor GC/MS.

PubMed

Watanabe, Atsushi; Kim, Young-Min; Hosaka, Akihiko; Watanabe, Chuichi; Teramae, Norio; Ohtani, Hajime; Kim, Seungdo; Park, Young-Kwon; Wang, Kaige; Freeman, Robert R

2017-01-01

When a GC/MS system is coupled with a pressurized reactor, the separation efficiency and the retention time are directly affected by the reactor pressure. To keep the GC column flow rate constant irrespective of the reaction pressure, a restrictor capillary tube and an open split interface are attached between the GC injection port and the head of a GC separation column. The capability of the attached modules is demonstrated for the on-line GC/MS analysis of catalytic reaction products of a bio-oil model sample (guaiacol), produced under a pressure of 1 to 3 MPa.

Centrifugal Microfluidic System for Nucleic Acid Amplification and Detection.

PubMed

Miao, Baogang; Peng, Niancai; Li, Lei; Li, Zheng; Hu, Fei; Zhang, Zengming; Wang, Chaohui

2015-11-04

We report here the development of a rapid PCR microfluidic system comprising a double-shaft turntable and centrifugal-based disc that rapidly drives the PCR mixture between chambers set at different temperatures, and the bidirectional flow improved the space utilization of the disc. Three heating resistors and thermistors maintained uniform, specific temperatures for the denaturation, annealing, and extension steps of the PCR. Infrared imaging showed that there was little thermal interference between reaction chambers; the system enabled the cycle number and reaction time of each step to be independently adjusted. To validate the function and efficiency of the centrifugal microfluidic system, a 350-base pair target gene from the hepatitis B virus was amplified and quantitated by fluorescence detection. By optimizing the cycling parameters, the reaction time was reduced to 32 min as compared to 120 min for a commercial PCR machine. DNA samples with concentrations ranging from 10 to 10⁶ copies/mL could be quantitatively analyzed using this system. This centrifugal-based microfluidic platform is a useful system and possesses industrialization potential that can be used for portable diagnostics.

Centrifugal Microfluidic System for Nucleic Acid Amplification and Detection

PubMed Central

Miao, Baogang; Peng, Niancai; Li, Lei; Li, Zheng; Hu, Fei; Zhang, Zengming; Wang, Chaohui

2015-01-01

We report here the development of a rapid PCR microfluidic system comprising a double-shaft turntable and centrifugal-based disc that rapidly drives the PCR mixture between chambers set at different temperatures, and the bidirectional flow improved the space utilization of the disc. Three heating resistors and thermistors maintained uniform, specific temperatures for the denaturation, annealing, and extension steps of the PCR. Infrared imaging showed that there was little thermal interference between reaction chambers; the system enabled the cycle number and reaction time of each step to be independently adjusted. To validate the function and efficiency of the centrifugal microfluidic system, a 350-base pair target gene from the hepatitis B virus was amplified and quantitated by fluorescence detection. By optimizing the cycling parameters, the reaction time was reduced to 32 min as compared to 120 min for a commercial PCR machine. DNA samples with concentrations ranging from 10 to 106 copies/mL could be quantitatively analyzed using this system. This centrifugal-based microfluidic platform is a useful system and possesses industrialization potential that can be used for portable diagnostics. PMID:26556354

Flow chemistry: intelligent processing of gas-liquid transformations using a tube-in-tube reactor.

PubMed

Brzozowski, Martin; O'Brien, Matthew; Ley, Steven V; Polyzos, Anastasios

2015-02-17

CONSPECTUS: The previous decade has witnessed the expeditious uptake of flow chemistry techniques in modern synthesis laboratories, and flow-based chemistry is poised to significantly impact our approach to chemical preparation. The advantages of moving from classical batch synthesis to flow mode, in order to address the limitations of traditional approaches, particularly within the context of organic synthesis are now well established. Flow chemistry methodology has led to measurable improvements in safety and reduced energy consumption and has enabled the expansion of available reaction conditions. Contributions from our own laboratories have focused on the establishment of flow chemistry methods to address challenges associated with the assembly of complex targets through the development of multistep methods employing supported reagents and in-line monitoring of reaction intermediates to ensure the delivery of high quality target compounds. Recently, flow chemistry approaches have addressed the challenges associated with reactions utilizing reactive gases in classical batch synthesis. The small volumes of microreactors ameliorate the hazards of high-pressure gas reactions and enable improved mixing with the liquid phase. Established strategies for gas-liquid reactions in flow have relied on plug-flow (or segmented flow) regimes in which the gas plugs are introduced to a liquid stream and dissolution of gas relies on interfacial contact of the gas bubble with the liquid phase. This approach confers limited control over gas concentration within the liquid phase and is unsuitable for multistep methods requiring heterogeneous catalysis or solid supported reagents. We have identified the use of a gas-permeable fluoropolymer, Teflon AF-2400, as a simple method of achieving efficient gas-liquid contact to afford homogeneous solutions of reactive gases in flow. The membrane permits the transport of a wide range of gases with significant control of the stoichiometry of reactive gas in a given reaction mixture. We have developed a tube-in-tube reactor device consisting of a pair of concentric capillaries in which pressurized gas permeates through an inner Teflon AF-2400 tube and reacts with dissolved substrate within a liquid phase that flows within a second gas impermeable tube. This Account examines our efforts toward the development of a simple, unified methodology for the processing of gaseous reagents in flow by way of development of a tube-in-tube reactor device and applications to key C-C, C-N, and C-O bond forming and hydrogenation reactions. We further describe the application to multistep reactions using solid-supported reagents and extend the technology to processes utilizing multiple gas reagents. A key feature of our work is the development of computer-aided imaging techniques to allow automated in-line monitoring of gas concentration and stoichiometry in real time. We anticipate that this Account will illustrate the convenience and benefits of membrane tube-in-tube reactor technology to improve and concomitantly broaden the scope of gas/liquid/solid reactions in organic synthesis.

Numerical study of chemically reacting viscous flow relevant to pulsed detonation engines

NASA Astrophysics Data System (ADS)

Yi, Tae-Hyeong

2005-11-01

A computational fluid dynamics code for two-dimensional, multi-species, laminar Navier-Stokes equations is developed to simulate a recently proposed engine concept for a pulsed detonation based propulsion system and to investigate the feasibility of the engine of the concept. The governing equations that include transport phenomena such as viscosity, thermal conduction and diffusion are coupled with chemical reactions. The gas is assumed to be thermally perfect and in chemically non-equilibrium. The stiffness due to coupling the fluid dynamics and the chemical kinetics is properly taken care of by using a time-operator splitting method and a variable coefficient ordinary differential equation solver. A second-order Roe scheme with a minmod limiter is explicitly used for space descretization, while a second-order, two-step Runge-Kutta method is used for time descretization. In space integration, a finite volume method and a cell-centered scheme are employed. The first-order derivatives in the equations of transport properties are discretized by a central differencing with Green's theorem. Detailed chemistry is involved in this study. Two chemical reaction mechanisms are extracted from GRI-Mech, which are forty elementary reactions with thirteen species for a hydrogen-air mixture and twenty-seven reactions with eight species for a hydrogen-oxygen mixture. The code is ported to a high-performance parallel machine with Message-Passing Interface. Code validation is performed with chemical kinetic modeling for a stoichiometric hydrogen-air mixture, an one-dimensional detonation tube, a two-dimensional, inviscid flow over a wedge and a viscous flow over a flat plate. Detonation is initiated using a numerically simulated arc-ignition or shock-induced ignition system. Various freestream conditions are utilized to study the propagation of the detonation in the proposed concept of the engine. Investigation of the detonation propagation is performed for a pulsed detonation rocket and a supersonic combustion chamber. For a pulsed detonation rocket case, the detonation tube is embedded in a mixing chamber where an initiator is added to the main detonation chamber. Propagating detonation waves in a supersonic combustion chamber is investigated for one- and two-dimensional cases. The detonation initiated by an arc and a shock wave is studied in the inviscid and viscous flow, respectively. Various features including a detonation-shock interaction, a detonation diffraction, a base flow and a vortex are observed.

Diels–Alder reactions of myrcene using intensified continuous-flow reactors

PubMed Central

Álvarez-Diéguez, Miguel Á; Kohl, Thomas M; Tsanaktsidis, John

2017-01-01

This work describes the Diels–Alder reaction of the naturally occurring substituted butadiene, myrcene, with a range of different naturally occurring and synthetic dienophiles. The synthesis of the Diels–Alder adduct from myrcene and acrylic acid, containing surfactant properties, was scaled-up in a plate-type continuous-flow reactor with a volume of 105 mL to a throughput of 2.79 kg of the final product per day. This continuous-flow approach provides a facile alternative scale-up route to conventional batch processing, and it helps to intensify the synthesis protocol by applying higher reaction temperatures and shorter reaction times. PMID:28228853

Characterization of Magma-Driven Hydrothermal Systems at Oceanic Spreading Centers

NASA Astrophysics Data System (ADS)

Farough, A.; Lowell, R. P.; Corrigan, R.

2012-12-01

Fluid circulation in high-temperature hydrothermal systems involves complex water-rock chemical reactions and phase separation. Numerical modeling of reactive transport in multi-component, multiphase systems is required to obtain a full understanding of the characteristics and evolution of hydrothermal vent systems. We use a single-pass parameterized model of high-temperature hydrothermal circulation at oceanic spreading centers constrained by observational parameters such as vent temperature, heat output, and vent field area, together with surface area and depth of the sub-axial magma chamber, to deduce fundamental hydrothermal parameters such as mass flow rate, bulk permeability, conductive boundary layer thickness at the base of the system, magma replenishment rate, and residence time in the discharge zone. All of these key subsurface characteristics are known for fewer than 10 sites out of 300 known hydrothermal systems. The principal limitations of this approach stem from the uncertainty in heat output and vent field area. For systems where data are available on partitioning of heat and chemical output between focused and diffuse flow, we determined the fraction of high-temperature vent fluid incorporated into diffuse flow using a two-limb single pass model. For EPR 9°50` N and ASHES, the diffuse flow temperatures calculated assuming conservative mixing are nearly equal to the observed temperatures indicating that approximately 80%-90% of the hydrothermal heat output occurs as high-temperature flow derived from magmatic heat even though most of the heat output appears as low-temperature diffuse discharge. For the Main Endeavour Field and Lucky Strike, diffuse flow fluids show significant conductive cooling and heating respectively. Finally, we calculate the transport of various geochemical constituents in focused and diffuse flow at the vent field scale and compare the results with estimates of geochemical transports from the Rainbow hydrothermal field where diffuse flow is absent.

Advanced CO2 Removal and Reduction System

NASA Technical Reports Server (NTRS)

Alptekin, Gokhan; Dubovik, Margarita; Copeland, Robert J.

2011-01-01

An advanced system for removing CO2 and H2O from cabin air, reducing the CO2, and returning the resulting O2 to the air is less massive than is a prior system that includes two assemblies . one for removal and one for reduction. Also, in this system, unlike in the prior system, there is no need to compress and temporarily store CO2. In this present system, removal and reduction take place within a single assembly, wherein removal is effected by use of an alkali sorbent and reduction is effected using a supply of H2 and Ru catalyst, by means of the Sabatier reaction, which is CO2 + 4H2 CH4 + O2. The assembly contains two fixed-bed reactors operating in alternation: At first, air is blown through the first bed, which absorbs CO2 and H2O. Once the first bed is saturated with CO2 and H2O, the flow of air is diverted through the second bed and the first bed is regenerated by supplying it with H2 for the Sabatier reaction. Initially, the H2 is heated to provide heat for the regeneration reaction, which is endothermic. In the later stages of regeneration, the Sabatier reaction, which is exothermic, supplies the heat for regeneration.

Optofluidic UV-Vis spectrophotometer for online monitoring of photocatalytic reactions

NASA Astrophysics Data System (ADS)

Wang, Ning; Tan, Furui; Zhao, Yu; Tsoi, Chi Chung; Fan, Xudong; Yu, Weixing; Zhang, Xuming

2016-06-01

On-chip integration of optical detection units into the microfluidic systems for online monitoring is highly desirable for many applications and is also well in line with the spirit of optofluidics technology-fusion of optics and microfluidics for advanced functionalities. This paper reports the construction of a UV-Vis spectrophotometer on a microreactor, and demonstrates the online monitoring of the photocatalytic degradations of methylene blue and methyl orange under different flow rates and different pH values by detecting the intensity change and/or the peak shift. The integrated device consists of a TiO2-coated glass substrate, a PDMS micro-sized reaction chamber and two flow cells. By comparing with the results of commercial equipment, we have found that the measuring range and the sensitivity are acceptable, especially when the transmittance is in the range of 0.01-0.9. This integrated optofluidic device can significantly cut down the test time and the sample volume, and would provide a versatile platform for real-time characterization of photochemical performance. Moreover, its online monitoring capability may enable to access the usually hidden information in biochemical reactions like intermediate products, time-dependent processes and reaction kinetics.

A new high temperature reactor for operando XAS: Application for the dry reforming of methane over Ni/ZrO2 catalyst.

PubMed

Aguilar-Tapia, Antonio; Ould-Chikh, Samy; Lahera, Eric; Prat, Alain; Delnet, William; Proux, Olivier; Kieffer, Isabelle; Basset, Jean-Marie; Takanabe, Kazuhiro; Hazemann, Jean-Louis

2018-03-01

The construction of a high-temperature reaction cell for operando X-ray absorption spectroscopy characterization is reported. A dedicated cell was designed to operate as a plug-flow reactor using powder samples requiring gas flow and thermal treatment at high temperatures. The cell was successfully used in the reaction of dry reforming of methane (DRM). We present X-ray absorption results in the fluorescence detection mode on a 0.4 wt. % Ni/ZrO 2 catalyst under realistic conditions at 750 °C, reproducing the conditions used for a conventional dynamic microreactor for the DRM reaction. The setup includes a gas distribution system that can be fully remotely operated. The reaction cell offers the possibility of transmission and fluorescence detection modes. The complete setup dedicated to the study of catalysts is permanently installed on the Collaborating Research Groups French Absorption spectroscopy beamline in Material and Environmental sciences (CRG-FAME) and French Absorption spectroscopy beamline in Material and Environmental sciences at Ultra-High Dilution (FAME-UHD) beamlines (BM30B and BM16) at the European Synchrotron Radiation Facility in Grenoble, France.

A new high temperature reactor for operando XAS: Application for the dry reforming of methane over Ni/ZrO2 catalyst

NASA Astrophysics Data System (ADS)

Aguilar-Tapia, Antonio; Ould-Chikh, Samy; Lahera, Eric; Prat, Alain; Delnet, William; Proux, Olivier; Kieffer, Isabelle; Basset, Jean-Marie; Takanabe, Kazuhiro; Hazemann, Jean-Louis

2018-03-01

The construction of a high-temperature reaction cell for operando X-ray absorption spectroscopy characterization is reported. A dedicated cell was designed to operate as a plug-flow reactor using powder samples requiring gas flow and thermal treatment at high temperatures. The cell was successfully used in the reaction of dry reforming of methane (DRM). We present X-ray absorption results in the fluorescence detection mode on a 0.4 wt. % Ni/ZrO2 catalyst under realistic conditions at 750 °C, reproducing the conditions used for a conventional dynamic microreactor for the DRM reaction. The setup includes a gas distribution system that can be fully remotely operated. The reaction cell offers the possibility of transmission and fluorescence detection modes. The complete setup dedicated to the study of catalysts is permanently installed on the Collaborating Research Groups French Absorption spectroscopy beamline in Material and Environmental sciences (CRG-FAME) and French Absorption spectroscopy beamline in Material and Environmental sciences at Ultra-High Dilution (FAME-UHD) beamlines (BM30B and BM16) at the European Synchrotron Radiation Facility in Grenoble, France.

Optofluidic UV-Vis spectrophotometer for online monitoring of photocatalytic reactions

PubMed Central

Wang, Ning; Tan, Furui; Zhao, Yu; Tsoi, Chi Chung; Fan, Xudong; Yu, Weixing; Zhang, Xuming

2016-01-01

On-chip integration of optical detection units into the microfluidic systems for online monitoring is highly desirable for many applications and is also well in line with the spirit of optofluidics technology–fusion of optics and microfluidics for advanced functionalities. This paper reports the construction of a UV-Vis spectrophotometer on a microreactor, and demonstrates the online monitoring of the photocatalytic degradations of methylene blue and methyl orange under different flow rates and different pH values by detecting the intensity change and/or the peak shift. The integrated device consists of a TiO2-coated glass substrate, a PDMS micro-sized reaction chamber and two flow cells. By comparing with the results of commercial equipment, we have found that the measuring range and the sensitivity are acceptable, especially when the transmittance is in the range of 0.01–0.9. This integrated optofluidic device can significantly cut down the test time and the sample volume, and would provide a versatile platform for real-time characterization of photochemical performance. Moreover, its online monitoring capability may enable to access the usually hidden information in biochemical reactions like intermediate products, time-dependent processes and reaction kinetics. PMID:27352840

Optofluidic UV-Vis spectrophotometer for online monitoring of photocatalytic reactions.

PubMed

Wang, Ning; Tan, Furui; Zhao, Yu; Tsoi, Chi Chung; Fan, Xudong; Yu, Weixing; Zhang, Xuming

2016-06-29

On-chip integration of optical detection units into the microfluidic systems for online monitoring is highly desirable for many applications and is also well in line with the spirit of optofluidics technology-fusion of optics and microfluidics for advanced functionalities. This paper reports the construction of a UV-Vis spectrophotometer on a microreactor, and demonstrates the online monitoring of the photocatalytic degradations of methylene blue and methyl orange under different flow rates and different pH values by detecting the intensity change and/or the peak shift. The integrated device consists of a TiO2-coated glass substrate, a PDMS micro-sized reaction chamber and two flow cells. By comparing with the results of commercial equipment, we have found that the measuring range and the sensitivity are acceptable, especially when the transmittance is in the range of 0.01-0.9. This integrated optofluidic device can significantly cut down the test time and the sample volume, and would provide a versatile platform for real-time characterization of photochemical performance. Moreover, its online monitoring capability may enable to access the usually hidden information in biochemical reactions like intermediate products, time-dependent processes and reaction kinetics.

Hydrochemical evolution of sodium-sulfate and sodium-chloride groundwater beneath the Northern Chihuahuan Desert, Trans-Pecos, Texas, USA

USGS Publications Warehouse

Fisher, R.S.; Mullican, W. F.

1997-01-01

Groundwater beneath the northern Chihuahuan Desert, Trans-Pecos, Texas, USA, occurs in both carbonate and siliciclastic aquifers beneath a thick unsaturated zone and in shallow Rio Grande alluvium. Groundwater hydrochemical evolution was investigated by analyzing soils, soil leachates, bolson-fill sediments, water from the unsaturated zone, and groundwater from three major aquifers. Ionic relations, mineral saturation states, and geochemical modeling show that groundwater compositions are controlled by reactions in the unsaturated zone, mineralogy of unsaturated sediments and aquifers, position in the groundwater flow system, and extensive irrigation. Recharge to aquifers unaffected by irrigation is initially a Ca-HCO3 type as a result of dissolving carbonate surficial salts. With continued flow and mineral-water interaction, saturation with calcite and dolomite is maintained, gypsum is dissolved, and aqueous Ca and Mg are exchanged for adsorbed Na to produce a Na-SO4 water. Groundwater in Rio Grande alluvium is a Na-Cl type, reflecting river-water composition and the effects of irrigation, evapotranspiration, and surficial salt recycling. These results document two hydrochemical evolution paths for groundwater in arid lands. If recharge is dilute precipitation, significant changes in water chemistry can occur in unsaturated media, ion exchange can be as important as dissolution-precipitation reactions in determining groundwater composition, and mineral-water reactions ultimately control groundwater composition. If recharge is return flow of irrigation water that already contains appreciable solutes, mineral-water reactions are less important than irrigation-water composition in determining groundwater chemistry.

A mathematical model for the iron/chromium redox battery

NASA Technical Reports Server (NTRS)

Fedkiw, P. S.; Watts, R. W.

1984-01-01

A mathematical model has been developed to describe the isothermal operation of a single anode-separator-cathode unit cell in a redox-flow battery and has been applied to the NASA iron/chromium system. The model, based on porous electrode theory, incorporates redox kinetics, mass transfer, and ohmic effects as well as the parasitic hydrogen reaction which occurs in the chromium electrode. A numerical parameter study was carried out to predict cell performance to aid in the rational design, scale-up, and operation of the flow battery. The calculations demonstrate: (1) an optimum electrode thickness and electrolyte flow rate exist; (2) the amount of hydrogen evolved and, hence, cycle faradaic efficiency, can be affected by cell geometry, flow rate, and charging procedure; (3) countercurrent flow results in enhanced cell performance over cocurrent flow; and (4) elevated temperature operation enhances cell performance.

Modeling variably saturated multispecies reactive groundwater solute transport with MODFLOW-UZF and RT3D

USGS Publications Warehouse

Bailey, Ryan T.; Morway, Eric D.; Niswonger, Richard G.; Gates, Timothy K.

2013-01-01

A numerical model was developed that is capable of simulating multispecies reactive solute transport in variably saturated porous media. This model consists of a modified version of the reactive transport model RT3D (Reactive Transport in 3 Dimensions) that is linked to the Unsaturated-Zone Flow (UZF1) package and MODFLOW. Referred to as UZF-RT3D, the model is tested against published analytical benchmarks as well as other published contaminant transport models, including HYDRUS-1D, VS2DT, and SUTRA, and the coupled flow and transport modeling system of CATHY and TRAN3D. Comparisons in one-dimensional, two-dimensional, and three-dimensional variably saturated systems are explored. While several test cases are included to verify the correct implementation of variably saturated transport in UZF-RT3D, other cases are included to demonstrate the usefulness of the code in terms of model run-time and handling the reaction kinetics of multiple interacting species in variably saturated subsurface systems. As UZF1 relies on a kinematic-wave approximation for unsaturated flow that neglects the diffusive terms in Richards equation, UZF-RT3D can be used for large-scale aquifer systems for which the UZF1 formulation is reasonable, that is, capillary-pressure gradients can be neglected and soil parameters can be treated as homogeneous. Decreased model run-time and the ability to include site-specific chemical species and chemical reactions make UZF-RT3D an attractive model for efficient simulation of multispecies reactive transport in variably saturated large-scale subsurface systems.

Pore and Continuum Scale Study of the Effect of Subgrid Transport Heterogeneity on Redox Reaction Rates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yuanyuan; Liu, Chongxuan; Zhang, Changyong

2015-08-01

A micromodel system with a pore structure for heterogeneous flow and transport was used to investigate the effect of subgrid transport heterogeneity on redox reaction rates. Hematite reductive dissolution by injecting a reduced form of flavin mononucleotide (FMNH2) at variable flow rates was used as an example to probe the variations of redox reaction rates in different subgrid transport domains. Experiments, pore-scale simulations, and macroscopic modeling were performed to measure and simulate in-situ hematite reduction and to evaluate the scaling behavior of the redox reaction rates from the pore to macroscopic scales. The results indicated that the measured pore-scale ratesmore » of hematite reduction were consistent with the predictions from a pore scale reactive transport model. A general trend is that hematite reduction followed reductant transport pathways, starting from the advection-dominated pores toward the interior of diffusion-dominated domains. Two types of diffusion domains were considered in the micromodel: a micropore diffusion domain, which locates inside solid grains or aggregates where reactant transport is limited by diffusion; and a macropore diffusion domain, which locates at wedged, dead-end pore spaces created by the grain-grain contacts. The rate of hematite reduction in the advection-dominated domain was faster than those in the diffusion-controlled domains, and the rate in the macropore diffusion domain was faster than that in the micropore domain. The reduction rates in the advection and macropore diffusion domains increased with increasing flow rate, but were affected by different mechanisms. The rate increase in the advection domain was controlled by the mass action effect as a faster flow supplied more reactants, and the rate increase in the macropore domain was more affected by the rate of mass exchange with the advection domain, which increased with increasing flow rate. The hematite reduction rate in the micropore domain was, however, not affected by the flow rate because molecular diffusion limits reductant supply to the micropore domain interior. Domain-based macroscopic models were evaluated to scale redox reaction rates from the pore to macroscopic scales. A single domain model, which ignores subgrid transport heterogeneity deviated significantly from the pore-scale results. Further analysis revealed that the rate expression for hematite reduction was not scalable from the pore to porous media using the single domain model. A three-domain model, which effectively considers subgrid reactive diffusion in the micropore and macropore domains, significantly improved model description. Overall this study revealed the importance of subgrid transport heterogeneity in the manifestation of redox reaction rates in porous media and in scaling reactions from the pore to porous media. The research also supported that the domain-based scaling approach can be used to directly scale redox reactions in porous media with subgrid transport heterogeneity.« less

Decoding Network Structure in On-Chip Integrated Flow Cells with Synchronization of Electrochemical Oscillators

NASA Astrophysics Data System (ADS)

Jia, Yanxin; Kiss, István Z.

2017-04-01

The analysis of network interactions among dynamical units and the impact of the coupling on self-organized structures is a challenging task with implications in many biological and engineered systems. We explore the coupling topology that arises through the potential drops in a flow channel in a lab-on-chip device that accommodates chemical reactions on electrode arrays. The networks are revealed by analysis of the synchronization patterns with the use of an oscillatory chemical reaction (nickel electrodissolution) and are further confirmed by direct decoding using phase model analysis. In dual electrode configuration, a variety coupling schemes, (uni- or bidirectional positive or negative) were identified depending on the relative placement of the reference and counter electrodes (e.g., placed at the same or the opposite ends of the flow channel). With three electrodes, the network consists of a superposition of a localized (upstream) and global (all-to-all) coupling. With six electrodes, the unique, position dependent coupling topology resulted spatially organized partial synchronization such that there was a synchrony gradient along the quasi-one-dimensional spatial coordinate. The networked, electrode potential (current) spike generating electrochemical reactions hold potential for construction of an in-situ information processing unit to be used in electrochemical devices in sensors and batteries.

Updated Chemical Kinetics and Sensitivity Analysis Code

NASA Technical Reports Server (NTRS)

Radhakrishnan, Krishnan

2005-01-01

An updated version of the General Chemical Kinetics and Sensitivity Analysis (LSENS) computer code has become available. A prior version of LSENS was described in "Program Helps to Determine Chemical-Reaction Mechanisms" (LEW-15758), NASA Tech Briefs, Vol. 19, No. 5 (May 1995), page 66. To recapitulate: LSENS solves complex, homogeneous, gas-phase, chemical-kinetics problems (e.g., combustion of fuels) that are represented by sets of many coupled, nonlinear, first-order ordinary differential equations. LSENS has been designed for flexibility, convenience, and computational efficiency. The present version of LSENS incorporates mathematical models for (1) a static system; (2) steady, one-dimensional inviscid flow; (3) reaction behind an incident shock wave, including boundary layer correction; (4) a perfectly stirred reactor; and (5) a perfectly stirred reactor followed by a plug-flow reactor. In addition, LSENS can compute equilibrium properties for the following assigned states: enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. For static and one-dimensional-flow problems, including those behind an incident shock wave and following a perfectly stirred reactor calculation, LSENS can compute sensitivity coefficients of dependent variables and their derivatives, with respect to the initial values of dependent variables and/or the rate-coefficient parameters of the chemical reactions.

Numerical Simulation of Permeability Change in Wellbore Cement Fractures after Geomechanical Stress and Geochemical Reactions Using X-ray Computed Tomography Imaging.

PubMed

Kabilan, Senthil; Jung, Hun Bok; Kuprat, Andrew P; Beck, Anthon N; Varga, Tamas; Fernandez, Carlos A; Um, Wooyong

2016-06-21

X-ray microtomography (XMT) imaging combined with three-dimensional (3D) computational fluid dynamics (CFD) modeling technique was used to study the effect of geochemical and geomechanical processes on fracture permeability in composite Portland cement-basalt caprock core samples. The effect of fluid density and viscosity and two different pressure gradient conditions on fracture permeability was numerically studied by using fluids with varying density and viscosity and simulating two different pressure gradient conditions. After the application of geomechanical stress but before CO2-reaction, CFD revealed fluid flow increase, which resulted in increased fracture permeability. After CO2-reaction, XMT images displayed preferential precipitation of calcium carbonate within the fractures in the cement matrix and less precipitation in fractures located at the cement-basalt interface. CFD estimated changes in flow profile and differences in absolute values of flow velocity due to different pressure gradients. CFD was able to highlight the profound effect of fluid viscosity on velocity profile and fracture permeability. This study demonstrates the applicability of XMT imaging and CFD as powerful tools for characterizing the hydraulic properties of fractures in a number of applications like geologic carbon sequestration and storage, hydraulic fracturing for shale gas production, and enhanced geothermal systems.

Microfluidic Device for Sequential Injection and Flushing of Solutions and its Application to Immunosensing

NASA Astrophysics Data System (ADS)

Nashida, Norihiro; Suzuki, Hiroaki

A microfluidic system with injecting and flushing functions was developed. In the system, hydrophilic flow channels have a dry-film photoresist layer which facilitates the introduction of solutions from four injection ports. The injection and flushing of solutions are controlled by valves operated by electrowetting. The valves consist of gold working electrodes in the flow channels or a through-hole in the glass substrate. Solutions can be sequentially introduced through the injection ports into a reaction chamber and flushed through a valve in the through-hole. Necessary immunoassay steps can be conducted on the chip, and a target antibody can be detected electrochemically.

Modeling Chemically Reactive Flow of Sutterby Nanofluid by a Rotating Disk in Presence of Heat Generation/Absorption

NASA Astrophysics Data System (ADS)

Hayat, T.; Ahmad, Salman; Ijaz Khan, M.; Alsaedi, A.

2018-05-01

In this article we investigate the flow of Sutterby liquid due to rotating stretchable disk. Mass and heat transport are analyzed through Brownian diffusion and thermophoresis. Further the effects of magnetic field, chemical reaction and heat source are also accounted. We employ transformation procedure to obtain a system of nonlinear ODE’s. This system is numerically solved by Built-in-Shooting method. Impacts of different involved parameter on velocity, temperature and concentration are described. Velocity, concentration and temperature gradients are numerically computed. Obtained results show that velocity is reduced through material parameter. Temperature and concentration are enhanced with thermophoresis parameter.

Product selectivity control induced by using liquid-liquid parallel laminar flow in a microreactor.

PubMed

Amemiya, Fumihiro; Matsumoto, Hideyuki; Fuse, Keishi; Kashiwagi, Tsuneo; Kuroda, Chiaki; Fuchigami, Toshio; Atobe, Mahito

2011-06-07

Product selectivity control based on a liquid-liquid parallel laminar flow has been successfully demonstrated by using a microreactor. Our electrochemical microreactor system enables regioselective cross-coupling reaction of aldehyde with allylic chloride via chemoselective cathodic reduction of substrate by the combined use of suitable flow mode and corresponding cathode material. The formation of liquid-liquid parallel laminar flow in the microreactor was supported by the estimation of benzaldehyde diffusion coefficient and computational fluid dynamics simulation. The diffusion coefficient for benzaldehyde in Bu(4)NClO(4)-HMPA medium was determined to be 1.32 × 10(-7) cm(2) s(-1) by electrochemical measurements, and the flow simulation using this value revealed the formation of clear concentration gradient of benzaldehyde in the microreactor channel over a specific channel length. In addition, the necessity of the liquid-liquid parallel laminar flow was confirmed by flow mode experiments.

A Stopped-Flow Kinetics Experiment for the Physical Chemistry Laboratory Using Noncorrosive Reagents

ERIC Educational Resources Information Center

Prigodich, Richard V.

2014-01-01

Stopped-flow kinetics techniques are important to the study of rapid chemical and biochemical reactions. Incorporation of a stopped-flow kinetics experiment into the physical chemistry laboratory curriculum would therefore be an instructive addition. However, the usual reactions studied in such exercises employ a corrosive reagent that can over…

Real-Time Optical Monitoring of Flow Kinetics and Gas Phase Reactions Under High-Pressure OMCVD Conditions

NASA Technical Reports Server (NTRS)

Dietz, N.; McCall, S.; Bachmann, K. J.

2001-01-01

This contribution addresses the real-time optical characterization of gas flow and gas phase reactions as they play a crucial role for chemical vapor phase depositions utilizing elevated and high pressure chemical vapor deposition (HPCVD) conditions. The objectives of these experiments are to validate on the basis of results on real-time optical diagnostics process models simulation codes, and provide input parameter sets needed for analysis and control of chemical vapor deposition at elevated pressures. Access to microgravity is required to retain high pressure conditions of laminar flow, which is essential for successful acquisition and interpretation of the optical data. In this contribution, we describe the design and construction of the HPCVD system, which include access ports for various optical methods of real-time process monitoring and to analyze the initial stages of heteroepitaxy and steady-state growth in the different pressure ranges. To analyze the onset of turbulence, provisions are made for implementation of experimental methods for in-situ characterization of the nature of flow. This knowledge will be the basis for the design definition of experiments under microgravity, where gas flow conditions, gas phase and surface chemistry, might be analyzed by remote controlled real-time diagnostics tools, developed in this research project.

Numerical Simulation of Permeability Change in Wellbore Cement Fractures after Geomechanical Stress and Geochemical Reactions Using X-ray Computed Tomography Imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kabilan, Senthil; Jung, Hun Bok; Kuprat, Andrew P.

X-ray microtomography (XMT) imaging combined with a three-dimensional (3D) computational fluid dynamics (CFD) modeling technique was used to study the effect of geochemical and geomechanical processes on fracture properties in composite Portland cement–basalt caprock core samples. The effect of fluid properties and flow conditions on fracture permeability was numerically studied by using fluids with varying physical properties and simulating different pressure conditions. CFD revealed that the application of geomechanical stress led to increased fluid flow, which resulted in increased fracture permeability. After CO2-reaction, XMT images displayed preferential precipitation of calcium carbonate within the fractures in the cement matrix and lessmore » precipitation in fractures located at the cement–basalt interface. CFD predicted changes in flow characteristics and differences in absolute values of flow properties due to different pressure gradients. CFD was able to highlight the profound effect of fluid properties on flow characteristics and hydraulic properties of fractures. This study demonstrates the applicability of XMT imaging and CFD as powerful tools for characterizing the hydraulic properties of fractures in a number of applications like geologic carbon sequestration and storage, hydraulic fracturing for shale gas production, and enhanced geothermal systems.« less

Characteristics of Atmospheric Pressure Rotating Gliding Arc Plasmas

NASA Astrophysics Data System (ADS)

Zhang, Hao; Zhu, Fengsen; Tu, Xin; Bo, Zheng; Cen, Kefa; Li, Xiaodong

2016-05-01

In this work, a novel direct current (DC) atmospheric pressure rotating gliding arc (RGA) plasma reactor has been developed for plasma-assisted chemical reactions. The influence of the gas composition and the gas flow rate on the arc dynamic behaviour and the formation of reactive species in the N2 and air gliding arc plasmas has been investigated by means of electrical signals, high speed photography, and optical emission spectroscopic diagnostics. Compared to conventional gliding arc reactors with knife-shaped electrodes which generally require a high flow rate (e.g., 10-20 L/min) to maintain a long arc length and reasonable plasma discharge zone, in this RGA system, a lower gas flow rate (e.g., 2 L/min) can also generate a larger effective plasma reaction zone with a longer arc length for chemical reactions. Two different motion patterns can be clearly observed in the N2 and air RGA plasmas. The time-resolved arc voltage signals show that three different arc dynamic modes, the arc restrike mode, takeover mode, and combined modes, can be clearly identified in the RGA plasmas. The occurrence of different motion and arc dynamic modes is strongly dependent on the composition of the working gas and gas flow rate. supported by National Natural Science Foundation of China (No. 51576174), the Specialized Research Fund for the Doctoral Program of Higher Education of China (No. 20120101110099) and the Fundamental Research Funds for the Central Universities (No. 2015FZA4011)

Heterogeneous Pd catalysts as emulsifiers in Pickering emulsions for integrated multistep synthesis in flow chemistry

PubMed Central

Hiebler, Katharina; Lichtenegger, Georg J; Maier, Manuel C; Park, Eun Sung; Gonzales-Groom, Renie

2018-01-01

Within the “compartmentalised smart factory” approach of the ONE-FLOW project the implementation of different catalysts in “compartments” provided by Pickering emulsions and their application in continuous flow is targeted. We present here the development of heterogeneous Pd catalysts that are ready to be used in combination with biocatalysts for catalytic cascade synthesis of active pharmaceutical ingredients (APIs). In particular, we focus on the application of the catalytic systems for Suzuki–Miyaura cross-coupling reactions, which is the key step in the synthesis of the targeted APIs valsartan and sacubitril. An immobilised enzyme will accomplish the final product formation via hydrolysis. In order to create a large interfacial area for the catalytic reactions and to keep the reagents separated until required, the catalyst particles are used to stabilise Pickering emulsions of oil and water. A set of Ce–Sn–Pd oxides with the molecular formula Ce0.99− xSnxPd0.01O2−δ (x = 0–0.99) has been prepared utilising a simple single-step solution combustion method. The high applicability of the catalysts for different functional groups and their minimal leaching behaviour is demonstrated with various Suzuki–Miyaura cross-coupling reactions in batch as well as in continuous flow employing the so-called “plug & play reactor”. Finally, we demonstrate the use of these particles as the sole emulsifier of oil–water emulsions for a range of oils. PMID:29623127

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

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

Studies in organic and physical photochemistry - an interdisciplinary approach.

PubMed

Oelgemöller, Michael; Hoffmann, Norbert

2016-08-21

Traditionally, organic photochemistry when applied to synthesis strongly interacts with physical chemistry. The aim of this review is to illustrate this very fruitful interdisciplinary approach and cooperation. A profound understanding of the photochemical reactivity and reaction mechanisms is particularly helpful for optimization and application of these reactions. Some typical reactions and particular aspects are reported such as the Norrish-Type II reaction and the Yang cyclization and related transformations, the [2 + 2] photocycloadditions, particularly the Paternò-Büchi reaction, photochemical electron transfer induced transformations, different kinds of catalytic reactions such as photoredox catalysis for organic synthesis and photooxygenation are discussed. Particular aspects such as the structure and reactivity of aryl cations, photochemical reactions in the crystalline state, chiral memory, different mechanisms of hydrogen transfer in photochemical reactions or fundamental aspects of stereoselectivity are discussed. Photochemical reactions are also investigated in the context of chemical engineering. Particularly, continuous flow reactors are of interest. Novel reactor systems are developed and modeling of photochemical transformations and different reactors play a key role in such studies. This research domain builds a bridge between fundamental studies of organic photochemical reactions and their industrial application.

Simulations of pattern dynamics for reaction-diffusion systems via SIMULINK.

PubMed

Wang, Kaier; Steyn-Ross, Moira L; Steyn-Ross, D Alistair; Wilson, Marcus T; Sleigh, Jamie W; Shiraishi, Yoichi

2014-04-11

Investigation of the nonlinear pattern dynamics of a reaction-diffusion system almost always requires numerical solution of the system's set of defining differential equations. Traditionally, this would be done by selecting an appropriate differential equation solver from a library of such solvers, then writing computer codes (in a programming language such as C or Matlab) to access the selected solver and display the integrated results as a function of space and time. This "code-based" approach is flexible and powerful, but requires a certain level of programming sophistication. A modern alternative is to use a graphical programming interface such as Simulink to construct a data-flow diagram by assembling and linking appropriate code blocks drawn from a library. The result is a visual representation of the inter-relationships between the state variables whose output can be made completely equivalent to the code-based solution. As a tutorial introduction, we first demonstrate application of the Simulink data-flow technique to the classical van der Pol nonlinear oscillator, and compare Matlab and Simulink coding approaches to solving the van der Pol ordinary differential equations. We then show how to introduce space (in one and two dimensions) by solving numerically the partial differential equations for two different reaction-diffusion systems: the well-known Brusselator chemical reactor, and a continuum model for a two-dimensional sheet of human cortex whose neurons are linked by both chemical and electrical (diffusive) synapses. We compare the relative performances of the Matlab and Simulink implementations. The pattern simulations by Simulink are in good agreement with theoretical predictions. Compared with traditional coding approaches, the Simulink block-diagram paradigm reduces the time and programming burden required to implement a solution for reaction-diffusion systems of equations. Construction of the block-diagram does not require high-level programming skills, and the graphical interface lends itself to easy modification and use by non-experts.

LSENS, The NASA Lewis Kinetics and Sensitivity Analysis Code

NASA Technical Reports Server (NTRS)

Radhakrishnan, K.

2000-01-01

A general chemical kinetics and sensitivity analysis code for complex, homogeneous, gas-phase reactions is described. The main features of the code, LSENS (the NASA Lewis kinetics and sensitivity analysis code), are its flexibility, efficiency and convenience in treating many different chemical reaction models. The models include: static system; steady, one-dimensional, inviscid flow; incident-shock initiated reaction in a shock tube; and a perfectly stirred reactor. In addition, equilibrium computations can be performed for several assigned states. An implicit numerical integration method (LSODE, the Livermore Solver for Ordinary Differential Equations), which works efficiently for the extremes of very fast and very slow reactions, is used to solve the "stiff" ordinary differential equation systems that arise in chemical kinetics. For static reactions, the code uses the decoupled direct method to calculate sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of dependent variables and/or the rate coefficient parameters. Solution methods for the equilibrium and post-shock conditions and for perfectly stirred reactor problems are either adapted from or based on the procedures built into the NASA code CEA (Chemical Equilibrium and Applications).

Generic Procedure for Coupling the PHREEQC Geochemical Modeling Framework with Flow and Solute Transport Simulators

NASA Astrophysics Data System (ADS)

Wissmeier, L. C.; Barry, D. A.

2009-12-01

Computer simulations of water availability and quality play an important role in state-of-the-art water resources management. However, many of the most utilized software programs focus either on physical flow and transport phenomena (e.g., MODFLOW, MT3DMS, FEFLOW, HYDRUS) or on geochemical reactions (e.g., MINTEQ, PHREEQC, CHESS, ORCHESTRA). In recent years, several couplings between both genres of programs evolved in order to consider interactions between flow and biogeochemical reactivity (e.g., HP1, PHWAT). Software coupling procedures can be categorized as ‘close couplings’, where programs pass information via the memory stack at runtime, and ‘remote couplings’, where the information is exchanged at each time step via input/output files. The former generally involves modifications of software codes and therefore expert programming skills are required. We present a generic recipe for remotely coupling the PHREEQC geochemical modeling framework and flow and solute transport (FST) simulators. The iterative scheme relies on operator splitting with continuous re-initialization of PHREEQC and the FST of choice at each time step. Since PHREEQC calculates the geochemistry of aqueous solutions in contact with soil minerals, the procedure is primarily designed for couplings to FST’s for liquid phase flow in natural environments. It requires the accessibility of initial conditions and numerical parameters such as time and space discretization in the input text file for the FST and control of the FST via commands to the operating system (batch on Windows; bash/shell on Unix/Linux). The coupling procedure is based on PHREEQC’s capability to save the state of a simulation with all solid, liquid and gaseous species as a PHREEQC input file by making use of the dump file option in the TRANSPORT keyword. The output from one reaction calculation step is therefore reused as input for the following reaction step where changes in element amounts due to advection/dispersion are introduced as irreversible reactions. An example for the coupling of PHREEQC and MATLAB for the solution of unsaturated flow and transport is provided.

Fast intraslab fluid-flow events linked to pulses of high pore fluid pressure at the subducted plate interface

NASA Astrophysics Data System (ADS)

Taetz, Stephan; John, Timm; Bröcker, Michael; Spandler, Carl; Stracke, Andreas

2018-01-01

A better understanding of the subduction zone fluid cycle and its chemical-mechanical feedback requires in-depth knowledge about how fluids flow within and out of descending slabs. Relicts of fluid-flow systems in exhumed rocks of fossil subduction zones allow for identification of the general relationships between dehydration reactions, fluid pathway formation, the dimensions and timescales of distinct fluid flow events; all of which are required for quantitative models for fluid-induced subduction zone processes. Two types of garnet-quartz-phengite veins can be distinguished in an eclogite-facies mélange block from the Pouébo Eclogite Mélange, New Caledonia. These veins record synmetamorphic internal fluid release by mineral breakdown reactions (type I veins), and infiltration of an external fluid (type II veins) with the associated formation of a reaction selvage. The dehydration and fluid migration documented by the type I veins likely occurred on a timescale of 105-106 years, based on average subduction rates and metamorphic conditions required for mineral dehydration and fluid flow. The timeframe of fluid-rock interaction between the external fluid and the wall-rock of the type II veins is quantified using a continuous bulk-rock Li-diffusion profile perpendicular to a vein and its metasomatic selvage. Differences in Li concentration between the internal and external fluid reservoirs resulted in a distinct diffusion profile (decreasing Li concentration and increasing δ7 Li) as the reaction front propagated into the host rock. Li-chronometric constraints indicate that the timescales of fluid-rock interaction associated with type II vein formation are on the order of 1 to 4 months (0.150-0.08+0.14 years). The short-lived, pulse-like character of this process is consistent with the notion that fluid flow caused by oceanic crust dehydration at the blueschist-to-eclogite transition contributes to or even dominates episodic pore fluid pressure increases at the plate interface, which in turn, may trigger slip events reported from many subduction zones.

Electron transfer in biology

NASA Astrophysics Data System (ADS)

Williams, R. J. P.

Electron transfer is one of the key reactions of biology not just in catalysis of oxidation/reduction reactions but in the conversion of sources of energy such as light to usable form for chemical transformations. There are then two intriguing problems. What is the nature of the matrix in which electrons flow in a biological cell after the initial charge separation due for example to the absorption of light. Here we are examining biological structures similar to man's electronic wires and the construction must be of low resistance in what are apparently insulators - organic polymers. It has been found that the electronic conduction system is largely made from metallo-proteins associated with lipid membranes. We understand much about these biological wires today. The second problem concerns the conversion of the energy captured from the light into usable chemical form. The major synthetic step in the production of biological polymers, including proteins, DNA, RNA, polysaccharides and fats, is condensation, i.e. the removal of water in the formation of amides, esters and so on. Now these condensation reactions are driven in biology by using a drying agent in water, namely the anhydride, pyrophosphate, in a special compound ATP, adenosine triphosphate. The central problem is to discover exactly how the flow of electrons can be related to the synthesis of (bound) pyrophosphate. (In a thermodynamic sense pyrophosphate is a water soluble kinetically stable drying agent comparable with solid P2O5.) In the biological systems the connection between these different classes of reaction, electron transfer and condensation, is known to be via the production of an energized gradient of protons across the biological membrane which arises from the flow of electrons across the same membrane in the electron transport wires of biology. However we do not understand thoroughly the steps which lead from electron flow in a membrane to proton gradients in that membrane, i.e. electron/proton coupling. Again we do not understand thoroughly how subsequently the proton gradient across a membrane makes ATP, pyrophosphate. Today there is good experimental evidence as to the likely answers in principle. These analyse the coupling devices in mechanical terms. In this article I describe at first the 'wires' of biology, uncoupled simple electron flow, and then go on to the ways in which electron flow could be transduced by mechanical devices, also proteins, into proton gradients and then ATP. This will be termed coupled electron flow. The objective of the article is to stimulate participation by physical chemists in the further description of biological energy capture from light or the oxidation of hydrocarbons to a form suitable for driving chemical syntheses in a controlled manner.

Forced-flow bioreactor for sucrose inversion using ceramic membrane activated by silanization.

PubMed

Nakajima, M; Watanabe, A; Jimbo, N; Nishizawa, K; Nakao, S

1989-02-20

A forced-flow enzyme membrane reactor system for sucrose inversion was investigated using three ceramic membranes having different pore sizes. Invertase was immobilized chemically to the inner surface of a ceramic membrane activated by a silane-glutaraldehyde technique. With the cross-flow filtration of sucrose solution, the reaction rate was a function of the permeate flux, easily controlled by pressure. Using 0.5 microm support pore size of membrane, the volumetric productivity obtained was 10 times higher than that in a reported immobilized enzyme column reactor, with a short residence time of 5 s and 100% conversion of the sucrose inversion.

Solutal and thermal buoyancy effects in self-powered phosphatase micropumps.

PubMed

Valdez, Lyanne; Shum, Henry; Ortiz-Rivera, Isamar; Balazs, Anna C; Sen, Ayusman

2017-04-12

Immobilized enzymes generate net fluid flow when exposed to specific reagents in solution. Thus, they function as self-powered platforms that combine sensing and on-demand fluid pumping. To uncover the mechanism of pumping, we examine the effects of solutal and thermal buoyancy on the behavior of phosphatase-based micropumps, using a series of reactants with known thermodynamic and kinetic parameters. By combining modeling and experiments, we perform the first quantitative comparison of thermal and solutal effects in an enzyme micropump system. Despite the significant exothermicity of the catalyzed reactions, we find that thermal effects play a minimal role in the observed fluid flow. Instead, fluid transport in phosphatase micropumps is governed by the density difference between the reactants and the products of the reaction. This surprising conclusion suggests new design principles for catalytic pumps.

Atmospheric pressure flow reactor: Gas phase chemical kinetics under tropospheric conditions without wall effects

NASA Technical Reports Server (NTRS)

Koontz, Steven L. (Inventor); Davis, Dennis D. (Inventor)

1991-01-01

A flow reactor for simulating the interaction in the troposphere is set forth. A first reactant mixed with a carrier gas is delivered from a pump and flows through a duct having louvers therein. The louvers straighten out the flow, reduce turbulence and provide laminar flow discharge from the duct. A second reactant delivered from a source through a pump is input into the flowing stream, the second reactant being diffused through a plurality of small diffusion tubes to avoid disturbing the laminar flow. The commingled first and second reactants in the carrier gas are then directed along an elongated duct where the walls are spaced away from the flow of reactants to avoid wall interference, disturbance or turbulence arising from the walls. A probe connected with a measuring device can be inserted through various sampling ports in the second duct to complete measurements of the first and second reactants and the product of their reaction at selected XYZ locations relative to the flowing system.

A bioreactor system for the nitrogen loop in a Controlled Ecological Life Support System

NASA Technical Reports Server (NTRS)

Saulmon, M. M.; Reardon, K. F.; Sadeh, W. Z.

1996-01-01

As space missions become longer in duration, the need to recycle waste into useful compounds rises dramatically. This problem can be addressed by the development of Controlled Ecological Life Support Systems (CELSS) (i.e., Engineered Closed/Controlled Eco-Systems (ECCES)), consisting of human and plant modules. One of the waste streams leaving the human module is urine. In addition to the reclamation of water from urine, recovery of the nitrogen is important because it is an essential nutrient for the plant module. A 3-step biological process for the recycling of nitrogenous waste (urea) is proposed. A packed-bed bioreactor system for this purpose was modeled, and the issues of reaction step segregation, reactor type and volume, support particle size, and pressure drop were addressed. Based on minimization of volume, a bioreactor system consisting of a plug flow immobilized urease reactor, a completely mixed flow immobilized cell reactor to convert ammonia to nitrite, and a plug flow immobilized cell reactor to produce nitrate from nitrite is recommended. It is apparent that this 3-step bioprocess meets the requirements for space applications.

Normal and reverse flow injection–spectrophotometric determination of thiamine hydrochloride in pharmaceutical preparations using diazotized metoclopramide

PubMed Central

Al Abachi, Mouayed Q.; Hadi, Hind

2012-01-01

Simple and sensitive normal and reverse flow injection methods for spectrophotometric determination of thiamine hydrochloride (THC) at the microgram level were proposed and optimized. Both methods are based on the reaction between THC and diazotized metoclopramide in alkaline medium. Beer’s law was obeyed over the range of 10–300 and 2–90 μg/mL, the limits of detection were 2.118 and 0.839 μg/mL and the sampling rates were 80 and 95 injections per hour for normal and reverse flow injection methods respectively. The application of both methods to commercially available pharmaceuticals produced acceptable results. The flow system is suitable for application in quality control processes. PMID:29403765

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nash, Connor P.; Farberow, Carrie A.; Hensley, Jesse E.

Temperature programmed reaction (TPRxn) is a simple yet powerful tool for screening solid catalyst performance at a variety of conditions. A TPRxn system includes a reactor, furnace, gas and vapor sources, flow control, instrumentation to quantify reaction products (e.g., gas chromatograph), and instrumentation to monitor the reaction in real time (e.g., mass spectrometer). Here, we apply the TPRxn methodology to study molybdenum carbide catalysts for the deoxygenation of acetic acid, an important reaction among many in the upgrading/stabilization of biomass pyrolysis vapors. TPRxn is used to evaluate catalyst activity and selectivity and to test hypothetical reaction pathways (e.g., decarbonylation, ketonization,more » and hydrogenation). Furthermore, the results of the TPRxn study of acetic acid deoxygenation show that molybdenum carbide is an active catalyst for this reaction at temperatures above ca. 300 °C and that the reaction favors deoxygenation (i.e., C-O bond-breaking) products at temperatures below ca. 400 °C and decarbonylation (i.e., C-C bond-breaking) products at temperatures above ca. 400 °C.« less

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

NASA Technical Reports Server (NTRS)

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

1984-01-01

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

Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis.

PubMed

Nguyen, Luan; Tao, Franklin Feng

2016-06-01

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

The application of a monolithic triphenylphosphine reagent for conducting Ramirez gem-dibromoolefination reactions in flow.

PubMed

Roper, Kimberley A; Berry, Malcolm B; Ley, Steven V

2013-01-01

The application of a monolithic form of triphenylphosphine to the Ramirez gem-dibromoolefination reaction using flow chemistry techniques is reported. A variety of gem-dibromides were synthesised in high purity and excellent yield following only removal of solvent and no further off-line purification. It is also possible to perform the Appel reaction using the same monolith and the relationship between the mechanisms of the two reactions is discussed.

The application of a monolithic triphenylphosphine reagent for conducting Ramirez gem-dibromoolefination reactions in flow

PubMed Central

Roper, Kimberley A; Berry, Malcolm B

2013-01-01

Summary The application of a monolithic form of triphenylphosphine to the Ramirez gem-dibromoolefination reaction using flow chemistry techniques is reported. A variety of gem-dibromides were synthesised in high purity and excellent yield following only removal of solvent and no further off-line purification. It is also possible to perform the Appel reaction using the same monolith and the relationship between the mechanisms of the two reactions is discussed. PMID:24062843

Receptor-mediated binding of IgE-sensitized rat basophilic leukemia cells to antigen-coated substrates under hydrodynamic flow.

PubMed Central

Tempelman, L A; Hammer, D A

1994-01-01

The physiological function of many cells is dependent on their ability to adhere via receptors to ligand-coated surfaces under fluid flow. We have developed a model experimental system to measure cell adhesion as a function of cell and surface chemistry and fluid flow. Using a parallel-plate flow chamber, we measured the binding of rat basophilic leukemia cells preincubated with anti-dinitrophenol IgE antibody to polyacrylamide gels covalently derivatized with 2,4-dinitrophenol. The rat basophilic leukemia cells' binding behavior is binary: cells are either adherent or continue to travel at their hydrodynamic velocity, and the transition between these two states is abrupt. The spatial location of adherent cells shows cells can adhere many cell diameters down the length of the gel, suggesting that adhesion is a probabilistic process. The majority of experiments were performed in the excess ligand limit in which adhesion depends strongly on the number of receptors but weakly on ligand density. Only 5-fold changes in IgE surface density or in shear rate were necessary to change adhesion from complete to indistinguishable from negative control. Adhesion showed a hyperbolic dependence on shear rate. By performing experiments with two IgE-antigen configurations in which the kinetic rates of receptor-ligand binding are different, we demonstrate that the forward rate of reaction of the receptor-ligand pair is more important than its thermodynamic affinity in the regulation of binding under hydrodynamic flow. In fact, adhesion increases with increasing receptor-ligand reaction rate or decreasing shear rate, and scales with a single dimensionless parameter which compares the relative rates of reaction to fluid shear. Images FIGURE 2 FIGURE 3 FIGURE 6 FIGURE 8 FIGURE 10 PMID:8038394

Integrated multiplexed capillary electrophoresis system

DOEpatents

Yeung, Edward S.; Tan, Hongdong

2002-05-14

The present invention provides an integrated multiplexed capillary electrophoresis system for the analysis of sample analytes. The system integrates and automates multiple components, such as chromatographic columns and separation capillaries, and further provides a detector for the detection of analytes eluting from the separation capillaries. The system employs multiplexed freeze/thaw valves to manage fluid flow and sample movement. The system is computer controlled and is capable of processing samples through reaction, purification, denaturation, pre-concentration, injection, separation and detection in parallel fashion. Methods employing the system of the invention are also provided.

Advanced Continuous Flow Platform for On-Demand Pharmaceutical Manufacturing.

PubMed

Zhang, Ping; Weeranoppanant, Nopphon; Thomas, Dale A; Tahara, Kohei; Stelzer, Torsten; Russell, Mary Grace; O'Mahony, Marcus; Myerson, Allan S; Lin, Hongkun; Kelly, Liam P; Jensen, Klavs F; Jamison, Timothy F; Dai, Chunhui; Cui, Yuqing; Briggs, Naomi; Beingessner, Rachel L; Adamo, Andrea

2018-02-21

As a demonstration of an alternative to the challenges faced with batch pharmaceutical manufacturing including the large production footprint and lengthy time-scale, we previously reported a refrigerator-sized continuous flow system for the on-demand production of essential medicines. Building on this technology, herein we report a second-generation, reconfigurable and 25 % smaller (by volume) continuous flow pharmaceutical manufacturing platform featuring advances in reaction and purification equipment. Consisting of two compact [0.7 (L)×0.5 (D)×1.3 m (H)] stand-alone units for synthesis and purification/formulation processes, the capabilities of this automated system are demonstrated with the synthesis of nicardipine hydrochloride and the production of concentrated liquid doses of ciprofloxacin hydrochloride, neostigmine methylsulfate and rufinamide that meet US Pharmacopeia standards. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Orion Service Module Reaction Control System Plume Impingement Analysis Using PLIMP/RAMP2

NASA Technical Reports Server (NTRS)

Wang, Xiao-Yen J.; Gati, Frank; Yuko, James R.; Motil, Brian J.; Lumpkin, Forrest E.

2009-01-01

The Orion Crew Exploration Vehicle Service Module Reaction Control System engine plume impingement was computed using the plume impingement program (PLIMP). PLIMP uses the plume solution from RAMP2, which is the refined version of the reacting and multiphase program (RAMP) code. The heating rate and pressure (force and moment) on surfaces or components of the Service Module were computed. The RAMP2 solution of the flow field inside the engine and the plume was compared with those computed using GASP, a computational fluid dynamics code, showing reasonable agreement. The computed heating rate and pressure using PLIMP were compared with the Reaction Control System plume model (RPM) solution and the plume impingement dynamics (PIDYN) solution. RPM uses the GASP-based plume solution, whereas PIDYN uses the SCARF plume solution. Three sets of the heating rate and pressure solutions agree well. Further thermal analysis on the avionic ring of the Service Module showed that thermal protection is necessary because of significant heating from the plume.

Oxidation kinetics and soot formation

NASA Technical Reports Server (NTRS)

Glassman, I.; Brezinsky, K.

1983-01-01

The research objective is to clarify the role of aromaticity in the soot nucleation process by determining the relative importance of phenyl radical/molecular oxygen and benzene/atomic oxygen reactions in the complex combustion of aromatic compounds. Three sets of chemical flow reactor experiments have been designed to determine the relative importance of the phenyl radical/molecular oxygen and benzene/atomic oxygen reactions. The essential elements of these experiments are 1) the use of cresols and anisole formed during the high temperature oxidation of toluene as chemical reaction indicators; 2) the in situ photolysis of molecular oxygen to provide an oxygen atom perturbation in the reacting aromatic system; and 3) the high temperature pyrolysis of phenol, the cresols and possibly anisole.

Kinetic Studies of Iron Deposition in Horse Spleen Ferritin Using H2O2 and O2 as Oxidants

NASA Technical Reports Server (NTRS)

Lowery, Thomas J., Jr.; Bunker, Jared; Zhang, Bo; Costen, Robert; Watt, Gerald D.

2004-01-01

The reaction of horse spleen ferritin (HoSF) with Fe(2+) at pH 6.5 and 7.5 using O2, H2O2 and 1:1 a mixture of both showed that the iron deposition reaction using H2O2 is approx. 20- to 50-fold faster than the reaction with O2 alone. When H2O2 was added during the iron deposition reaction initiated with O2 as oxidant, Fe(2+) was preferentially oxidized by H2O2, consistent with the above kinetic measurements. Both the O2 and H202 reactions were well defined from 15 to 40 C from which activation parameters were determined. The iron deposition reaction was also studied using O2 as oxidant in the presence and absence of catalase using both stopped-flow and pumped-flow measurements. The presence of catalase decreased the rate of iron deposition by approx. 1.5-fold, and gave slightly smaller absorbance changes than in its absence. From the rate constants for the O2 (0.044 per second) and H2O2 (0.67 per second) iron-deposition reactions at pH 7.5, simulations of steady-state H2O2 concentrations were computed to be 0.45 micromolar. This low value and reported Fe2(+)/O2 values of 2.0-2.5 are consistent with H2O2 rapidly reacting by an alternate but unidentified pathway involving a system component such as the protein shell or the mineral core as previously postulated.

Reactive-brittle dynamics in peridotite alteration

NASA Astrophysics Data System (ADS)

Evans, O.; Spiegelman, M. W.; Kelemen, P. B.

2017-12-01

The interactions between reactive fluids and brittle solids are critical in Earth dynamics. Implications of such processes are wide-ranging: from earthquake physics to geologic carbon sequestration and the cycling of fluids and volatiles through subduction zones. Peridotite alteration is a common feature in many of these processes, which - despite its obvious importance - is relatively poorly understood from a geodynamical perspective. In particular, alteration reactions are thought to be self-limiting in nature, contradicting observations of rocks that have undergone 100% hydration/carbonation. One potential explanation of this observation is the mechanism of "reaction-driven cracking": that volume changes associated with these reactions are large enough to fracture the surrounding rock, leading to a positive feedback where new reactive surfaces are exposed and fluid pathways are created. The purpose of this study is to investigate the relative roles of reaction, elastic stresses and surface tension in alteration reactions. In this regard we derive a system of equations describing reactive fluid flow in an elastically deformable porous media, and explore them via a combination of analytic and numerical solutions. Using this model we show that the final stress state of a dry peridotite that has undergone reaction depends strongly on the rates of reaction versus fluid transport: significant fluid flow driven by pressure and/or surface tension gradients implies higher fractions of serpentinization, leaving behind a highly stressed residuum of partially reacted material. Using a model set-up that mimics a cylindrical triaxial apparatus we predict that the resulting stresses would lead to tensile failure and the generation of radially oriented cracks.

Flows, scaling, and the control of moment hierarchies for stochastic chemical reaction networks

NASA Astrophysics Data System (ADS)

Smith, Eric; Krishnamurthy, Supriya

2017-12-01

Stochastic chemical reaction networks (CRNs) are complex systems that combine the features of concurrent transformation of multiple variables in each elementary reaction event and nonlinear relations between states and their rates of change. Most general results concerning CRNs are limited to restricted cases where a topological characteristic known as deficiency takes a value 0 or 1, implying uniqueness and positivity of steady states and surprising, low-information forms for their associated probability distributions. Here we derive equations of motion for fluctuation moments at all orders for stochastic CRNs at general deficiency. We show, for the standard base case of proportional sampling without replacement (which underlies the mass-action rate law), that the generator of the stochastic process acts on the hierarchy of factorial moments with a finite representation. Whereas simulation of high-order moments for many-particle systems is costly, this representation reduces the solution of moment hierarchies to a complexity comparable to solving a heat equation. At steady states, moment hierarchies for finite CRNs interpolate between low-order and high-order scaling regimes, which may be approximated separately by distributions similar to those for deficiency-zero networks and connected through matched asymptotic expansions. In CRNs with multiple stable or metastable steady states, boundedness of high-order moments provides the starting condition for recursive solution downward to low-order moments, reversing the order usually used to solve moment hierarchies. A basis for a subset of network flows defined by having the same mean-regressing property as the flows in deficiency-zero networks gives the leading contribution to low-order moments in CRNs at general deficiency, in a 1 /n expansion in large particle numbers. Our results give a physical picture of the different informational roles of mean-regressing and non-mean-regressing flows and clarify the dynamical meaning of deficiency not only for first-moment conditions but for all orders in fluctuations.

Multi-scale modeling of multi-component reactive transport in geothermal aquifers

NASA Astrophysics Data System (ADS)

Nick, Hamidreza M.; Raoof, Amir; Wolf, Karl-Heinz; Bruhn, David

2014-05-01

In deep geothermal systems heat and chemical stresses can cause physical alterations, which may have a significant effect on flow and reaction rates. As a consequence it will lead to changes in permeability and porosity of the formations due to mineral precipitation and dissolution. Large-scale modeling of reactive transport in such systems is still challenging. A large area of uncertainty is the way in which the pore-scale information controlling the flow and reaction will behave at a larger scale. A possible choice is to use constitutive relationships relating, for example the permeability and porosity evolutions to the change in the pore geometry. While determining such relationships through laboratory experiments may be limited, pore-network modeling provides an alternative solution. In this work, we introduce a new workflow in which a hybrid Finite-Element Finite-Volume method [1,2] and a pore network modeling approach [3] are employed. Using the pore-scale model, relevant constitutive relations are developed. These relations are then embedded in the continuum-scale model. This approach enables us to study non-isothermal reactive transport in porous media while accounting for micro-scale features under realistic conditions. The performance and applicability of the proposed model is explored for different flow and reaction regimes. References: 1. Matthäi, S.K., et al.: Simulation of solute transport through fractured rock: a higher-order accurate finite-element finite-volume method permitting large time steps. Transport in porous media 83.2 (2010): 289-318. 2. Nick, H.M., et al.: Reactive dispersive contaminant transport in coastal aquifers: Numerical simulation of a reactive Henry problem. Journal of contaminant hydrology 145 (2012), 90-104. 3. Raoof A., et al.: PoreFlow: A Complex pore-network model for simulation of reactive transport in variably saturated porous media, Computers & Geosciences, 61, (2013), 160-174.

Stopped-in-loop flow analysis system for successive determination of trace vanadium and iron in drinking water using their catalytic reactions.

PubMed

Ayala Quezada, Alejandro; Ohara, Keisuke; Ratanawimarnwong, Nuanlaor; Nacapricha, Duangjai; Murakami, Hiroya; Teshima, Norio; Sakai, Tadao

2015-11-01

An automated stopped-in-loop flow analysis (SILFA) system is proposed for the successive catalytic determination of vanadium and iron. The determination of vanadium was based on the p-anisidine oxidation by potassium bromate in the presence of Tiron as an activator to form a reddish dye, which has an absorption maximum at 510 nm. The selectivity of the vanadium determination was greatly improved by adding diphosphate as a masking agent of iron. For the iron determination, an iron-catalyzed oxidative reaction of p-anisidine by hydrogen peroxide with 1,10-phenanthroline as an activator to produce a reddish dye (510 nm) was employed. The SILFA system consisted of two peristaltic pumps, two six-port injection valves, a four-port selection valve, a heater device, a spectrophotometric detector and a data acquisition device. One six-port injection valve was used for the isolation of a mixed solution of standard/sample and reagent to promote each catalytic reaction, and another six-port injection valve was used for switching the reagent for vanadium or iron to achieve selective determination of each analyte. The above mentioned four-port selection valve was used to select standard solutions or sample. These three valves and the two peristaltic pumps were controlled by a built-in programmable logic controller in a touchscreen controller. The obtained results showed that the proposed SILFA monitoring system constituted an effective approach for the selective determination of vanadium and iron. The limits of detection, 0.052 and 0.55 µg L(-1), were obtained for vanadium and iron, respectively. The proposed system was successfully applied to drinking water samples without any preconcentration procedures. Copyright © 2015 Elsevier B.V. All rights reserved.

Capturing poromechanical coupling effects of the reactive fracturing process in porous rock via a DEM-network model

NASA Astrophysics Data System (ADS)

Ulven, Ole Ivar; Sun, WaiChing

2016-04-01

Fluid transport in a porous medium has important implications for understanding natural geological processes. At a sufficiently large scale, a fluid-saturated porous medium can be regarded as a two-phase continuum, with the fluid constituent flowing in the Darcian regime. Nevertheless, a fluid mediated chemical reaction can in some cases change the permeability of the rock locally: Mineral dissolution can cause increased permeability, whereas mineral precipitation can reduce the permeability. This might trigger a complicated hydro-chemo-mechanical coupling effect that causes channeling of fluids or clogging of the system. If the fluid is injected or produced at a sufficiently high rate, the pressure might increase enough to cause the onset and propagation of fractures. Fractures in return create preferential flow paths that enhance permeability, localize fluid flow and chemical reaction, prevent build-up of pore pressure and cause anisotropy of the hydro-mechanical responses of the effective medium. This leads to a complex coupled process of solid deformation, chemical reaction and fluid transport enhanced by the fracture formation. In this work, we develop a new coupled numerical model to study the complexities of feedback among fluid pressure evolution, fracture formation and permeability changes due to a chemical process in a 2D system. We combine a discrete element model (DEM) previously used to study a volume expanding process[1, 2] with a new fluid transport model based on poroelasticity[3] and a fluid-mediated chemical reaction that changes the permeability of the medium. This provides new insights into the hydro-chemo-mechanical process of a transforming porous medium. References [1] Ulven, O. I., Storheim, H., Austrheim, H., and Malthe-Sørenssen, A. "Fracture Initiation During Volume Increasing Reactions in Rocks and Applications for CO2 Sequestration", Earth Planet. Sc. Lett. 389C, 2014a, pp. 132 - 142, doi:10.1016/j.epsl.2013.12.039. [2] Ulven, O. I., Jamtveit, B., and Malthe-Sørenssen, A., "Reaction-driven fracturing of porous rock", J. Geophys. Res. Solid Earth 119, 2014b, doi:10.1002/2014JB011102. [3] Ulven, O. I., and Sun, W.C., "A locally mass-conserving dual-graph lattice model for fluid-driven fracture", in prep.

Controlling energy flow in multimetallic nanostructures for plasmonic catalysis

NASA Astrophysics Data System (ADS)

Aslam, Umar; Chavez, Steven; Linic, Suljo

2017-10-01

It has been shown that photoexcitation of plasmonic metal nanoparticles (Ag, Au and Cu) can induce direct photochemical reactions. However, the widespread application of this technology in catalysis has been limited by the relatively poor chemical reactivity of noble metal surfaces. Despite efforts to combine plasmonic and catalytic metals, the physical mechanisms that govern energy transfer from plasmonic metals to catalytic metals remain unclear. Here we show that hybrid core-shell nanostructures in which a core plasmonic metal harvests visible-light photons can selectively channel that energy into catalytically active centres on the nanostructure shell. To accomplish this, we developed a synthetic protocol to deposit a few monolayers of Pt onto Ag nanocubes. This model system allows us to conclusively separate the optical and catalytic functions of the hybrid nanomaterial and determine that the flow of energy is strongly biased towards the excitation of energetic charge carriers in the Pt shell. We demonstrate the utility of these nanostructures for photocatalytic chemical reactions in the preferential oxidation of CO in excess H2. Our data demonstrate that the reaction occurs exclusively on the Pt surface.

Stopped-flow enzyme assays on a chip using a microfabricated mixer.

PubMed

Burke, Brian J; Regnier, Fred E

2003-04-15

This paper describes a microfabricated enzyme assay system including a micromixer that can be used to perform stopped-flow reactions. Samples and reagents were transported into the system by electroosmotic flow (EOF). Streams of reagents were merged and passed through the 100-pL micromixer in < 1 s. The objective of the work was to perform kinetically based enzyme assays in the stopped-flow mode using a system of roughly 6 nL volume. Beta-galactosidase (beta-Gal) was chosen as a model enzyme for these studies and was used to convert the substrate fluorescein mono-beta-D-galactopyranoside (FMG) into fluorescein. Results obtained with microfabricated systems using the micromixer compared well to those obtained with an external T mixing device. In contrast, assays performed in a microfabricated device by merging two streams and allowing mixing to occur by lateral diffusion did not compare well. Using the microfabricated mixer, Km and kcat values of 75 +/- 13 microM and 44 +/- 3 s(-1) were determined. These values compare well to those obtained with the conventional stopped-flow apparatus for which Km was determined to be 60 +/- 6 microM and kcat was 47 +/- 4 s(-1). Enzyme inhibition assays with phenylethyl-beta-D-thiogalactoside (PETG) were also comparable. It was concluded that kinetically based, stopped-flow enzyme assays can be performed in 60 s or less with a miniaturized system of roughly 6 nL liquid volume when mixing is assisted with the described device.

Scientific Transactions No. 11 of the Institute of Mechanics, Moscow State University. [supersonic and hypersonic gas flow and the movement of gas with exothermic reactions

NASA Technical Reports Server (NTRS)

Gonor, A. L. (Editor)

1982-01-01

The results of flow around wings, the determination of the optimal form, and the interaction of the wake with the accompanying flow at supersonic and hypersonic speeds of the free-stream flow are given. Methods of numerical and analytical calculation of one dimensional unsteady and two dimensional steady motions of fuel-gas mixtures with exothermic reactions are also considered.

Design and validation of an advanced entrained flow reactor system for studies of rapid solid biomass fuel particle conversion and ash formation reactions

NASA Astrophysics Data System (ADS)

Wagner, David R.; Holmgren, Per; Skoglund, Nils; Broström, Markus

2018-06-01

The design and validation of a newly commissioned entrained flow reactor is described in the present paper. The reactor was designed for advanced studies of fuel conversion and ash formation in powder flames, and the capabilities of the reactor were experimentally validated using two different solid biomass fuels. The drop tube geometry was equipped with a flat flame burner to heat and support the powder flame, optical access ports, a particle image velocimetry (PIV) system for in situ conversion monitoring, and probes for extraction of gases and particulate matter. A detailed description of the system is provided based on simulations and measurements, establishing the detailed temperature distribution and gas flow profiles. Mass balance closures of approximately 98% were achieved by combining gas analysis and particle extraction. Biomass fuel particles were successfully tracked using shadow imaging PIV, and the resulting data were used to determine the size, shape, velocity, and residence time of converting particles. Successful extractive sampling of coarse and fine particles during combustion while retaining their morphology was demonstrated, and it opens up for detailed time resolved studies of rapid ash transformation reactions; in the validation experiments, clear and systematic fractionation trends for K, Cl, S, and Si were observed for the two fuels tested. The combination of in situ access, accurate residence time estimations, and precise particle sampling for subsequent chemical analysis allows for a wide range of future studies, with implications and possibilities discussed in the paper.

Multi-pumping flow system for the determination of boron in eye drops, drinking water and ocean water.

PubMed

González, Pablo; Sixto, Alexandra; Knochen, Moisés

2017-05-01

A novel automated method for the determination of boron based on the use of pulsed flows was developed and applied to the determination of this element in samples of tap water, ocean water and eye drops. The method was implemented by means of a multi-pumping system consisting of three solenoid micropumps and a photometric detector and exploits the reaction of azomethine-H in the presence of boron. The system runs under control of an open-source microcontroller. The main operational parameters were optimized. Given the particular kinetics of the reaction, a stopped-flow period (1 or 5min) was included to allow for color development. The method presents linearity in the range 0.35-3.0mgL -1 , good precision (s r <3%), and detection and quantification limits of 0.10 and 0.35mgL -1 respectively. Samples of tap water or eye drops could be successfully analyzed employing a 1-minute stop time, providing a maximum sampling frequency of 32 samples h -1 . In order to overcome matrix effect caused by the high saline concentration, ocean water samples required stop times of 5min, providing a sampling frequency of 10 samples h -1 . Recoveries of 102% (eye drops), 94% (drinking water) and 93% (ocean water) were obtained. The method was considered accurate and fit for the purpose. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of homogenous-heterogeneous reactions on MHD Prandtl fluid flow over a stretching sheet

NASA Astrophysics Data System (ADS)

Khan, Imad; Malik, M. Y.; Hussain, Arif; Salahuddin, T.

An analysis is performed to explore the effects of homogenous-heterogeneous reactions on two-dimensional flow of Prandtl fluid over a stretching sheet. In present analysis, we used the developed model of homogeneous-heterogeneous reactions in boundary layer flow. The mathematical configuration of presented flow phenomenon yields the nonlinear partial differential equations. Using scaling transformations, the governing partial differential equations (momentum equation and homogenous-heterogeneous reactions equations) are transformed into non-linear ordinary differential equations (ODE's). Then, resulting non-linear ODE's are solved by computational scheme known as shooting method. The quantitative and qualitative manners of concerned physical quantities (velocity, concentration and drag force coefficient) are examined under prescribed physical constrained through figures and tables. It is observed that velocity profile enhances verses fluid parameters α and β while Hartmann number reduced it. The homogeneous and heterogeneous reactions parameters have reverse effects on concentration profile. Concentration profile shows retarding behavior for large values of Schmidt number. Skin fraction coefficient enhances with increment in Hartmann number H and fluid parameter α .

Control of topography gradients on residence time distributions, mixing dynamics and reactive hotspot development

NASA Astrophysics Data System (ADS)

Bandopadhyay, Aditya; Le Borgne, Tanguy; Davy, Philippe

2017-04-01

Topography-driven subsurface flows are thought to play a central role in determining solute turnover and biogeochemical processes at different scales in the critical zone, including river-hyporheic zone exchanges, hillslope solute transport and reactions, and catchment biogeochemical cycles. Hydraulic head gradients, induced by topography gradients at different scales, generate a distribution of streamlines at depth, dictating the spatial distribution of redox sensitive species, the magnitude of surface water - ground water exchanges and ultimately the source/sink function of the subsurface. Flow velocities generally decrease with depth, leading to broad residence time distributions, which have been shown to affect river chemistry and geochemical reactions in catchments. In this presentation, we discuss the impact of topography-driven flows on mixing processes and the formation of localized reactive hotspots. For this, we solve analytically the coupled flow, mixing and reaction equations in two-dimensional vertical cross-sections of subsurface domains with different topography gradients. For a given topography gradient, we derive the spatial distribution of subsurface velocities, the rates of solute mixing accross streamlines and the induced kinetics of redox, precipitation and dissolution reactions using a Lagrangian approach (Le Borgne et al. 2014). We demonstrate that vertical velocity profiles driven by topography variations, act effectively as shear flows, hence stretching continuously the mixing fronts between recently infiltrated and resident water (Bandopadhyay et al. 2017). We thus derive analytical expressions for residence time distributions, mixing rates and kinetics of chemical reactions as a function of the topography gradients. We show that the rates dissolution and precipitation reactions are significantly enhanced by the existence of vertical velocity gradients and that reaction rates reach a maximum in a localized subsurface reactive layer, whose location and intensity depends on topography gradients. As a consequence of these findings, we discuss the links between topography variations, subsurface velocity gradients and biogeochemical processes in the critical zone. References: Bandopadhyay A., T. Le Borgne, Y. Méheust and M. Dentz (2017) Enhanced reaction kinetics and reactive mixing scale dynamics in mixing fronts under shear flow for arbitrary Damkohler numbers, Adv. in Water Resour. Vol. 100, p. 78-95 Le Borgne T., T. Ginn and M. Dentz (2014) Impact of Fluid Deformation on Mixing-Induced Chemical Reactions in Heterogeneous Flows, Geophys. Res. Lett., Vol. 41, 22, p. 7898-790

A convenient enantioselective CBS-reduction of arylketones in flow-microreactor systems.

PubMed

De Angelis, Sonia; De Renzo, Maddalena; Carlucci, Claudia; Degennaro, Leonardo; Luisi, Renzo

2016-05-04

A convenient, versatile, and green CBS-asymmetric reduction of aryl and heteroaryl ketones has been developed by using the microreactor technology. The study demonstrates that it is possible to handle borane solution safely within microreactors and that the reaction performs well using 2-MeTHF as a greener solvent.

Low archaeal diversity linked to subseafloor geochemical processes at the Lost City Hydrothermal Field, Mid-Atlantic Ridge.

PubMed

Schrenk, Matthew O; Kelley, Deborah S; Bolton, Sheryl A; Baross, John A

2004-10-01

The recently discovered Lost City Hydrothermal Field (LCHF) represents a new type of submarine hydrothermal system driven primarily by exothermic serpentinization reactions in ultramafic oceanic crust. Highly reducing, alkaline hydrothermal environments at the LCHF produce considerable quantities of hydrogen, methane and organic molecules through chemo- and biosynthetic reactions. Here, we report the first analyses of microbial communities inhabiting carbonate chimneys awash in warm, high pH fluids at the LCHF and the predominance of a single group of methane-metabolizing Archaea. The predominant phylotype, related to the Methanosarcinales, formed tens of micrometre-thick biofilms in regions adjacent to hydrothermal flow. Exterior portions of active structures harboured a diverse microbial community composed primarily of filamentous Eubacteria that resembled sulphide-oxidizing species. Inactive samples, away from regions of hydrothermal flow, contained phylotypes related to pelagic microorganisms. The abundance of organisms linked to the volatile chemistry at the LCHF hints that similar metabolic processes may operate in the subseafloor. These results expand the range of known geological settings that support biological activity to include submarine hydrothermal systems that are not dependent upon magmatic heat sources.

Chemical reaction for Carreau-Yasuda nanofluid flow past a nonlinear stretching sheet considering Joule heating

NASA Astrophysics Data System (ADS)

Khan, Mair; Shahid, Amna; Malik, M. Y.; Salahuddin, T.

2018-03-01

Current analysis has been made to scrutinize the consequences of chemical response against magneto-hydrodynamic Carreau-Yasuda nanofluid flow induced by a non-linear stretching surface considering zero normal flux, slip and convective boundary conditions. Joule heating effect is also considered. Appropriate similarity approach is used to convert leading system of PDE's for Carreau-Yasuda nanofluid into nonlinear ODE's. Well known mathematical scheme namely shooting method is utilized to solve the system numerically. Physical parameters, namely Weissenberg number We , thermal slip parameter δ , thermophoresis number NT, non-linear stretching parameter n, magnetic field parameter M, velocity slip parameter k , Lewis number Le, Brownian motion parameter NB, Prandtl number Pr, Eckert number Ec and chemical reaction parameter γ upon temperature, velocity and concentration profiles are visualized through graphs and tables. Numerical influence of mass and heat transfer rates and friction factor are also represented in tabular as well as graphical form respectively. Skin friction coefficient reduces when Weissenberg number We is incremented. Rate of heat transfer enhances for large values of Brownian motion constraint NB. By increasing Lewis quantity Le rate of mass transfer declines.

Rapid identification of Yersinia pestis and Brucella melitensis by chip-based continuous flow PCR

NASA Astrophysics Data System (ADS)

Dietzsch, Michael; Hlawatsch, Nadine; Melzer, Falk; Tomaso, Herbert; Gärtner, Claudia; Neubauer, Heinrich

2012-06-01

To combat the threat of biological agents like Yersinia pestis and Brucella melitensis in bioterroristic scenarios requires fast, easy-to-use and safe identification systems. In this study we describe a system for rapid amplification of specific genetic markers for the identification of Yersinia pestis and Brucella melitensis. Using chip based PCR and continuous flow technology we were able to amplify the targets simultaneously with a 2-step reaction profile within 20 minutes. The subsequent analysis of amplified fragments by standard gel electrophoresis requires another 45 minutes. We were able to detect both pathogens within 75 minutes being much faster than most other nucleic acid amplification technologies.

Microwave treatment of dairy manure for resource recovery: Reaction kinetics and energy analysis.

PubMed

Srinivasan, Asha; Liao, Ping H; Lo, Kwang V

2016-12-01

A newly designed continuous-flow 915 MHz microwave wastewater treatment system was used to demonstrate the effectiveness of the microwave enhanced advanced oxidation process (MW/H 2 O 2 -AOP) for treating dairy manure. After the treatment, about 84% of total phosphorus and 45% of total chemical oxygen demand were solubilized with the highest H 2 O 2 dosage (0.4% H 2 O 2 per %TS). The reaction kinetics of soluble chemical oxygen demand revealed activation energy to be in the range of 5-22 kJ mole -1 . The energy required by the processes was approximately 0.16 kWh per liter of dairy manure heated. A higher H 2 O 2 dosage used in the system had a better process performance in terms of solids solubilization, reaction kinetics, and energy consumption. Cost-benefit analysis for a farm-scale MW/H 2 O 2 -AOP treatment system was also presented. The results obtained from this study would provide the basic knowledge for designing an effective farm-scale dairy manure treatment system.

Constraining Path-Dependent Processes During Basalt-CO2 Interactions with Observations From Flow-Through and Batch Experiments

NASA Astrophysics Data System (ADS)

Thomas, D.; Garing, C.; Zahasky, C.; Harrison, A. L.; Bird, D. K.; Benson, S. M.; Oelkers, E. H.; Maher, K.

2017-12-01

Predicting the timing and magnitude of CO2 storage in basaltic rocks relies partly on quantifying the dependence of reactivity on flow path and mineral distribution. Flow-through experiments that use intact cores are advantageous because the spatial heterogeneity of pore space and reactive phases is preserved. Combining aqueous geochemical analyses and petrologic characterization with non-destructive imaging techniques (e.g. micro-computed tomography) constrains the relationship between irreversible reactions, pore connectivity and accessible surface area. Our work enhances these capabilities by dynamically imaging flow through vesicular basalts with Positron Emission Tomography (PET) scanning. PET highlights the path a fluid takes by detecting photons produced during radioactive decay of an injected radiotracer (FDG). We have performed single-phase, CO2-saturated flow-through experiments with basaltic core from Iceland at CO2 sequestration conditions (50 °C; 76-90 bar Ptot). Constant flow rate and continuous pressure measurements at the inlet and outlet of the core constrain permeability. We monitor geochemical evolution through cation and anion analysis of outlet fluid sampled periodically. Before and after reaction, we perform PET scans and characterize the core using micro-CT. The PET scans indicate a discrete, localized flow path that appears to be a micro-crack connecting vesicles, suggesting that vesicle-lining minerals are immediately accessible and important reactants. Rapid increases in aqueous cation concentration, pH and HCO3- indicate that the rock reacts nearly immediately after CO2 injection. After 24 hours the solute release decreases, which may reflect a transition to reaction with phases with slower kinetic dissolution rates (e.g. zeolites and glasses to feldspar), a decrease in available reactive surface area or precipitation. We have performed batch experiments using crushed material of the same rock to elucidate the effect of flow path geometry and mineral accessibility on geochemical evolution. Interestingly, surface area-normalized dissolution rates as evinced by SiO2 release in all experiments approach similar values ( 10-15 mol/cm2/s). Our experiments show how imaging techniques are helpful in interpreting path-dependent processes in open systems.

Spatial and Temporal Scales of Surface Water-Groundwater Interactions

NASA Astrophysics Data System (ADS)

Boano, F.

2016-12-01

The interfaces between surface water and groundwater (i.e., river and lake sediments) represent hotspots for nutrient transformation in watersheds. This intense biochemical activity stems from the peculiar physicochemical properties of these interface areas. Here, the exchange of water and nutrients between surface and subsurface environments creates an ecotone region that can support the presence of different microbial species responsible for nutrient transformation. Previous studies have elucidated that water exchange between rivers and aquifers is organized in a complex system of nested flow cells. Each cell entails a range of residence timescales spanning multiple order of magnitudes, providing opportunities for different biochemical reactions to occur. Physically-bases models represent useful tools to deal with the wide range of spatial and temporal scales that characterize surface-subsurface water exchange. This contribution will present insights about how hydrodynamic processes control scale organization for surface water - groundwater interactions. The specific focus will be the influence of exchange processes on microbial activity and nutrient transformation, discussing how groundwater flow at watershed scale controls flow conditions and hence constrain microbial reactions at much smaller scales.

Metal-Organic Frameworks as Highly Active Electrocatalysts for High-Energy Density, Aqueous Zinc-Polyiodide Redox Flow Batteries.

PubMed

Li, Bin; Liu, Jian; Nie, Zimin; Wang, Wei; Reed, David; Liu, Jun; McGrail, Pete; Sprenkle, Vincent

2016-07-13

The new aqueous zinc-polyiodide redox flow battery (RFB) system with highly soluble active materials as well as ambipolar and bifunctional designs demonstrated significantly enhanced energy density, which shows great potential to reduce RFB cost. However, the poor kinetic reversibility and electrochemical activity of the redox reaction of I3(-)/I(-) couples on graphite felts (GFs) electrode can result in low energy efficiency. Two nanoporous metal-organic frameworks (MOFs), MIL-125-NH2 and UiO-66-CH3, that have high surface areas when introduced to GF surfaces accelerated the I3(-)/I(-) redox reaction. The flow cell with MOF-modified GFs serving as a positive electrode showed higher energy efficiency than the pristine GFs; increases of about 6.4% and 2.7% occurred at the current density of 30 mA/cm(2) for MIL-125-NH2 and UiO-66-CH3, respectively. Moreover, UiO-66-CH3 is more promising due to its excellent chemical stability in the weakly acidic electrolyte. This letter highlights a way for MOFs to be used in the field of RFBs.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lai, Canhai; Xu, Zhijie; Li, Tingwen

In virtual design and scale up of pilot-scale carbon capture systems, the coupled reactive multiphase flow problem must be solved to predict the adsorber’s performance and capture efficiency under various operation conditions. This paper focuses on the detailed computational fluid dynamics (CFD) modeling of a pilot-scale fluidized bed adsorber equipped with vertical cooling tubes. Multiphase Flow with Interphase eXchanges (MFiX), an open-source multiphase flow CFD solver, is used for the simulations with custom code to simulate the chemical reactions and filtered models to capture the effect of the unresolved details in the coarser mesh for simulations with reasonable simulations andmore » manageable computational effort. Previously developed two filtered models for horizontal cylinder drag, heat transfer, and reaction kinetics have been modified to derive the 2D filtered models representing vertical cylinders in the coarse-grid CFD simulations. The effects of the heat exchanger configurations (i.e., horizontal or vertical) on the adsorber’s hydrodynamics and CO2 capture performance are then examined. The simulation result subsequently is compared and contrasted with another predicted by a one-dimensional three-region process model.« less

A rapid and accurate method for determining protein content in dairy products based on asynchronous-injection alternating merging zone flow-injection spectrophotometry.

PubMed

Liang, Qin-Qin; Li, Yong-Sheng

2013-12-01

An accurate and rapid method and a system to determine protein content using asynchronous-injection alternating merging zone flow-injection spectrophotometry based on reaction between coomassie brilliant blue G250 (CBBG) and protein was established. Main merit of our approach is that it can avoid interferences of other nitric-compounds in samples, such as melamine and urea. Optimized conditions are as follows: Concentrations of CBBG, polyvinyl alcohol (PVA), NaCl and HCl are 150 mg/l, 30 mg/l, 0.1 mol/l and 1.0% (v/v), respectively; volumes of the sample and reagent are 150 μl and 30 μl, respectively; length of a reaction coil is 200 cm; total flow rate is 2.65 ml/min. The linear range of the method is 0.5-15 mg/l (BSA), its detection limit is 0.05 mg/l, relative standard deviation is less than 1.87% (n=11), and analytical speed is 60 samples per hour. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ground-water-quality assessment of the Central Oklahoma Aquifer, Oklahoma: geochemical and geohydrologic investigations

USGS Publications Warehouse

Parkhurst, David L.; Christenson, Scott C.; Breit, George N.

1993-01-01

The National Water-Quality Assessment pilot project for the Central Oklahoma aquifer examined the chemical and isotopic composition of ground water, the abundances and textures of minerals in core samples, and water levels and hydraulic properties in the flow system to identify geochemical reactions occurring in the aquifer and rates and directions of ground-water flow. The aquifer underlies 3,000 square miles of central Oklahoma and consists of Permian red beds, including parts of the Permian Garber Sandstone, Wellington Formation, and Chase, Council Grove, and Admire Groups, and Quaternary alluvium and terrace deposits.In the part of the Garber Sandstone and Wellington Formation that is not confined by the Permian Hennessey Group, calcium, magnesium, and bicarbonate are the dominant ions in ground water; in the confined part of the Garber Sandstone and Wellington Formation and in the Chase, Council Grove, and Admire Groups, sodium and bicarbonate are the dominant ions in ground water. Nearly all of the Central Oklahoma aquifer has an oxic or post-oxic environment as indicated by the large dissolved concentrations of oxygen, nitrate, arsenic(V), chromium(VI), selenium(VI), vanadium, and uranium. Sulfidic and methanic environments are virtually absent.Petrographic textures indicate dolomite, calcite, sodic plagioclase, potassium feldspars, chlorite, rock fragments, and micas are dissolving, and iron oxides, manganese oxides, kaolinite, and quartz are precipitating. Variations in the quantity of exchangeable sodium in clays indicate that cation exchange is occurring within the aquifer. Gypsum may dissolve locally within the aquifer, as indicated by ground water with large concentra-tions of sulfate, but gypsum was not observed in core samples. Rainwater is not a major source for most elements in ground water, but evapotranspiration could cause rainwater to be a significant source of potassium, sulfate, phosphate and nitrogen species. Brines derived from seawater are the most likely source of bromide and chloride in the aquifer.The dominant reaction in recharge is the uptake of carbon dioxide gas from the unsaturated zone (about 2.0 to 4.0 millimoles per liter) and the dissolution of dolomite (about 0.3 to 1.0 millimoles per liter). This reaction generates calcium, magnesium, and bicarbonate water composition. If dolomite does not dissolve to equilibrium, pH values range from 6.0 to 7.3; if dolomite dissolves to equilibrium, pH values are about 7.5. By the time recharge enters the deeper flow system, all ground water is saturated or supersaturated with dolomite and calcite.After carbonate-mineral equilibration has occurred, cation exchange of calcium and magnesium for sodium is the dominant geochemical reaction, which occurs to a substantial extent only in parts of the aquifer. Mass transfers of cation exchange greater than 2.0 millimoles per liter occur in the confined part of the Garber Sandstone and Wellington Formation and in parts of the Chase, Council Grove, and Admire Groups. Associated with cation exchange is dissolution of small quantities of dolomite, calcite, biotite, chlorite, plagioclase, or potassium feldspar, which produces pH values that range from 8.6 to 9.1.Large tritium concentrations indicate ground-water ages of less than about 40 years for most samples of recharge. Carbon-14 ages for samples from the unconfined aquifer generally are less than 10,000 years. Carbon-14 ages of ground water in the confined part of the aquifer range from about 10,000 to 30,000 years or older. These ages produce a time trend in deuterium values that qualitatively is consistent with the timing of the transition from the last glacial maximum to the present interglacial period.The most transmissive geologic units in the Central Oklahoma aquifer are the Garber Sandstone and Wellington Formation and the alluvium and terrace deposits; the Chase, Council Grove, and Admire Groups are less transmissive on the basis of available specific-capacity data. The transmissivities of the Permian geologic units depend largely on the percentage of sandstone; the percentage is greatest in the central part of the aquifer and decreases in all directions from this central part. Because of large mudstone and siltstone contents, the Hennessey Group and the Vanoss Formation are assumed to be confining units above and below the aquifer. The Cimarron and Canadian Rivers are defined to be the northern and southern extent of the aquifer because of decreases in transmissivity beyond the rivers and because there is no indication of ground-water underflow at these rivers. The eastern boundary of the aquifer is the limit of the outcrop of the Chase, Council Grove, and Admire Groups. The presence of brines in the western part of the study unit and below the aquifer indicate the extent of the freshwater flow system in these directions.Regional ground-water flow is west to east; the Deep Fork is a major discharge area for the regional flow system. Local flow systems are present within the unconfined part of the study unit. Most streams are gaining streams, and very few losing streams are evident.Median values of aquifer properties were estimated as follows: recharge to the saturated zone, 1.6 inches per year; evapotranspiration of water that never reaches the saturated zone, 25 to 30 inches per year; porosity, 0.22; storage coefficient, 0.0002; transmissivity, 260 to 450 feet squared per day; horizontal hydraulic conductivity, 4.5 feet per day; and the ratio of horizontal to vertical hydraulic conductivity, 10,000. Reported ground-water withdrawals peaked in 1985 at 13,900 million gallons but had decreased to 7,860 million gallons by 1989. Unreported domestic withdrawals were estimated to be 1,685 million gallons in 1980.The flow system in the aquifer can be considered to have three major components: (1) A shallow, local flow system in the unconfined part of the aquifer, (2) a deep, regional flow system in the unconfined part of the aquifer, and (3) a deep, regional flow system in the confined part of the aquifer. In the shallow, local flow system, water flows relatively quickly along short flowlines from the point of recharge to the point of discharge at the nearest stream. Many water samples from shallow wells contain large concentrations of tritium, which indicate ground-water ages of less than 40 years. In the deep, regional flow system in the unconfined part of the aquifer, water takes more time to flow along longer flowlines than in the shallow, local flow system. Much of the water in this flow system is recharged along ridges that correspond to ground-water divides between drainage basins. Transit times for water recharging the aquifer along ridges is greater than 5,000 years, computed using a numerical flow model in conjunction with a particle-tracking model. The deep, regional flow system in the confined part of the Garber Sandstone and Wellington Formation is recharged from a small part of the outcrop area of the Garber Sandstone. From the recharge area, water flows west under the confining unit to discharge to streams as far away as the Cimarron River. Flowpaths are relatively long, as much as 50 miles. The transit times in this flow system range from thousands to tens of thousands of years.The long-term hydrogeochemical process occurring in the Central Oklahoma aquifer is removal of unstable minerals, including dolomite, calcite, biotite, chlorite, and feldspars, and the replacement of exchangeable sodium on clays with calcium and magnesium. Over geologic time, the flux of water through the rapidly moving, local flow system has been sufficient to remove most of the dolomite, calcite, and exchangeable sodium. In places, chlorite and feldspars have been removed. In the deep, regional flow system of the unconfined part of the Garber Sandstone and Wellington Formation, the flux of water has been sufficient to remove most of the exchangeable sodium, but carbonate minerals remain sufficiently abundant to maintain dolomite and calcite equilibrium. In the confined part of the Garber Sandstone and Wellington Formation and in the less transmissive parts of the unconfined aquifer, including the Chase, Council Grove, and Admire Groups, ground-water flow is slowest, and the flux of water and extent of reaction have been insufficient to remove either the carbonate minerals or the exchangeable sodium on clays.

Using a reactive transport model to elucidate differences between laboratory and field dissolution rates in regolith

NASA Astrophysics Data System (ADS)

Moore, Joel; Lichtner, Peter C.; White, Art F.; Brantley, Susan L.

2012-09-01

The reactive transport model FLOTRAN was used to forward-model weathering profiles developed on granitic outwash alluvium over 40-3000 ka from the Merced, California (USA) chronosequence as well as deep granitic regolith developed over 800 ka near Davis Run, Virginia (USA). Baseline model predictions that used laboratory rate constants (km), measured fluid flow velocities (v), and BET volumetric surface areas for the parent material (AB,mo) were not consistent with measured profiles of plagioclase, potassium feldspar, and quartz. Reaction fronts predicted by the baseline model are deeper and thinner than the observed, consistent with faster rates of reaction in the model. Reaction front depth in the model depended mostly upon saturated versus unsaturated hydrologic flow conditions, rate constants controlling precipitation of secondary minerals, and the average fluid flow velocity (va). Unsaturated hydrologic flow conditions (relatively open with respect to CO2(g)) resulted in the prediction of deeper reaction fronts and significant differences in the separation between plagioclase and potassium feldspar reaction fronts compared to saturated hydrologic flow (relatively closed with respect to CO2(g)). Under saturated or unsaturated flow conditions, the rate constant that controls precipitation rates of secondary minerals must be reduced relative to laboratory rate constants to match observed reaction front depths and measured pore water chemistry. Additionally, to match the observed reaction front depths, va was set lower than the measured value, v, for three of the four profiles. The reaction front gradients in mineralogy and pore fluid chemistry could only be modeled accurately by adjusting values of the product kmAB,mo. By assuming km values were constrained by laboratory data, field observations were modeled successfully with TST-like rate equations by dividing measured values of AB,mo by factors from 50 to 1700. Alternately, with sigmoidal or Al-inhibition rate models, this adjustment factor ranges from 5 to 170. Best-fit models of the wetter, hydrologically saturated Davis Run profile required a smaller adjustment to AB,mo than the drier hydrologically unsaturated Merced profiles. We attributed the need for large adjustments in va and AB,mo necessary for the Merced models to more complex hydrologic flow that decreased the reactive surface area in contact with bulk flow water, e.g., dead-end pore spaces containing fluids that are near or at chemical equilibrium. Thus, rate models from the laboratory can successfully predict weathering over millions of years, but work is needed to understand how to incorporate changes in what controls the relationship between reactive surface area and hydrologic flow.

Thermally-actuated, phase change flow control for microfluidic systems.

PubMed

Chen, Zongyuan; Wang, Jing; Qian, Shizhi; Bau, Haim H

2005-11-01

An easy to implement, thermally-actuated, noninvasive method for flow control in microfluidic devices is described. This technique takes advantage of the phase change of the working liquid itself-the freezing and melting of a portion of a liquid slug-to noninvasively close and open flow passages (referred to as a phase change valve). The valve was designed for use in a miniature diagnostic system for detecting pathogens in oral fluids at the point of care. The paper describes the modeling, construction, and characteristics of the valve. The experimental results favorably agree with theoretical predictions. In addition, the paper demonstrates the use of the phase change valves for flow control, sample metering and distribution into multiple analysis paths, sealing of a polymerase chain reaction (PCR) chamber, and sample introduction into and withdrawal from a closed loop. The phase change valve is electronically addressable, does not require any moving parts, introduces only minimal dead volume, is leakage and contamination free, and is biocompatible.

Complex Wall Boundary Conditions for Modeling Combustion in Catalytic Channels

NASA Astrophysics Data System (ADS)

Zhu, Huayang; Jackson, Gregory

2000-11-01

Monolith catalytic reactors for exothermic oxidation are being used in automobile exhaust clean-up and ultra-low emissions combustion systems. The reactors present a unique coupling between mass, heat, and momentum transport in a channel flow configuration. The use of porous catalytic coatings along the channel wall presents a complex boundary condition when modeled with the two-dimensional channel flow. This current work presents a 2-D transient model for predicting the performance of catalytic combustion systems for methane oxidation on Pd catalysts. The model solves the 2-D compressible transport equations for momentum, species, and energy, which are solved with a porous washcoat model for the wall boundary conditions. A time-splitting algorithm is used to separate the stiff chemical reactions from the convective/diffusive equations for the channel flow. A detailed surface chemistry mechanism is incorporated for the catalytic wall model and is used to predict transient ignition and steady-state conversion of CH4-air flows in the catalytic reactor.

Metamorphic assemblages and the direction of flow of metamorphic fluids in four instances of serpentinization

USGS Publications Warehouse

Barnes, I.; Rapp, J.B.; O'Neil, J.R.; Sheppard, R.A.; Gude, A.J.

1972-01-01

Fluids related to Serpentinization are of at least three types. The first reported (Barnes and O'Neil, 1969) is a fluid of local meteoric origin, the chemical and thermodynamic properties of which are entirely controlled by olivine, orthopyroxene, brucite, and serpentine reactions. It is a Ca+2-OH-1 type and is shown experimentally to be capable of reacting with albite to yield calcium hydroxy silicates. Rodingites may form where the Ca+2-OH-1 type waters flow across the ultramafic contact and react with siliceous country rock. The second type of fluid has its chemical composition largely controlled before it enters the ultramafic rocks, but reactions within the ultramafic rocks fix the thermodynamic properties by reactions of orthopyroxene, olivine, calcite, brucite, and serpentine. The precipitation of brucite from this fluid clearly shows that fluid flow allows reaction products to be deposited at a distance from the point of solution. Thus, textural evidence for volume relations during Serpentinization may not be valid. The third type of fluid has its chemical properties fixed in part before the reactions with ultramafic rocks, in part by the reactions of orthopyroxene, olivine, and serpentine and in part by reactions with siliceous country rock at the contact. The reactions of the ultramafic rock and country rock with the fluid must be contemporaneous and require flow to be along the contact. This third type of fluid is grossly supersaturated with talc and tremolite, both found along the contact. The occurrence of magadiite, kenyaite, mountainite, and rhodesite along the contact is probably due to a late stage low-temperature reaction of fluids of the same thermodynamic properties as those that formed the talc and tremolite at higher temperatures. Oxygen isotope analyses of some of these minerals supports this conclusion. Rodingites form from Ca+2-rich fluids flowing across the contact; talc and tremolite form from silica-rich fluids flowing along the contact. Isotopic analyses of the fluids indicate varied origins including unaltered local meteoric water and connate water. Complexion Spring water may be a sample of only slightly altered Jurassic or Cretaceous sea water. ?? 1972 Springer-Verlag.

Frontiers in Fluid Mechanics: A Collection of Research Papers Written in Commemoration of the 65th Birthday of Stanley Corrsin.

DTIC Science & Technology

1985-04-30

analogous fashion. If the flow variable lFtis taken at x and F 6(xi,t) > d , - 1, . n, n > 1 is required, various subsets of the flow domain atare obtained...discussed: non-premixed and premixed combustion. The chemistry of combustion in the gas phase involves complex systems of reaction steps with numerous...components. In order to keep the problem tractable, only a greatly simplified and global description of chemistry will be employed. In both cases V

Process for depositing hard coating in a nozzle orifice

DOEpatents

Flynn, P.L.; Giammarise, A.W.

1991-10-29

The present invention is directed to a process for coating the interior surfaces of an orifice in a substrate that forms a slurry fuel injection nozzle. In a specific embodiment, the nozzle is part of a fuel injection system for metering a coal-water slurry into a large, medium-speed, multi-cylinder diesel engine. In order to retard erosion of the orifice, the substrate is placed in a chemical vapor deposition (CVD) reaction chamber. A reaction gas is passed into the chamber at a gas temperature below its reaction temperature and is directed through the orifice in the substrate. The gas reaction temperature is a temperature at and above which the reaction gas deposits as a coating, and the reaction gas is of a composition whereby improved resistance to erosion by flow of the particulates in the slurry fuel is imparted by the deposited coating. Only the portion of the substrate in proximity to the orifice to be coated is selectively heated to at least the gas reaction temperature for effecting coating of the orifice's interior surfaces by the vapor deposited coating formed from the reaction gas. 2 figures.

Apparatus for depositing hard coating in a nozzle orifice

DOEpatents

Flynn, P.L.; Giammarise, A.W.

1995-02-21

The present invention is directed to a process for coating the interior surfaces of an orifice in a substrate that forms a slurry fuel injection nozzle. In a specific embodiment, the nozzle is part of a fuel injection system for metering a coal-water slurry into a large, medium-speed, multi-cylinder diesel engine. In order to retard erosion of the orifice, the substrate is placed in a chemical vapor deposition (CVD) reaction chamber. A reaction gas is passed into the chamber at a gas temperature below its reaction temperature and is directed through the orifice in the substrate. The gas reaction temperature is a temperature at and above which the reaction gas deposits as a coating, and the reaction gas is of a composition whereby improved resistance to erosion by flow of the particulates in the slurry fuel is imparted by the deposited coating. Only the portion of the substrate in proximity to the orifice to be coated is selectively heated to at least the gas reaction temperature for effecting coating of the orifice`s interior surfaces by the vapor deposited coating formed from the reaction gas. 2 figs.

Apparatus for depositing hard coating in a nozzle orifice

DOEpatents

Flynn, Paul L.; Giammarise, Anthony W.

1995-01-01

The present invention is directed to a process for coating the interior surfaces of an orifice in a substrate that forms a slurry fuel injection nozzle. In a specific embodiment, the nozzle is part of a fuel injection system for metering a coal-water slurry into a large, medium-speed, multi-cylinder diesel engine. In order to retard erosion of the orifice, the substrate is placed in a chemical vapor deposition (CVD) reaction chamber. A reaction gas is passed into the chamber at a gas temperature below its reaction temperature and is directed through the orifice in the substrate. The gas reaction temperature is a temperature at and above which the reaction gas deposits as a coating, and the reaction gas is of a composition whereby improved resistance to erosion by flow of the particulates in the slurry fuel is imparted by the deposited coating. Only the portion of the substrate in proximity to the orifice to be coated is selectively heated to at least the gas reaction temperature for effecting coating of the orifice's interior surfaces by the vapor deposited coating formed from the reaction gas.

Apparatus and process for depositing hard coating in a nozzle orifice

DOEpatents

Flynn, Paul L.; Giammarise, Anthony W.

1994-01-01

The present invention is directed to a process for coating the interior surfaces of an orifice in a substrate that forms a slurry fuel injection nozzle. In a specific embodiment, the nozzle is part of a fuel injection system for metering a coal-water slurry into a large, medium-speed, multi-cylinder diesel engine. In order to retard erosion of the orifice, the substrate is placed in a chemical vapor deposition (CVD) reaction chamber. A reaction gas is passed into the chamber at a gas temperature below its reaction temperature and is directed through the orifice in the substrate. The gas reaction temperature is a temperature at and above which the reaction gas deposits as a coating, and the reaction gas is of a composition whereby improved resistance to erosion by flow of the particulates in the slurry fuel is imparted by the deposited coating. Only the portion of the substrate in proximity to the orifice to be coated is selectively heated to at least the gas reaction temperature for effecting coating of the orifice's interior surfaces by the vapor deposited coating formed from the reaction gas.

Process for depositing hard coating in a nozzle orifice

DOEpatents

Flynn, Paul L.; Giammarise, Anthony W.

1991-01-01

The present invention is directed to a process for coating the interior surfaces of an orifice in a substrate that forms a slurry fuel injection nozzle. In a specific embodiment, the nozzle is part of a fuel injection system for metering a coal-water slurry into a large, medium-speed, multi-cylinder diesel engine. In order to retard erosion of the orifice, the substrate is placed in a chemical vapor deposition (CVD) reaction chamber. A reaction gas is passed into the chamber at a gas temperature below its reaction temperature and is directed through the orifice in the substrate. The gas reaction temperature is a temperature at and above which the reaction gas deposits as a coating, and the reaction gas is of a composition whereby improved resistance toerosion by flow of the particulates in the slurry fuel is imparted by the deposited coating. Only the portion of the substrate in proximity to the orifice to be coated is selectively heated to at least the gas reaction temperature for effecting coating of the orifice's interior surfaces by the vapor deposited coating formed from the reaction gas.

Simulations of pattern dynamics for reaction-diffusion systems via SIMULINK

PubMed Central

2014-01-01

Background Investigation of the nonlinear pattern dynamics of a reaction-diffusion system almost always requires numerical solution of the system’s set of defining differential equations. Traditionally, this would be done by selecting an appropriate differential equation solver from a library of such solvers, then writing computer codes (in a programming language such as C or Matlab) to access the selected solver and display the integrated results as a function of space and time. This “code-based” approach is flexible and powerful, but requires a certain level of programming sophistication. A modern alternative is to use a graphical programming interface such as Simulink to construct a data-flow diagram by assembling and linking appropriate code blocks drawn from a library. The result is a visual representation of the inter-relationships between the state variables whose output can be made completely equivalent to the code-based solution. Results As a tutorial introduction, we first demonstrate application of the Simulink data-flow technique to the classical van der Pol nonlinear oscillator, and compare Matlab and Simulink coding approaches to solving the van der Pol ordinary differential equations. We then show how to introduce space (in one and two dimensions) by solving numerically the partial differential equations for two different reaction-diffusion systems: the well-known Brusselator chemical reactor, and a continuum model for a two-dimensional sheet of human cortex whose neurons are linked by both chemical and electrical (diffusive) synapses. We compare the relative performances of the Matlab and Simulink implementations. Conclusions The pattern simulations by Simulink are in good agreement with theoretical predictions. Compared with traditional coding approaches, the Simulink block-diagram paradigm reduces the time and programming burden required to implement a solution for reaction-diffusion systems of equations. Construction of the block-diagram does not require high-level programming skills, and the graphical interface lends itself to easy modification and use by non-experts. PMID:24725437

Miniaturization of environmental chemical assays in flowing systems: the lab-on-a-valve approach vis-à-vis lab-on-a-chip microfluidic devices.

PubMed

Miró, Manuel; Hansen, Elo Harald

2007-09-26

The analytical capabilities of the microminiaturized lab-on-a-valve (LOV) module integrated into a microsequential injection (muSI) fluidic system in terms of analytical chemical performance, microfluidic handling and on-line sample processing are compared to those of the micro total analysis systems (muTAS), also termed lab-on-a-chip (LOC). This paper illustrates, via selected representative examples, the potentials of the LOV scheme vis-à-vis LOC microdevices for environmental assays. By means of user-friendly programmable flow and the exploitation of the interplay between the thermodynamics and the kinetics of the chemical reactions at will, LOV allows accommodation of reactions which, at least at the present stage, are not feasible by application of microfluidic LOC systems. Thus, in LOV one may take full advantage of kinetic discriminations schemes, where even subtle differences in reactions are utilized for analytical purposes. Furthermore, it is also feasible to handle multi-step sequential reactions of divergent kinetics; to conduct multi-parametric determinations without manifold reconfiguration by utilization of the inherent open-architecture of the micromachined unit for implementation of peripheral modules and automated handling of a variety of reagents; and most importantly, it offers itself as a versatile front end to a plethora of detection schemes. Not the least, LOV is regarded as an emerging downscaled tool to overcome the dilemma of LOC microsystems to admit real-life samples. This is nurtured via its intrinsic flexibility for accommodation of sample pre-treatment schemes aimed at the on-line manipulation of complex samples. Thus, LOV is playing a prominent role in the environmental field, whenever the monitoring of trace level concentration of pollutants is pursued, because both matrix isolation and preconcentration of target analytes is most often imperative, or in fact necessary, prior to sample presentation to the detector.

High speed turbulent reacting flows: DNS and LES

NASA Technical Reports Server (NTRS)

Givi, Peyman

1990-01-01

Work on understanding the mechanisms of mixing and reaction in high speed turbulent reacting flows was continued. Efforts, in particular, were concentrated on taking advantage of modern computational methods to simulate high speed turbulent flows. In doing so, two methodologies were used: large eddy simulations (LES) and direct numerical simulations (DNS). In the work related with LES the objective is to study the behavior of the probability density functions (pdfs) of scalar properties within the subgrid in reacting turbulent flows. The data base obtained by DNS for a detailed study of the pdf characteristics within the subgrid was used. Simulations are performed for flows under various initializations to include the effects of compressibility on mixing and chemical reactions. In the work related with DNS, a two-dimensional temporally developing high speed mixing layer under the influence of a second-order non-equilibrium chemical reaction of the type A + B yields products + heat was considered. Simulations were performed with different magnitudes of the convective Mach numbers and with different chemical kinetic parameters for the purpose of examining the isolated effects of the compressibility and the heat released by the chemical reactions on the structure of the layer. A full compressible code was developed and utilized, so that the coupling between mixing and chemical reactions is captured in a realistic manner.

Modeling of multiphase flow with solidification and chemical reaction in materials processing

NASA Astrophysics Data System (ADS)

Wei, Jiuan

Understanding of multiphase flow and related heat transfer and chemical reactions are the keys to increase the productivity and efficiency in industrial processes. The objective of this thesis is to utilize the computational approaches to investigate the multiphase flow and its application in the materials processes, especially in the following two areas: directional solidification, and pyrolysis and synthesis. In this thesis, numerical simulations will be performed for crystal growth of several III-V and II-VI compounds. The effects of Prandtl and Grashof numbers on the axial temperature profile, the solidification interface shape, and melt flow are investigated. For the material with high Prandtl and Grashof numbers, temperature field and growth interface will be significantly influenced by melt flow, resulting in the complicated temperature distribution and curved interface shape, so it will encounter tremendous difficulty using a traditional Bridgman growth system. A new design is proposed to reduce the melt convection. The geometric configuration of top cold and bottom hot in the melt will dramatically reduce the melt convection. The new design has been employed to simulate the melt flow and heat transfer in crystal growth with large Prandtl and Grashof numbers and the design parameters have been adjusted. Over 90% of commercial solar cells are made from silicon and directional solidification system is the one of the most important method to produce multi-crystalline silicon ingots due to its tolerance to feedstock impurities and lower manufacturing cost. A numerical model is developed to simulate the silicon ingot directional solidification process. Temperature distribution and solidification interface location are presented. Heat transfer and solidification analysis are performed to determine the energy efficiency of the silicon production furnace. Possible improvements are identified. The silicon growth process is controlled by adjusting heating power and moving the side insulation layer upward. It is possible to produce high quality crystal with a good combination of heating and cooling. SiC based ceramic materials fabricated by polymer pyrolysis and synthesis becomes a promising candidate for nuclear applications. To obtain high uniformity of microstructure/concentration fuel without crack at high operating temperature, it is important to understand transport phenomena in material processing at different scale levels. In our prior work, a system level model based on reactive porous media theory was developed to account for the pyrolysis process in uranium-ceramic nuclear fabrication In this thesis, a particle level mesoscopic model based on the Smoothed Particle Hydrodynamics (SPH) is developed for modeling the synthesis of filler U3O8 particles and SiC matrix. The system-level model provides the thermal boundary conditions needed in the particle level simulation. The evolution of particle concentration and structure as well as composition of composite produced will be investigated. Since the process temperature and heat flux play the important roles in material quality and uniformity, the effects of heating rate at different directions, filler particle size and distribution on uniformity and microstructure of the final product are investigated. Uncertainty issue is also discussed. For the multiphase flow with directional solidification, a system level based on FVM is established. In this model, melt convection, temperature distribution, phase change and solidification interface can be investigated. For the multiphase flow with chemical reaction, a particle level model based on SPH method is developed to describe the pyrolysis and synthesis process of uranium-ceramic nuclear fuel. Due to its mesh-free nature, SPH can easily handle the problems with multi phases and components, large deformation, chemical reactions and even solidifications. A multi-scale meso-macroscopic approach, which combine a mesoscopic model based on SPH method and macroscopic model based on FVM, FEM and FDM, can be applied to even more complicated system. In the mesoscopic model by SPH method, some fundamental mesoscopic phenomena, such as the microstructure evolution, interface morphology represented by high resolution, particle entrapment in solidification can be studied. In the macroscopic model, the heat transfer, fluid flow, species transport can be modeled, and the simulation results provided the velocity, temperature and species boundary condition necessary for the mesoscopic model. This part falls into the region of future work. (Abstract shortened by UMI.)

Application of a Burkholderia cepacia lipase-immobilized silica monolith to batch and continuous biodiesel production with a stoichiometric mixture of methanol and crude Jatropha oil

PubMed Central

2011-01-01

Background The enzymatic production of biodiesel through alcoholysis of triglycerides has become more attractive because it shows potential in overcoming the drawbacks of chemical processes. In this study, we investigate the production of biodiesel from crude, non-edible Jatropha oil and methanol to characterize Burkholderia cepacia lipase immobilized in an n-butyl-substituted hydrophobic silica monolith. We also evaluate the performance of a lipase-immobilized silica monolith bioreactor in the continuous production of biodiesel. Results The Jatropha oil used contained 18% free fatty acids, which is problematic in a base-catalyzed process. In the lipase-catalyzed reaction, the presence of free fatty acids made the reaction mixture homogeneous and allowed bioconversion to proceed to 90% biodiesel yield after a 12 hour reaction time. The optimal molar ratio of methanol to oil was 3.3 to 3.5 parts methanol to one part oil, with water content of 0.6% (w/w). Further experiments revealed that B. cepacia lipase immobilized in hydrophobic silicates was sufficiently tolerant to methanol, and glycerol adsorbed on the support disturbed the reaction to some extent in the present reaction system. The continuous production of biodiesel was performed at steady state using a lipase-immobilized silica monolith bioreactor loaded with 1.67 g of lipase. The yield of 95% was reached at a flow rate of 0.6 mL/h, although the performance of the continuous bioreactor was somewhat below that predicted from the batch reactor. The bioreactor was operated successfully for almost 50 days with 80% retention of the initial yield. Conclusions The presence of free fatty acids originally contained in Jatropha oil improved the reaction efficiency of the biodiesel production. A combination of B. cepacia lipase and its immobilization support, n-butyl-substituted silica monolith, was effective in the production of biodiesel. This procedure is easily applicable to the design of a continuous flow-through bioreactor system. PMID:22013896

A compilation of rate parameters of water-mineral interaction kinetics for application to geochemical modeling

USGS Publications Warehouse

Palandri, James L.; Kharaka, Yousif K.

2004-01-01

Geochemical reaction path modeling is useful for rapidly assessing the extent of water-aqueous-gas interactions both in natural systems and in industrial processes. Modeling of some systems, such as those at low temperature with relatively high hydrologic flow rates, or those perturbed by the subsurface injection of industrial waste such as CO2 or H2S, must account for the relatively slow kinetics of mineral-gas-water interactions. We have therefore compiled parameters conforming to a general Arrhenius-type rate equation, for over 70 minerals, including phases from all the major classes of silicates, most carbonates, and many other non-silicates. The compiled dissolution rate constants range from -0.21 log moles m-2 s-1 for halite, to -17.44 log moles m-2 s-1 for kyanite, for conditions far from equilibrium, at 25 ?C, and pH near neutral. These data have been added to a computer code that simulates an infinitely well-stirred batch reactor, allowing computation of mass transfer as a function of time. Actual equilibration rates are expected to be much slower than those predicted by the selected computer code, primarily because actual geochemical processes commonly involve flow through porous or fractured media, wherein the development of concentration gradients in the aqueous phase near mineral surfaces, which results in decreased absolute chemical affinity and slower reaction rates. Further differences between observed and computed reaction rates may occur because of variables beyond the scope of most geochemical simulators, such as variation in grain size, aquifer heterogeneity, preferred fluid flow paths, primary and secondary mineral coatings, and secondary minerals that may lead to decreased porosity and clogged pore throats.

The effect of viscous flow and thermal flux on the rate of chemical reaction in dilute gases

NASA Astrophysics Data System (ADS)

Cukrowski, A. S.; Popielawski, J.

1986-11-01

Expression for the corrections describing the effect of viscous flow and thermal flux on the rate of chemical reaction have been derived for the reaction A + A = B + C described by Prigogine-Xhrouet and Present. These corrections are calculated for the velocity distribution function up to the second-order approximation for the Chapman-Enskog solution of the Boltzmann equation. These corrections are shown to be the same as those which would follow after application of the method of linearized-moments equations described by Eu and Li. The effects of viscous flow and thermal flux are presented as functions of activation energy of chemical reaction, temperature, density, coefficients of shear viscosity of thermal conductivity, and relevant gradients of mean molecular velocity or temperature. It is pointed out that for very slow reactions and for very large gradients (e.g. in shock waves) these effects can be quite significant.

Role of Hydrodynamic and Mineralogical Heterogeneities on Reactive Transport Processes.

NASA Astrophysics Data System (ADS)

Luquot, L.; Garcia-Rios, M.; soler Sagarra, J.; Gouze, P.; Martinez-Perez, L.; Carrera, J.

2017-12-01

Predicting reactive transport at large scale, i.e., Darcy- and field- scale, is still challenging considering the number of heterogeneities that may be present from nm- to pore-scale. It is well documented that conventional continuum-scale approaches oversimplify and/or ignore many important aspects of rock structure, chemical reactions, fluid displacement and transport, which, as a consequence, results in uncertainties when applied to field-scale operations. The changes in flow and reactive transport across the different spatial and temporal scales are of central concern in many geological applications such as groundwater systems, geo-energy, rock building heritage and geological storage... In this presentation, we will discuss some laboratory and numerical results on how local heterogeneities (structural, hydrodynamic and mineralogical) can affect the localization and the rate of the reaction processes. Different flow through laboratory experiments using various rock samples will be presented, from simple monomineral rocks such as limestone samples, and more complex rocks composed of different minerals with a large range of kinetic reactions. A new numerical approach based on multirate water mixing approach will be presented and applied to one of the laboratory experiment in order to analyze and distinguish the effect of the mineralogy distribution and the hydrodynamic heterogeneity on the total reaction rate.

Convective instability and boundary driven oscillations in a reaction-diffusion-advection model

NASA Astrophysics Data System (ADS)

Vidal-Henriquez, Estefania; Zykov, Vladimir; Bodenschatz, Eberhard; Gholami, Azam

2017-10-01

In a reaction-diffusion-advection system, with a convectively unstable regime, a perturbation creates a wave train that is advected downstream and eventually leaves the system. We show that the convective instability coexists with a local absolute instability when a fixed boundary condition upstream is imposed. This boundary induced instability acts as a continuous wave source, creating a local periodic excitation near the boundary, which initiates waves travelling both up and downstream. To confirm this, we performed analytical analysis and numerical simulations of a modified Martiel-Goldbeter reaction-diffusion model with the addition of an advection term. We provide a quantitative description of the wave packet appearing in the convectively unstable regime, which we found to be in excellent agreement with the numerical simulations. We characterize this new instability and show that in the limit of high advection speed, it is suppressed. This type of instability can be expected for reaction-diffusion systems that present both a convective instability and an excitable regime. In particular, it can be relevant to understand the signaling mechanism of the social amoeba Dictyostelium discoideum that may experience fluid flows in its natural habitat.

A PDF closure model for compressible turbulent chemically reacting flows

NASA Technical Reports Server (NTRS)

Kollmann, W.

1992-01-01

The objective of the proposed research project was the analysis of single point closures based on probability density function (pdf) and characteristic functions and the development of a prediction method for the joint velocity-scalar pdf in turbulent reacting flows. Turbulent flows of boundary layer type and stagnation point flows with and without chemical reactions were be calculated as principal applications. Pdf methods for compressible reacting flows were developed and tested in comparison with available experimental data. The research work carried in this project was concentrated on the closure of pdf equations for incompressible and compressible turbulent flows with and without chemical reactions.

Infiltration Processes and Flow Velocities Across the Landscape: When and Where is Macropore Flow Relevant?

NASA Astrophysics Data System (ADS)

Demand, D.; Blume, T.; Weiler, M.

2017-12-01

Preferential flow in macropores significantly affects the distributions of water and solutes in soil and many studies showed its relevance worldwide. Although some models include this process as a second pore domain, little is known about the spatial patterns and temporal dynamics. For example, while flow in the matrix is usually modeled and parameterized based on soil texture, an influence of texture on non-capillary flow for a given land-use class is poorly understood. To investigate the temporal and spatial dynamics on preferential flow we used a four-year soil moisture dataset from the mesoscale Attert catchment (288 km²) in Luxembourg. This dataset contains time series from 126 soil profiles in different textures and two land-use classes (forest, grassland). The soil moisture probes were installed in 10, 30 and 50 cm depth and measured in a 5-minute temporal resolution. Events were defined by a soil moisture increase higher than the instrument noise after a precipitation sum of more than 1 mm. Precipitation was measured next to the profiles so that each location could be associated to its unique precipitation characteristics. For every event and profile the soil moisture reaction was classified in sequential (ordered by depth) and non-sequential response. A non-sequential soil moisture reaction was used as an indicator of preferential flow. For sequential flow, the velocity was determined by the first reaction between two vertically adjacent sensors. The sensor reaction and wetting front velocity was analyzed in the context of precipitation characteristics and initial soil water content. Grassland sites showed a lower proportion of non-sequential flow than forest sites. For forest, non-sequential response is dependent on texture, rainfall intensity and initial water content. This is less distinct for the grassland sites. Furthermore, sequential reactions show higher flow velocities at sites, which also have high percentage of non-sequential response. In contrast, grassland sites show a more homogenous wetting front independent of soil texture. Compared against common modelling approaches of soil water flow, measured velocities show clear evidence of preferential flow, especially for forest soils. The analysis also shows that vegetation can alter the soil properties above the textural properties alone.

Self-powered enzyme micropumps

NASA Astrophysics Data System (ADS)

Sengupta, Samudra; Patra, Debabrata; Ortiz-Rivera, Isamar; Agrawal, Arjun; Shklyaev, Sergey; Dey, Krishna K.; Córdova-Figueroa, Ubaldo; Mallouk, Thomas E.; Sen, Ayusman

2014-05-01

Non-mechanical nano- and microscale pumps that function without the aid of an external power source and provide precise control over the flow rate in response to specific signals are needed for the development of new autonomous nano- and microscale systems. Here we show that surface-immobilized enzymes that are independent of adenosine triphosphate function as self-powered micropumps in the presence of their respective substrates. In the four cases studied (catalase, lipase, urease and glucose oxidase), the flow is driven by a gradient in fluid density generated by the enzymatic reaction. The pumping velocity increases with increasing substrate concentration and reaction rate. These rechargeable pumps can be triggered by the presence of specific analytes, which enables the design of enzyme-based devices that act both as sensor and pump. Finally, we show proof-of-concept enzyme-powered devices that autonomously deliver small molecules and proteins in response to specific chemical stimuli, including the release of insulin in response to glucose.

Spectrophotometric determination of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride by flow injection analysis.

PubMed

Seno, Kunihiko; Matumura, Kazuki; Oshima, Mitsuko; Motomizu, Shoji

2008-04-01

1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC.HCl) is a very useful agent to form amide bonds (peptide bonds) in an aqueous medium. A simple and fast detection system was developed using the reaction with pyridine and ethylenediamine in acidic aqueous solution and spectrophotometric flow injection analysis. The absorbances were measured at 400 nm and the reaction was accelerated at 40 degrees C. The calibration graph showed good linearity from 0 to 10% of EDC.HCl solutions: the regression equation was y=3.15x10(4)x (y, peak area; x, % concentration of EDC.HCl). The RSD was under 1.0%. Sample throughput was 15 h(-1). This method was applied to monitoring the EDC.HCl concentration that remained after the anhydration of phthalic acid in water, esterification of acetic acid in methanol or dehydration condensation of malonic acid and ethylenediamine in water.

Analytical exploration of a TiO2 nanofluid along a rotating disk with homogeneous-heterogeneous chemical reactions and non-uniform heat source/sink

NASA Astrophysics Data System (ADS)

Das, Kalidas; Chakraborty, Tanmoy; Kumar Kundu, Prabir

2017-12-01

Comparative flow features of two different nanofluids containing TiO2 nanoparticles along a rotating disk near a stagnation point are theoretically addressed here. The primary fluids are presumed as ethylene glycol and water. The influences of non-uniform heat absorption/generation with homogeneous and heterogeneous chemical reactions have been integrated to modify the energy and concentration profiles. By virtue of similarity conversions, the leading partial differential system has been standardized into non-linear ODEs and then cracked analytically by NDM and numerically by RK-4 based shooting practice. Impressions of emerging parameters on the flow regime have been reported by tables and graphs coupled with required discussions. One of our results predicts that, with the augmentation of TiO2 nanoparticles concentration, the rate of heat transport for ethylene glycol nanofluid becomes 30-36% higher compared to that of a water nanofluid.

Effect of scaled Gaussian width (SGW) on fragment flow and multifragmentation in heavy-ion collisions

NASA Astrophysics Data System (ADS)

Rajni; Kumar, Suneel

2012-02-01

We have analyzed the role of interaction range on multifragmentation within the isospin-dependent quantum molecular dynamic (IQMD) model. We find that the effect of width of Gaussian wave packet associated with a nucleon depends on the mass of the colliding system. For a given set of input parameters, we find that width has a sizable effect. At the same time, we know that a different set of parameters can influence the reaction dynamics drastically. Hence, in our opinion it may not be possible to pin down the width to a very narrow level. A systematic study of mass effect ( 197Au, 124La, 124Sn, 107Sn in the breakup of a projectile spectator at intermediate energies has been performed. We also studied the disapperance of flow which demonstrates the effect of the scaled Gaussian width (SGW). Our studies shows that SGW influences the reaction dynamics.

Modelling of reactive fluid transport in deformable porous rocks

NASA Astrophysics Data System (ADS)

Yarushina, V. M.; Podladchikov, Y. Y.

2009-04-01

One outstanding challenge in geology today is the formulation of an understanding of the interaction between rocks and fluids. Advances in such knowledge are important for a broad range of geologic settings including partial melting and subsequent migration and emplacement of a melt into upper levels of the crust, or fluid flow during regional metamorphism and metasomatism. Rock-fluid interaction involves heat and mass transfer, deformation, hydrodynamic flow, and chemical reactions, thereby necessitating its consideration as a complex process coupling several simultaneous mechanisms. Deformation, chemical reactions, and fluid flow are coupled processes. Each affects the others. Special effort is required for accurate modelling of the porosity field through time. Mechanical compaction of porous rocks is usually treated under isothermal or isoentropic simplifying assumptions. However, joint consideration of both mechanical compaction and reactive porosity alteration requires somewhat greater than usual care about thermodynamic consistency. Here we consider the modelling of multi-component, multi-phase systems, which is fundamental to the study of fluid-rock interaction. Based on the conservation laws for mass, momentum, and energy in the form adopted in the theory of mixtures, we derive a thermodynamically admissible closed system of equations describing the coupling of heat and mass transfer, chemical reactions, and fluid flow in a deformable solid matrix. Geological environments where reactive transport is important are located at different depths and accordingly have different rheologies. In the near surface, elastic or elastoplastic properties would dominate, whereas viscoplasticity would have a profound effect deeper in the lithosphere. Poorly understood rheologies of heterogeneous porous rocks are derived from well understood processes (i.e., elasticity, viscosity, plastic flow, fracturing, and their combinations) on the microscale by considering a representative volume element and subsequent averaging of microscopic constitutive laws. Micromechanical and thermodynamic modelling is performed in such a way that the consistency of the obtained rheology and thermodynamically admissible closed system of equations with the exact Gassman's relationship and Terzaghi effective stress law in the simplified case of poroelasticity is guaranteed. In such environments as subduction zones or mid-ocean ridge, metamorphic rocks exhibit a lack of chemical homogenisation. Geochemistry suggests that in order to produce chemical heterogeneity, the fluids generated during high-pressure metamorphism must have been strongly channelled. The following three major mechanisms of fluid flow focusing have been proposed: fluid flow in open fractures and two different types of flow instabilities that do not require the pre-existing fracture network. Of the latter, the first represents a purely mechanical instability of Darcian flow through the deformable porous rock while the second is reactive infiltration instability. Both mechanical and reactive instabilities are expected to occur in the mantle and should probably reinforce each other. However, little research has been done in this direction. In order to investigate how the focusing of a fluid flow occurs, how mechanical and reactive infiltration instabilities influence each other, and what their relative importance in rocks with different rheologies is, linear and non-linear stability analysis is applied to derived governing equations.

Aerodynamic Interactions of Propulsive Deceleration and Reaction Control System Jets on Mars-Entry Aeroshells

NASA Astrophysics Data System (ADS)

Alkandry, Hicham

Future missions to Mars, including sample-return and human-exploration missions, may require alternative entry, descent, and landing technologies in order to perform pinpoint landing of heavy vehicles. Two such alternatives are propulsive deceleration (PD) and reaction control systems (RCS). PD can slow the vehicle during Mars atmospheric descent by directing thrusters into the incoming freestream. RCS can provide vehicle control and steering by inducing moments using thrusters on the hack of the entry capsule. The use of these PD and RCS jets, however, involves complex flow interactions that are still not well understood. The fluid interactions induced by PD and RCS jets for Mars-entry vehicles in hypersonic freestream conditions are investigated using computational fluid dynamics (CFD). The effects of central and peripheral PD configurations using both sonic and supersonic jets at various thrust conditions are examined in this dissertation. The RCS jet is directed either parallel or transverse to the freestream flow at different thrust conditions in order to examine the effects of the thruster orientation with respect to the center of gravity of the aeroshell. The physical accuracy of the computational method is also assessed by comparing the numerical results with available experimental data. The central PD configuration decreases the drag force acting on the entry capsule due to a shielding effect that prevents mass and momentum in the hypersonic freestream from reaching the aeroshell. The peripheral PD configuration also decreases the drag force by obstructing the flow around the aeroshell and creating low surface pressure regions downstream of the PD nozzles. The Mach number of the PD jets, however, does not have a significant effect on the induced fluid interactions. The reaction control system also alters the flowfield, surface, and aerodynamic properties of the aeroshell, while the jet orientation can have a significant effect on the control effectiveness of the RCS.

Apparatus for focusing flowing gas streams

DOEpatents

Nogar, N.S.; Keller, R.A.

1985-05-20

Apparatus for focusing gas streams. The principle of hydrodynamic focusing is applied to flowing gas streams in order to provide sample concentration for improved photon and sample utilization in resonance ionization mass spectrometric analysis. In a concentric nozzle system, gas samples introduced from the inner nozzle into the converging section of the outer nozzle are focused to streams 50-250-..mu..m in diameter. In some cases diameters of approximately 100-..mu..m are maintained over distances of several centimeters downstream from the exit orifice of the outer nozzle. The sheath gas employed has been observed to further provide a protective covering around the flowing gas sample, thereby isolating the flowing gas sample from possible unwanted reactions with nearby surfaces. A single nozzle variation of the apparatus for achieving hydrodynamic focusing of gas samples is also described.

Liquid Oxygen/Liquid Methane Integrated Propulsion System Test Bed

NASA Technical Reports Server (NTRS)

Flynn, Howard; Lusby, Brian; Villemarette, Mark

2011-01-01

In support of NASA?s Propulsion and Cryogenic Advanced Development (PCAD) project, a liquid oxygen (LO2)/liquid methane (LCH4) Integrated Propulsion System Test Bed (IPSTB) was designed and advanced to the Critical Design Review (CDR) stage at the Johnson Space Center. The IPSTB?s primary objectives are to study LO2/LCH4 propulsion system steady state and transient performance, operational characteristics and to validate fluid and thermal models of a LO2/LCH4 propulsion system for use in future flight design work. Two phase thermal and dynamic fluid flow models of the IPSTB were built to predict the system performance characteristics under a variety of operating modes and to aid in the overall system design work. While at ambient temperature and simulated altitude conditions at the White Sands Test Facility, the IPSTB and its approximately 600 channels of system instrumentation would be operated to perform a variety of integrated main engine and reaction control engine hot fire tests. The pressure, temperature, and flow rate data collected during this testing would then be used to validate the analytical models of the IPSTB?s thermal and dynamic fluid flow performance. An overview of the IPSTB design and analytical model development will be presented.

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

NASA Astrophysics Data System (ADS)

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

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Luan; Tao, Franklin, E-mail: franklin.tao.2011@gmail.com; Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ studymore » of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.« less

Chemical, isotopic, and dissolved gas compositions of the hydrothermal system in Twin Falls and Jerome counties, Idaho

USGS Publications Warehouse

Mariner, R.H.; Young, H.W.; Evans, W. E.; Parliman, D.J.

1991-01-01

The chemical, isotopic, and gas compositions of the hydrothermal system in Twin Falls and Jerome counties, Idaho, change systematically as the water moves northward from the Idaho-Nevada boundary toward the Snake River. Sodium, chloride, fluoride, alkalinity, dissolved helium, and carbon-13 increase as calcium and carbon-14 decrease. Water-rock reactions may result in dissolution of plagioclase or volcanic glass and calcite, followed by precipitation of zeolites and clays. On the basis of carbon-14 age dating, apparent water ages range from 2,000 to more than 26,000 years; most apparent ages range from about 4,000 to 10,000 years. The older waters, north of the Snake River, are isotopically depleted in deuterium and are enriched in chloride relative to waters to the south. Thermal waters flowing northward beneath the Snake River may join a westward flow of older thermal water slightly north of the river. The direction of flow in the hydrothermal system seems to parallel the surface drainage.

Summer Work Experience: Determining Methane Combustion Mechanisms and Sub-Scale Diffuser Properties for Space Transporation System Engine Testing

NASA Technical Reports Server (NTRS)

Williams, Powtawche N.

1998-01-01

To assess engine performance during the testing of Space Shuttle Main Engines (SSMEs), the design of an optimal altitude diffuser is studied for future Space Transportation Systems (STS). For other Space Transportation Systems, rocket propellant using kerosene is also studied. Methane and dodecane have similar reaction schemes as kerosene, and are used to simulate kerosene combustion processes at various temperatures. The equations for the methane combustion mechanism at high temperature are given, and engine combustion is simulated on the General Aerodynamic Simulation Program (GASP). The successful design of an altitude diffuser depends on the study of a sub-scaled diffuser model tested through two-dimensional (2-D) flow-techniques. Subroutines given calculate the static temperature and pressure at each Mach number within the diffuser flow. Implementing these subroutines into program code for the properties of 2-D compressible fluid flow determines all fluid characteristics, and will be used in the development of an optimal diffuser design.

Determination of Reaction Stoichiometries by Flow Injection Analysis.

ERIC Educational Resources Information Center

Rios, Angel; And Others

1986-01-01

Describes a method of flow injection analysis intended for calculation of complex-formation and redox reaction stoichiometries based on a closed-loop configuration. The technique is suitable for use in undergraduate laboratories. Information is provided for equipment, materials, procedures, and sample results. (JM)

Flash chemistry: flow chemistry that cannot be done in batch.

PubMed

Yoshida, Jun-ichi; Takahashi, Yusuke; Nagaki, Aiichiro

2013-11-04

Flash chemistry based on high-resolution reaction time control using flow microreactors enables chemical reactions that cannot be done in batch and serves as a powerful tool for laboratory synthesis of organic compounds and for production in chemical and pharmaceutical industries.

Micro-scale thermal imaging of CO2 absorption in the thermochemical energy storage of Li metal oxides at high temperature

NASA Astrophysics Data System (ADS)

Morikawa, Junko; Takasu, Hiroki; Zamengo, Massimiliano; Kato, Yukitaka

2017-05-01

Li-Metal oxides (typical example: lithium ortho-silicate Li4SiO4) are regarded as a novel solid carbon dioxide CO2 absorbent accompanied by an exothermic reaction. At temperatures above 700°C the sorbent is regenerated with the release of the captured CO2 in an endothermic reaction. As the reaction equilibrium of this reversible chemical reaction is controllable only by the partial pressure of CO2, the system is regarded as a potential candidate for chemical heat storage at high temperatures. In this study, we applied our recent developed mobile type instrumentation of micro-scale infrared thermal imaging system to observe the heat of chemical reaction of Li4SiO4 and CO2 at temperature higher than 600°C or higher. In order to quantify the micro-scale heat transfer and heat exchange in the chemical reaction, the superimpose signal processing system is setup to determine the precise temperature. Under an ambient flow of carbon dioxide, a powder of Li4SiO4 with a diameter 50 micron started to shine caused by an exothermic chemical reaction heat above 600°C. The phenomena was accelerated with increasing temperature up to 700°C. At the same time, the reaction product lithium carbonate (Li2CO3) started to melt with endothermic phase change above 700°C, and these thermal behaviors were captured by the method of thermal imaging. The direct measurement of multiple thermal phenomena at high temperatures is significant to promote an efficient design of chemical heat storage materials. This is the first observation of the exothermic heat of the reaction of Li4SiO4 and CO2 at around 700°C by the thermal imaging method.

Modeling the Migration of Fluids in Subduction Zones

NASA Astrophysics Data System (ADS)

Wilson, C. R.; Spiegelman, M.; Van Keken, P. E.; Vrijmoed, J. C.; Hacker, B. R.

2011-12-01

Fluids play a major role in the formation of arc volcanism and the generation of continental crust. Progressive dehydration reactions in the downgoing slab release fluids to the hot overlying mantle wedge, causing flux melting and the migration of melts to the volcanic front. While the qualitative concept is well established, the quantitative details of fluid release and especially that of fluid migration and generation of hydrous melting in the wedge is still poorly understood. Here we present new models of the fluid migration through the mantle wedge for subduction zones. We use an existing set of high resolution metamorphic models (van Keken et al, 2010) to predict the regions of water release from the sediments, upper and lower crust, and upper most mantle. We use this water flux as input for the fluid migration calculation based on new finite element models built on advanced computational libraries (FEniCS/PETSc) for efficient and flexible solution of coupled multi-physics problems. The first generation of one-way coupled models solves for the evolution of porosity and fluid-pressure/flux throughout the slab and wedge given solid flow, viscosity and thermal fields from separate solutions to the incompressible Stokes and energy equations in the mantle wedge. These solutions are verified by comparing to previous benchmark studies (van Keken et al, 2008) and global suites of thermal subduction models (Syracuse et al, 2010). Fluid flow depends on both permeability and the rheology of the slab-wedge system as interaction with rheological variability can induce additional pressure gradients that affect the fluid flow pathways. These non-linearities have been shown to explain laboratory-scale observations of melt band orientation in labratory experiments and numerical simulations of melt localization in shear bands (Katz et al 2006). Our second generation of models dispense with the pre-calculation of incompressible mantle flow and fully couple the now compressible system of mantle and fluid flow equations, introducing complex feedbacks between the rheology, temperature, permeability, strain rate and porosity. Using idealized subduction zone geometries we investigate the effects of this non-linearity and explore the sensitivity of fluid flow paths for a range of fluid flow parameters with emphasis on variability of the location of the volcanic arc with respect to flow paths. We also estimate the expected degrees of hydrous melting using a variety of wet-melting parameterizations (e.g., Katz et al, 2003, Kelley et al, 2010). The current models only include dehydration reactions but work continues on the next generation of models which will include both dehydration and hydration reactions as well as parameterized flux melting in a consistent reactive-flow framework.

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

NASA Technical Reports Server (NTRS)

Chinitz, W.

1986-01-01

A computationally-viable model describing the interaction between fluid-mechanical turbulence and finite-rate combustion reactions, principally in high-speed flows was developed. Chemical kinetic mechanisms, complete and global, were developed describing the finite rate reaction of fuels of interest to NASA. These fuels included principally hydrogen and silane, although a limited amount of work involved hydrocarbon fuels as well.

A simple recirculating flow system for the calibration of polar organic chemical integrative samplers (POCIS): effect of flow rate on different water pollutants.

PubMed

Di Carro, Marina; Bono, Luca; Magi, Emanuele

2014-03-01

A calibration system for POCIS was developed and used to calculate the sampling rates of eight analytes belonging to pesticides, non-steroidal anti-inflammatory drugs and perfluorinated compounds: atrazine, propazine, terbutylazine, diclofenac, ibuprofen, ketoprofen, perfluorooctanoic acid and perfluorooctanesulfonate. Experiments with a linear velocity of 2.0, 5.1, 10.2 and 15.3 cm/s were carried out for 96 h using two different analyte concentrations. POCIS extracts were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS), using multiple reaction monitoring to maximize sensitivity. Results highlighted that the calculated sampling rates are rather constant at the considered concentrations and flow rates. Obtained values of sampling rates were then employed to calculate Time-Weighted Average concentration of the analytes in river and drinking waters. © 2013 Published by Elsevier B.V.

Photo-actuation of liquids for light-driven microfluidics: state of the art and perspectives.

PubMed

Baigl, Damien

2012-10-07

Using light to control liquid motion is a new paradigm for the actuation of microfluidic systems. We review here the different principles and strategies to induce or control liquid motion using light, which includes the use of radiation pressure, optical tweezers, light-induced wettability gradients, the thermocapillary effect, photosensitive surfactants, the chromocapillary effect, optoelectrowetting, photocontrolled electroosmotic flows and optical dielectrophoresis. We analyze the performance of these approaches to control using light many kinds of microfluidic operations involving discrete pL- to μL-sized droplets (generation, driving, mixing, reaction, sorting) or fluid flows in microchannels (valve operation, injection, pumping, flow rate control). We show that a complete toolbox is now available to control microfluidic systems by light. We finally discuss the perspectives of digital optofluidics as well as microfluidics based on all optical fluidic chips and optically reconfigurable devices.

CFD for hypersonic propulsion

NASA Technical Reports Server (NTRS)

Povinelli, Louis A.

1991-01-01

An overview is given of research activity on the application of computational fluid dynamics (CDF) for hypersonic propulsion systems. After the initial consideration of the highly integrated nature of air-breathing hypersonic engines and airframe, attention is directed toward computations carried out for the components of the engine. A generic inlet configuration is considered in order to demonstrate the highly three dimensional viscous flow behavior occurring within rectangular inlets. Reacting flow computations for simple jet injection as well as for more complex combustion chambers are then discussed in order to show the capability of viscous finite rate chemical reaction computer simulations. Finally, the nozzle flow fields are demonstrated, showing the existence of complex shear layers and shock structure in the exhaust plume. The general issues associated with code validation as well as the specific issue associated with the use of CFD for design are discussed. A prognosis for the success of CFD in the design of future propulsion systems is offered.

CFD for hypersonic propulsion

NASA Technical Reports Server (NTRS)

Povinelli, Louis A.

1990-01-01

An overview is given of research activity on the application of computational fluid dynamics (CDF) for hypersonic propulsion systems. After the initial consideration of the highly integrated nature of air-breathing hypersonic engines and airframe, attention is directed toward computations carried out for the components of the engine. A generic inlet configuration is considered in order to demonstrate the highly three dimensional viscous flow behavior occurring within rectangular inlets. Reacting flow computations for simple jet injection as well as for more complex combustion chambers are then discussed in order to show the capability of viscous finite rate chemical reaction computer simulations. Finally, the nozzle flow fields are demonstrated, showing the existence of complex shear layers and shock structure in the exhaust plume. The general issues associated with code validation as well as the specific issue associated with the use of CFD for design are discussed. A prognosis for the success of CFD in the design of future propulsion systems is offered.