Synthesis of nanoparticles from malleable and ductile metals using powder-free, reactant-assisted mechanical attrition.

PubMed

McMahon, Brandon W; Perez, Jesus Paulo L; Yu, Jiang; Boatz, Jerry A; Anderson, Scott L

2014-11-26

A reactant-assisted mechanochemical method was used to produce copious nanoparticles from malleable/ductile metals, demonstrated here for aluminum, iron, and copper. The milling media is intentionally degraded via a reactant-accelerated wear process, where the reactant aids particle production by binding to the metal surfaces, enhancing particle production, and reducing the tendency toward mechanochemical (cold) welding. The mechanism is explored by comparing the effects of different types of solvents and solvent mixtures on the amount and type of particles produced. Particles were functionalized with oleic acid to aid in particle size separation, enhance dispersion in hydrocarbon solvents, and protect the particles from oxidation. For aluminum and iron, the result is air-stable particles, but for copper, the suspended particles are found to dissolve when exposed to air. Characterization was performed using electron microscopy, dynamic light scattering, Fourier transform infrared spectroscopy, solid state nuclear magnetic resonance, and X-ray photoelectron spectroscopy. Density functional theory was used to examine the nature of carboxylic acid binding to the aluminum surface, confirming the dominance of bridging bidentate binding.

Diffusion and reactivity of ground-state nitrogen atoms N(4S) between 3 and 15 K: application to the hydrogen abstraction reaction from methane under non-energetic conditions

NASA Astrophysics Data System (ADS)

Nourry, Sendres; Krim, Lahouari

2015-07-01

We have characterized the CH4 + N(4S) reaction in solid phase, at very low temperature, under non-energetic conditions and where the CH4 and N reactants are in their ground states. A microwave-driven atomic source has been used to generate ground-state nitrogen atoms N(4S), and experiments have been carried out at temperatures as low as 3 K to reduce the mobility of the trapped species in solid phase and hence to freeze the first step of the CH4 + N reaction pathway. Leaving the formed solid sample in the dark for a while allows all trapped reactants to relax to the ground state, specifically radicals and excited species streaming from the plasma discharge. Such a method could be the only possibility of proving that the CH4 + N reaction occurs between CH4 and N reactants in their ground states without any additional energy to initiate the chemical process. The appearance of the CH3 reaction product, just by inducing the mobility of N atoms between 3 and 11 K, translates that a hydrogen abstraction reaction from methane, under non-energetic conditions, will start occurring at very low temperature. The formation of methyl radical, under these experimental conditions, is due to recombination processes N(4S)-N(4S) of ground-state nitrogen atoms without any contribution of cosmic ray particles or high-energy photons.

Mechanisms by which moisture generates cocrystals.

PubMed

Jayasankar, Adivaraha; Good, David J; Rodríguez-Hornedo, Naír

2007-01-01

The purpose of this study is to determine the mechanisms by which moisture can generate cocrystals when solid particles of cocrystal reactants are exposed to deliquescent conditions (when moisture sorption forms an aqueous solution). It is based on the hypothesis that cocrystallization behavior during water uptake can be derived from solution chemistry using models that describe cocrystal solubility and reaction crystallization of molecular complexes. Cocrystal systems were selected with active pharmaceutical ingredients (APIs) that form hydrates and include carbamazepine, caffeine, and theophylline. Moisture uptake and crystallization behavior were studied by gravimetric vapor sorption, X-ray powder diffraction, and on-line Raman spectroscopy. Results indicate that moisture uptake generates cocrystals of carbamazepine-nicotinamide, carbamazepine-saccharin, and caffeine or theophylline with dicarboxylic acid ligands (oxalic acid, maleic acid, glutaric acid, and malonic acid) when solid mixtures with cocrystal reactants deliquesce. Microscopy studies revealed that the transformation mechanism to cocrystal involves (1) moisture uptake, (2) dissolution of reactants, and (3) cocrystal nucleation and growth. Studies of solid blends of reactants in a macro scale show that the rate and extent of cocrystal formation are a function of relative humidity, moisture uptake, deliquescent material, and dissolution rates of reactants. It is shown that the interplay between moisture uptake and dissolution determines the liquid phase composition, supersaturation, and cocrystal formation rates. Differences in the behavior of deliquescent additives (sucrose and fructose) are associated with moisture uptake and composition of the deliquesced solution. Our results show that deliquescence can transform API to cocrystal or reverse the reaction given the right conditions. Key indicators of cocrystal formation and stability are (1) moisture uptake, (2) cocrystal aqueous solubility, (3) solubility and dissolution of cocrystal reactants, and (4) transition concentration.

Recent advances in solid polymer electrolyte fuel cell technology with low platinum loading electrodes

NASA Technical Reports Server (NTRS)

Srinivasan, Supramaniam; Manko, David J.; Enayatullah, Mohammad; Appleby, A. John

1989-01-01

High power density fuel cell systems for defense and civilian applications are being developed. Taking into consideration the main causes for efficiency losses (activation, mass transport and ohmic overpotentials) the only fuel cell systems capable of achieving high power densities are the ones with alkaline and solid polymer electrolyte. High power densities (0.8 W/sq cm at 0.8 V and 1 A/sq cm with H2 and O2 as reactants), were already used in NASA's Apollo and Space Shuttle flights as auxiliary power sources. Even higher power densities (4 W/sq cm - i.e., 8 A sq cm at 0.5 V) were reported by the USAF/International Fuel Cells in advanced versions of the alkaline system. High power densities (approximately 1 watt/sq cm) in solid polymer electrolyte fuel cells with ten times lower platinum loading in the electrodes (i.e., 0.4 mg/sq cm) were attained. It is now possible to reach a cell potential of 0.620 V at a current density of 2 A/sq cm and at a temperature of 95 C and pressure of 4/5 atm with H2/O2 as reactants. The slope of the linear region of the potential-current density plot for this case is 0.15 ohm-sq cm. With H2/air as reactants and under the same operating conditions, mass transport limitations are encountered at current densities above 1.4 A/sq cm. Thus, the cell potential at 1 A/sq cm with H2/air as reactants is less than that with H2/O2 as reactants by 40 mV, which is the expected value based on electrode kinetics of the oxygen reduction reaction, and at 2 A/sq cm with H2/air as reactant is less than the corresponding value with H2/O2 as reactants by 250 mV, which is due to the considerably greater mass transport limitations in the former case.

Solid Reactants for Fluorine Gas Generators

DTIC Science & Technology

1976-03-15

manager and Dr. J. D. Breaseale was the project Scientist. Significant contribut ions to this progra were made by Mr. C.1E.Fogle and M .r. Do . Matthews...CONCLUS IONS 57 BIBLIOGRAPHY 59 APPENDIX A: REACTANTS CONSIDERED LIST 63 APPENDIX B: THEORETICAL ANALYSIS OF REACTANT SYSTEM 73 APPENDIX C: X-RAY...K, while the upper Lxmit is imposed by ŝ TABLE 1. RELATIVE STABILITY OF GASEOUS SPECIES CONTAIMING FLIJORIME a Decoposit ion Species Decompostiioa

Atmospheric Transformation of Volatile Organic Compounds

DTIC Science & Technology

2008-03-01

Study Analysis Reactant mixtures and standards from product identification experiments were sampled by exposing a 100% polydimethylsiloxane solid...later using the DNPH derivatization method described above and confirmed against a commercial standard. HPLC analysis of the DNPH cartridges also...reaction mixture for a combined total photolysis time ofapproximately 50 seconds. 2.3. Kinetic Study Analysis Samples from kinetic studies were

Reaction growth of MF2/a-C (M = Ca, Mg) core/shell nanowires at the interface of vapor and solid reactants.

PubMed

Huang, Chih-Hao; Chang, Yu-Hsu; Lee, Chi-Young; Chiu, Hsin-Tien

2006-01-03

C(6)F(6) vapor is employed to react with CaC(2) and Mg(3)N(2) to grow CaF(2)/a-C and Mg(2)F(2)/a-C core/shell nanowires (tens of micrometers in length, tens to hundreds of nanometers in wire diameter, and tens of nanometers in core diameter), respectively, in high yields. The growth mechanism is proposed to proceed via a reaction at the interface of the vapor and solid reactants.

Method for silicon nitride precursor solids recovery

DOEpatents

Crosbie, Gary M.; Predmesky, Ronald L.; Nicholson, John M.

1992-12-15

Method and apparatus are provided for collecting reaction product solids entrained in a gaseous outflow from a reaction situs, wherein the gaseous outflow includes a condensable vapor. A condensate is formed of the condensable vapor on static mixer surfaces within a static mixer heat exchanger. The entrained reaction product solids are captured in the condensate which can be collected for further processing, such as return to the reaction situs. In production of silicon imide, optionally integrated into a production process for making silicon nitride caramic, wherein reactant feed gas comprising silicon halide and substantially inert carrier gas is reacted with liquid ammonia in a reaction vessel, silicon imide reaction product solids entrained in a gaseous outflow comprising residual carrier gas and vaporized ammonia can be captured by forming a condensate of the ammonia vapor on static mixer surfaces of a static mixer heat exchanger.

Hydrocarbon synthesis catalyst and method of preparation

DOEpatents

Sapienza, R.S.; Sansone, M.J.; Slegeir, W.A.R.

1983-08-02

A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint. 9 figs.

Hydrocarbon synthesis catalyst and method of preparation

DOEpatents

Sapienza, Richard S.; Sansone, Michael J.; Slegeir, William A. R.

1983-08-02

A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint.

Applying Molecular Bonding Concepts to the Solid State

NASA Astrophysics Data System (ADS)

Dunnington, Benjamin D.

In this thesis, we describe the extension and application of Natural Bond Orbital (NBO) analysis to periodic systems. This enables the translation of rigorous, quantum mechanical calculation results of solid systems into the localized lone pairs and two-center bonds of Lewis structures. Such localized bonding descriptions form the basic language of chemistry, and application of these ideas to solids allows for the understanding of complex phenomena in bulk systems using readily accessible concepts from molecular science. In addition to the algorithmic adjustments needed for to account for periodic boundary conditions in the NBO process, we also discuss methodology to interface the ubiquitous plane wave basis sets of the solid state with the atom-centered basis functions needed as input for NBO analysis. We will describe one method using projection of the plane wave eigenstates, and a second projection-free method that involves the direct calculation of matrix elements of the plane wave Hamiltonian in an atom-centered basis. The reliance of many localized, post-computational analysis techniques on an atom-centered description of the orbitals, means these interfaces will have applicability beyond our NBO development. An ideal area for application of such molecular descriptions of periodic systems is heterogeneous catalysis, where reactants from a gas/liquid phase react on a solid catalyst surface. Previous studies of these systems have originated from the delocalized perspective of the bulk catalyst. NBO provides an explicit description of the perturbative effect of the catalyst on the covalent bonds of the reactant, which is correlated with the catalytic activity of the material. Such a shift to an adsorbate focused description of surface reactivity will enable understanding of catalysis across a variety of materials.

Combustion synthesis of ceramic-metal composite materials in microgravity

NASA Technical Reports Server (NTRS)

Moore, John

1995-01-01

Combustion synthesis, self-propagating high temperature synthesis (SHS) or reactive synthesis provides an attractive alternative to conventional methods of producing advanced materials since this technology is based on the ability of highly exothermic reactions to be self sustaining and, therefore, energetically efficient. The exothermic SHS reaction is initiated at the ignition temperature, T(sub ig), and generates heat which is manifested in a maximum or combustion temperature, T(sub c), which can exceed 3000 K . Such high combustion temperatures are capable of melting and/or volatilizing reactant and product species and, therefore, present an opportunity for producing structure and property modification and control through liquid-solid, vapor-liquid-solid, and vapor-solid transformations.

Sustainability of natural attenuation of nitrate in agricultural aquifers

USGS Publications Warehouse

Green, Christopher T.; Bekins, Barbara A.

2010-01-01

Increased concentrations of nitrate in groundwater in agricultural areas, coinciding with increased use of chemical and organic fertilizers, have raised concern because of risks to environmental and human health. At some sites, these problems are mitigated by natural attenuation of nitrate as a result of microbially mediated reactions. Results from U.S. Geological Survey (USGS) research under the National Water-Quality Assessment (NAWQA) program show that reactions of dissolved nitrate with solid aquifer minerals and organic carbon help lower nitrate concentrations in groundwater beneath agricultural fields. However, increased fluxes of nitrate cause ongoing depletion of the finite pool of solid reactants. Consumption of the solid reactants diminishes the capacity of the aquifer to remove nitrate, calling into question the long-term sustainability of these natural attenuation processes.

Using Silica Sol as a Nanoglue to Prepare Nanoscale Mesoporous Composite Gel and Aerogels

DTIC Science & Technology

2000-03-31

solution-phase reactants remain unaltered. Furthermore, the composite constitutes a rigid solid architecture, such that the silica aerogel structure...nm) was immobilized in a silica aerogel structure according to the method of the present invention. The optical properties of 9 these materials...Aerogel Preparation. Acid- and base-catalyzed silica aerogels were prepared by procedures similarto those previously published in Russo et al.J.Non

Mechanochemical stabilization and sintering of nanocrystalline the (ZrO2)0.97 (Y2O3)0.03 solid solution from pure oxides

NASA Astrophysics Data System (ADS)

Rendtorff, N. M.; Suárez, G.; Sakka, Y.; Aglietti, E. F.

2011-10-01

The mechanochemical activation processing has proved to be an effective technique to enhance a solid-state reaction at relatively low temperatures. In such a process, the mechanical effects of milling, such as reduction of particle size and mixture homogenization, are accompanied by chemical effects, such as partial decomposition of salts or hydroxides resulting in very active reactants. The objective of the present work is to obtain (ZrO2)0.97(Y2O3)0.03 nanocrystalline tetragonal solid solution powders directly using a high energy milling on a mixture of the pure oxides. A second objective is to evaluate the efficiency of the processing proposed and to characterize both textural and structural evolution of the mixtures during the milling processes and throughout posterior low temperature treatments. The Textural and structural evolution were studied by XRD analysis, specific area measurements (BET) and SEM. Firstly a decrease of the crystallinity of the reactants was observed, followed by the disappearance of Y2O3 diffraction peaks and the partial appearance of the tetragonal phase at room temperature. The solid solution proportion was increased with the high energy milling time, obtaining complete stabilization of the tetragonal solid solution with long milling treatments (60 min).The obtained powders were uniaxially pressed and sintered at different temperatures (600-1400°C) the influence of the milling time was correlated with the sinterization degree and final crystalline composition of the materials. Finally, fully stabilized nanocrystalline zirconia materials were obtained satisfactorily by the proposed method.

Method of synthesizing a plurality of reactants and producing thin films of electro-optically active transition metal oxides

DOEpatents

Tracy, C.E.; Benson, D.K.; Ruth, M.R.

1985-08-16

A method of synthesizing a plurality of reactants by inducing a reaction by plasma deposition among the reactants. The plasma reaction is effective for consolidating the reactants and producing thin films of electro-optically active transition metal oxides.

Apparatus for silicon nitride precursor solids recovery

DOEpatents

Crosbie, Gary M.; Predmesky, Ronald L.; Nicholson, John M.

1995-04-04

Method and apparatus are provided for collecting reaction product solids entrained in a gaseous outflow from a reaction situs, wherein the gaseous outflow includes a condensable vapor. A condensate is formed of the condensable vapor on static mixer surfaces within a static mixer heat exchanger. The entrained reaction product solids are captured in the condensate which can be collected for further processing, such as return to the reaction situs. In production of silicon imide, optionally integrated into a production process for making silicon nitride caramic, wherein reactant feed gas comprising silicon halide and substantially inert carrier gas is reacted with liquid ammonia in a reaction vessel, silicon imide reaction product solids entrained in a gaseous outflow comprising residual carrier gas and vaporized ammonia can be captured by forming a condensate of the ammonia vapor on static mixer surfaces of a static mixer heat exchanger.

Bipolar plate/diffuser for a proton exchange membrane fuel cell

DOEpatents

Besmann, Theodore M.; Burchell, Timothy D.

2001-01-01

A combination bipolar plate/diffuser fuel cell component includes an electrically conducting solid material having: a porous region having a porous surface; and a hermetic region, the hermetic region defining at least a portion of at least one coolant channel, the porous region defining at least a portion of at least one reactant channel, the porous region defining a flow field medium for diffusing the reactant to the porous surface.

Bipolar plate/diffuser for a proton exchange membrane fuel cell

DOEpatents

Besmann, Theodore M.; Burchell, Timothy D.

2000-01-01

A combination bipolar plate/diffuser fuel cell component includes an electrically conducting solid material having: a porous region having a porous surface; and a hermetic region, the hermetic region defining at least a portion of at least one coolant channel, the porous region defining at least a portion of at least one reactant channel, the porous region defining a flow field medium for diffusing the reactant to the porous surface.

Method of synthesizing a plurality of reactants and producing thin films of electro-optically active transition metal oxides

DOEpatents

Tracy, C. Edwin; Benson, David K.; Ruth, Marta R.

1987-01-01

A method of synthesizing electro-optically active reaction products from a plurality of reactants by inducing a reaction by plasma deposition among the reactants. The plasma reaction is effective for consolidating the reactants and producing thin films of electro-optically active transition metal oxides.

Advancing polymers of intrinsic microporosity by mechanochemistry

DOE PAGES

Zhang, Pengfei; Jiang, Xueguang; Wan, Shun; ...

2015-02-20

Herein, we report a fast (15 min) and solvent-free mechanochemical approach to construct polymers of intrinsic microporosity (PIMs) with high molecular mass and low polydispersity by solid grinding. The enhanced reaction efficiency results from the instantaneous frictional heating and continuous exposure of active sites within those solid reactants.

Separation Method for Oxygen Mass Transport Coefficient in Two Phase Porous Air Electrodes - Transport in Gas and Solid Polymer or Liquid Electrolyte Phases

DTIC Science & Technology

2013-08-06

of the problem studied Proton exchange membrane fuel cells ( PEMFCs ) are the most promising candidate systems for alternative electricity...characteristic. The limiting current can be used as a tool to study mass transport phenomena in PEMFC because it can provide experimental data for the...coefficient for PEMFCs under in situ conditions based on the galvanostatic discharge of a cell with an interrupted reactant supply. The results indicated

Small-Sized Mg–Al LDH Nanosheets Supported on Silica Aerogel with Large Pore Channels: Textural Properties and Basic Catalytic Performance after Activation

PubMed Central

Wang, Yusen; Wang, Xiaoxia; Feng, Xiaolan; Ye, Xiao; Fu, Jie

2018-01-01

Layered double hydroxides (LDHs) have been widely used as an important subset of solid base catalysts. However, developing low-cost, small-sized LDH nanoparticles with enhanced surface catalytic sites remains a challenge. In this work, silica aerogel (SA)-supported, small-sized Mg–Al LDH nanosheets were successfully prepared by one-pot coprecipitation of Mg and Al ions in an alkaline suspension of crushed silica aerogel. The supported LDH nanosheets were uniformly dispersed in the SA substrate with the smallest average radial diameter of 19.2 nm and the thinnest average thickness of 3.2 nm, both dimensions being significantly less than those of the vast majority of LDH nanoparticles reported. The SA/LDH composites also showed large pore volume (up to 1.3 cm3·g) and pore diameter (>9 nm), and therefore allow efficient access of reactants to the edge catalytic sites of LDH nanosheets. In a base-catalyzed Henry reaction of benzaldehyde with nitromethane, the SA/LDH catalysts showed high reactant conversions and favorable stability in 6 successive cycles of reactions. The low cost of the SA carrier and LDH precursors, easy preparation method, and excellent catalytic properties make these SA/LDH composites a competitive example of solid-base catalysts. PMID:29462941

Small-Sized Mg-Al LDH Nanosheets Supported on Silica Aerogel with Large Pore Channels: Textural Properties and Basic Catalytic Performance after Activation.

PubMed

Wang, Lijun; Wang, Yusen; Wang, Xiaoxia; Feng, Xiaolan; Ye, Xiao; Fu, Jie

2018-02-16

Layered double hydroxides (LDHs) have been widely used as an important subset of solid base catalysts. However, developing low-cost, small-sized LDH nanoparticles with enhanced surface catalytic sites remains a challenge. In this work, silica aerogel (SA)-supported, small-sized Mg-Al LDH nanosheets were successfully prepared by one-pot coprecipitation of Mg and Al ions in an alkaline suspension of crushed silica aerogel. The supported LDH nanosheets were uniformly dispersed in the SA substrate with the smallest average radial diameter of 19.2 nm and the thinnest average thickness of 3.2 nm, both dimensions being significantly less than those of the vast majority of LDH nanoparticles reported. The SA/LDH composites also showed large pore volume (up to 1.3 cm3·g) and pore diameter (>9 nm), and therefore allow efficient access of reactants to the edge catalytic sites of LDH nanosheets. In a base-catalyzed Henry reaction of benzaldehyde with nitromethane, the SA/LDH catalysts showed high reactant conversions and favorable stability in 6 successive cycles of reactions. The low cost of the SA carrier and LDH precursors, easy preparation method, and excellent catalytic properties make these SA/LDH composites a competitive example of solid-base catalysts.

Method for selective detection of explosives in mass spectrometer or ion mobility spectrometer at parts-per-quadrillion level

DOEpatents

Ewing, Robert G.; Atkinson, David A.; Clowers, Brian H.

2015-09-01

A method for selective detection of volatile and non-volatile explosives in a mass spectrometer or ion mobility spectrometer at a parts-per-quadrillion level without preconcentration is disclosed. The method comprises the steps of ionizing a carrier gas with an ionization source to form reactant ions or reactant adduct ions comprising nitrate ions (NO.sub.3.sup.-); selectively reacting the reactant ions or reactant adduct ions with at least one volatile or non-volatile explosive analyte at a carrier gas pressure of at least about 100 Ton in a reaction region disposed between the ionization source and an ion detector, the reaction region having a length which provides a residence time (tr) for reactant ions therein of at least about 0.10 seconds, wherein the selective reaction yields product ions comprising reactant ions or reactant adduct ions that are selectively bound to the at least one explosive analyte when present therein; and detecting product ions with the ion detector to determine presence or absence of the at least one explosive analyte.

Method of winning aluminum metal from aluminous ore

DOEpatents

Loutfy, Raouf O.; Keller, Rudolf; Yao, Neng-Ping

1981-01-01

Aluminous ore such as bauxite containing alumina is blended with coke or other suitable form of carbon and reacted with sulfur gas at an elevated temperature. For handling, the ore and coke can be extruded into conveniently sized pellets. The reaction with sulfur gas produces molten aluminum sulfide which is separated from residual solid reactants and impurities. The aluminum sulfide is further increased in temperature to cause its decomposition or sublimation, yielding aluminum subsulfide liquid (AlS) and sulfur gas that is recycled. The aluminum monosulfide is then cooled to below its disproportionation temperature to again form molten aluminum sulfide and aluminum metal. A liquid-liquid or liquid-solid separation, depending on the separation temperature, provides product aluminum and aluminum sulfide for recycle to the disproportionation step.

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.

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.

Apparatus and method for depositing coating onto porous substrate

DOEpatents

Isenberg, Arnold O.; Zymboly, Gregory E.

1986-01-01

Disclosed is an apparatus for forming a chemically vapor deposited coating on a porous substrate where oxygen from a first gaseous reactant containing a source of oxygen permeates through the pores of the substrate to react with a second gaseous reactant that is present on the other side of the substrate. The apparatus includes means for controlling the pressure and flow rate of each gaseous reactant, a manometer for measuring the difference in pressure between the gaseous reactants on each side of the substrate, and means for changing the difference in pressure between the gaseous reactants. Also disclosed is a method of detecting and closing cracks in the coating by reducing the pressure difference between the two gaseous reactants whenever the pressure difference falls suddenly after gradually rising, then again increasing the pressure difference on the two gases. The attack by the by-products of the reaction on the substrate are reduced by maintaining the flow rate of the first reactant through the pores of the substrate.

Ion mobility spectrometer, spectrometer analyte detection and identification verification system, and method

DOEpatents

Atkinson, David A.

2002-01-01

Methods and apparatus for ion mobility spectrometry and analyte detection and identification verification system are disclosed. The apparatus is configured to be used in an ion mobility spectrometer and includes a plurality of reactant reservoirs configured to contain a plurality of reactants which can be reacted with the sample to form adducts having varying ion mobilities. A carrier fluid, such as air or nitrogen, is used to carry the sample into the spectrometer. The plurality of reactants are configured to be selectively added to the carrier stream by use inlet and outlet manifolds in communication with the reagent reservoirs, the reservoirs being selectively isolatable by valves. The invention further includes a spectrometer having the reagent system described. In the method, a first reactant is used with the sample. Following a positive result, a second reactant is used to determine whether a predicted response occurs. The occurrence of the second predicted response tends to verify the existence of a component of interest within the sample. A third reactant can also be used to provide further verification of the existence of a component of interest. A library can be established of known responses of compounds of interest with various reactants and the results of a specific multi-reactant survey of a sample can be compared against the library to determine whether a component detected in the sample is likely to be a specific component of interest.

Process for producing high purity silicon nitride by the direct reaction between elemental silicon and nitrogen-hydrogen liquid reactants

DOEpatents

Pugar, Eloise A.; Morgan, Peter E. D.

1990-01-01

A process is disclosed for producing, at a low temperature, a high purity reaction product consisting essentially of silicon, nitrogen, and hydrogen which can then be heated to produce a high purity alpha silicon nitride. The process comprises: reacting together a particulate elemental high purity silicon with a high purity nitrogen-hydrogen reactant in its liquid state (such as ammonia or hydrazine) having the formula: N.sub.n H.sub.(n+m) wherein: n=1-4 and m=2 when the nitrogen-hydrogen reactant is straight chain, and 0 when the nitrogen-hydrogen reactant is cyclic. High purity silicon nitride can be formed from this intermediate product by heating the intermediate product at a temperature of from about 1200.degree.-1700.degree. C. for a period from about 15 minutes up to about 2 hours to form a high purity alpha silicon nitride product. The discovery of the existence of a soluble Si-N-H intermediate enables chemical pathways to be explored previously unavailable in conventional solid state approaches to silicon-nitrogen ceramics.

Process for producing high purity silicon nitride by the direct reaction between elemental silicon and nitrogen-hydrogen liquid reactants

DOEpatents

Pugar, E.A.; Morgan, P.E.D.

1987-09-15

A process is disclosed for producing, at a low temperature, a high purity reaction product consisting essentially of silicon, nitrogen, and hydrogen which can then be heated to produce a high purity alpha silicon nitride. The process comprises: reacting together a particulate elemental high purity silicon with a high purity nitrogen-hydrogen reactant in its liquid state (such as ammonia or hydrazine) having the formula: N/sub n/H/sub (n+m)/ wherein: n = 1--4 and m = 2 when the nitrogen-hydrogen reactant is straight chain, and 0 when the nitrogen-hydrogen reactant is cyclic. High purity silicon nitride can be formed from this intermediate product by heating the intermediate product at a temperature of from about 1200--1700/degree/C for a period from about 15 minutes up to about 2 hours to form a high purity alpha silicon nitride product. The discovery of the existence of a soluble Si/endash/N/endash/H intermediate enables chemical pathways to be explored previously unavailable in conventional solid-state approaches to silicon-nitrogen ceramics

Chapter 28: Nanomaterials for Energy Applications

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

Hurst, Katherine E; Luther, Joseph M; Ban, Chunmei

2017-01-02

A wide variety of nanomaterials have been applied to energy related applications, including nanofibers, nanocrystalline materials, nanoparticles, and thin film nanocoatings. Solid-state lighting offers significant advantages in energy efficiency compared to traditional lighting technologies. The potential for nanostructured solid-state lighting devices is excellent as it enjoys significant economic drivers in energy efficiency. Fuel cells convert chemical energy to electrical energy through electrochemical reactions at an anode and cathode. The conversion of biomass to fuels and chemicals offers great potential to reduce energy dependence on petroleum and reduce green house gas emissions. Batteries involve the production and storage of electrical charge,more » the transfer of cations and electrical current, each based on electrochemical reactions and chemical reactants. Battery performance relies on the complex processes and factors that affect the transport of charge in the reactants, and across the interface between the chemical phases.« less

Laser-driven fusion etching process

DOEpatents

Ashby, Carol I. H.; Brannon, Paul J.; Gerardo, James B.

1989-01-01

The surfaces of solid ionic substrates are etched by a radiation-driven chemical reaction. The process involves exposing an ionic substrate coated with a layer of a reactant material on its surface to radiation, e.g. a laser, to induce localized melting of the substrate which results in the occurrance of a fusion reaction between the substrate and coating material. The resultant reaction product and excess reactant salt are then removed from the surface of the substrate with a solvent which is relatively inert towards the substrate. The laser-driven chemical etching process is especially suitable for etching ionic salt substrates, e.g., a solid inorganic salt such as LiNbO.sub.3, such as used in electro-optical/acousto-optic devices. It is also suitable for applications wherein the etching process is required to produce an etched ionic substrate having a smooth surface morphology or when a very rapid etching rate is desired.

Cyclodextrin inclusion complex formation and solid-state characterization of the natural antioxidants alpha-tocopherol and quercetin.

PubMed

Koontz, John L; Marcy, Joseph E; O'Keefe, Sean F; Duncan, Susan E

2009-02-25

Cyclodextrin (CD) complexation procedures are relatively simple processes, but these techniques often require very specific conditions for each individual guest molecule. Variations of the coprecipitation from aqueous solution technique were optimized for the CD complexation of the natural antioxidants alpha-tocopherol and quercetin. Solid inclusion complex products of alpha-tocopherol/beta-CD and quercetin/gamma-CD had molar ratios of 1.7:1, which were equivalent to 18.1% (w/w) alpha-tocopherol and 13.0% (w/w) quercetin. The molar reactant ratios of CD/antioxidant were optimized at 8:1 to improve the yield of complexation. The product yields of alpha-tocopherol/beta-CD and quercetin/gamma-CD complexes from their individual reactants were calculated as 24 and 21% (w/w), respectively. ATR/FT-IR, 13C CP/MAS NMR, TGA, and DSC provided evidence of antioxidant interaction with CD at the molecular level, which indicated true CD inclusion complexation in the solid state. Natural antioxidant/CD inclusion complexes may serve as novel additives in controlled-release active packaging to extend the oxidative stability of foods.

Formation of sodium bismuth titanate-barium titanate during solid-state synthesis

DOE PAGES

Hou, Dong; Aksel, Elena; Fancher, Chris M.; ...

2017-01-12

Phase formation of sodium bismuth titanate (Na 0.5Bi 0.5TiO 3 or NBT) and its solid solution with barium titanate (BaTiO 3 or BT) during the calcination process is studied using in situ high-temperature diffraction. The reactant powders were mixed and heated to 1000°C, while X-ray diffraction patterns were recorded continuously. Phase evolutions from starting materials to final perovskite products are observed, and different transient phases are identified. The formation mechanism of NBT and NBT–xBT perovskite structures is discussed, and a reaction sequence is suggested based on the observations. The in situ study leads to a new processing approach, which ismore » the use of nano-TiO 2, and gives insights to the particle size effect for solid-state synthesis products. Lastly, it was found that the use of nano-TiO 2 as reactant powder accelerates the synthesis process, decreases the formation of transient phases, and helps to obtain phase-pure products using a lower thermal budget.« less

Method of winning aluminum metal from aluminous ore

DOEpatents

Loutfy, R.O.; Keller, R.; Yao, N.P.

Aluminous ore such as bauxite containing alumina is blended with coke or other suitable form of carbon and reacted with sulfur gas at an elevated temperature. For handling, the ore and coke can be extruded into conveniently sized pellets. The reaction with sulfur gas produces molten aluminum sulfide which is separated from residual solid reactants and impurities. The aluminum sulfide is further increased in temperature to cause its decomposition or sublimation, yielding aluminum subsulfide liquid (A1S) and sulfur gas that is recycled. The aluminum monosulfide is then cooled to below its disproportionation temperature to again form molten aluminum sulfide and aluminum metal. A liquid-liquid or liquid-solid separation, depending on the separation temperature, provides product aluminum and aluminum sulfide for recycle to the disproportionation step.

STRUCTURAL DYNAMICS OF METAL PARTITIONING TO MINERAL SURFACES

EPA Science Inventory

The conceptual understanding of surface complexation reactions that control trace element partitioning to mineral surfaces is limited by the assumption that the solid reactant possesses a finite, time-invariant population of surface functional groups. This assumption has limited...

Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction.

PubMed

Zhu, Di; Zhang, Linghong; Ruther, Rose E; Hamers, Robert J

2013-09-01

The photocatalytic reduction of N₂ to NH₃ is typically hampered by poor binding of N₂ to catalytic materials and by the very high energy of the intermediates involved in this reaction. Solvated electrons directly introduced into the reactant solution can provide an alternative pathway to overcome such limitations. Here we demonstrate that illuminated hydrogen-terminated diamond yields facile electron emission into water, thus inducing reduction of N₂ to NH₃ at ambient temperature and pressure. Transient absorption measurements at 632 nm reveal the presence of solvated electrons adjacent to the diamond after photoexcitation. Experiments using inexpensive synthetic diamond samples and diamond powder show that photocatalytic activity is strongly dependent on the surface termination and correlates with the production of solvated electrons. The use of diamond to eject electrons into a reactant liquid represents a new paradigm for photocatalytic reduction, bringing electrons directly to reactants without requiring molecular adsorption to the surface.

High temperature solid oxide regenerative fuel cell for solar photovoltaic energy storage

NASA Technical Reports Server (NTRS)

Bents, David J.

1987-01-01

A hydrogen-oxygen regenerative fuel cell (RFC) energy storage system based on high temperature solid oxide fuel cell (SOFC) technology is described. The reactants are stored as gases in lightweight insulated pressure vessels. The product water is stored as a liquid in saturated equilibrium with the fuel gas. The system functions as a secondary battery and is applicable to darkside energy storage for solar photovoltaics.

Kinetics of struvite to newberyite transformation in the precipitation system MgCl2-NH4H2PO4NaOH-H2O.

PubMed

Babić-Ivancić, Vesna; Kontrec, Jasminka; Brecević, Ljerka; Kralj, Damir

2006-10-01

The influence of the initial reactant concentrations on the composition of the solid phases formed in the precipitation system MgCl(2)-NH(4)H(2)PO(4)-NaOH-H(2)O was investigated. The precipitation diagram constructed shows the approximate concentration regions within which struvite, newberyite, and their mixtures exist at 25 degrees C and an aging time of 60 min. It was found that immediately after mixing the reactant solutions, struvite (MgNH(4)PO(4).6H(2)O) precipitated in nearly the whole concentration area, while newberyite (MgHPO(4).3H(2)O) appeared mostly within the region of the excess of magnesium concentration. It was also found that after aging time of 60 min the precipitation domain of struvite alone is much broader than that of newberyite or the domain of their coexistence, and shows that struvite is more abundant in the systems in which the initial concentration of ammonium phosphate is higher than that of magnesium. The kinetics of struvite to newberyite transformation (conversion) was systematically studied under the conditions of different initial reactant concentrations and different initial pH in the systems in which a mixture of both phases precipitated spontaneously. The struvite to newberyite conversion period was found to be strongly related to the ratio of initial supersaturations, S(N)/S(S), rather than to the any particular physical quantity that can describe and predict the behavior of the precipitation system. Experimental data suggest a solution-mediated process as a most possible transformation mechanism. Along with a continuous monitoring of the changes in the liquid phase, the content of struvite in the solid phase was estimated by means of a Fourier transform infrared (FT-IR) method, developed for this particular precipitation system.

Method for forming H2-permselective oxide membranes

DOEpatents

Gavalas, George R.; Nam, Suk Woo; Tsapatsis, Michael; Kim, Soojin

1995-01-01

Methods of forming permselective oxide membranes that are highly selective to permeation of hydrogen by chemical deposition of reactants in the pore of porous tubes, such as Vycor.TM. glass or Al.sub.2 O.sub.3 tubes. The porous tubes have pores extending through the tube wall. The process involves forming a stream containing a first reactant of the formula RX.sub.n, wherein R is silicon, titanium, boron or aluminum, X is chlorine, bromine or iodine, and n is a number which is equal to the valence of R; and forming another stream containing water vapor as the second reactant. Both of the reactant streams are passed along either the outside or the inside surface of a porous tube and the streams react in the pores of the porous tube to form a nonporous layer of R-oxide in the pores. The membranes are formed by the hydrolysis of the respective halides. In another embodiment, the first reactant stream contains a first reactant having the formula SiH.sub.n Cl.sub.4-n where n is 1, 2 or 3; and the second reactant stream contains water vapor and oxygen. In still another embodiment the first reactant stream containing a first reactant selected from the group consisting of Cl.sub.3 SiOSiCl.sub.3, Cl.sub.3 SiOSiCl.sub.2 OSiCl.sub.3, and mixtures thereof and the second reactant stream contains water vapor. In still another embodiment, membrane formation is carried out by an alternating flow deposition method. This involves a sequence of cycles, each cycle comprising introduction of the halide-containing stream and allowance of a specific time for reaction followed by purge and flow of the water vapor containing stream for a specific length of time. In all embodiments the nonporous layers formed are selectively permeable to hydrogen.

Method for forming H2-permselective oxide membranes

DOEpatents

Gavalas, G.R.; Nam, S.W.; Tsapatsis, M.; Kim, S.

1995-09-26

Methods are disclosed for forming permselective oxide membranes that are highly selective to permeation of hydrogen by chemical deposition of reactants in the pore of porous tubes, such as Vycor{trademark} glass or Al{sub 2}O{sub 3} tubes. The porous tubes have pores extending through the tube wall. The process involves forming a stream containing a first reactant of the formula RX{sub n}, wherein R is silicon, titanium, boron or aluminum, X is chlorine, bromine or iodine, and n is a number which is equal to the valence of R; and forming another stream containing water vapor as the second reactant. Both of the reactant streams are passed along either the outside or the inside surface of a porous tube and the streams react in the pores of the porous tube to form a nonporous layer of R-oxide in the pores. The membranes are formed by the hydrolysis of the respective halides. In another embodiment, the first reactant stream contains a first reactant having the formula SiH{sub n}Cl{sub 4{minus}n} where n is 1, 2 or 3; and the second reactant stream contains water vapor and oxygen. In still another embodiment the first reactant stream containing a first reactant selected from the group consisting of Cl{sub 3}SiOSiCl{sub 3}, Cl{sub 3}SiOSiCl{sub 2}OSiCl{sub 3}, and mixtures thereof and the second reactant stream contains water vapor. In still another embodiment, membrane formation is carried out by an alternating flow deposition method. This involves a sequence of cycles, each cycle comprising introduction of the halide-containing stream and allowance of a specific time for reaction followed by purge and flow of the water vapor containing stream for a specific length of time. In all embodiments the nonporous layers formed are selectively permeable to hydrogen. 11 figs.

Fuel cell generator

DOEpatents

Isenberg, Arnold O.

1983-01-01

High temperature solid oxide electrolyte fuel cell generators which allow controlled leakage among plural chambers in a sealed housing. Depleted oxidant and fuel are directly reacted in one chamber to combust remaining fuel and preheat incoming reactants. The cells are preferably electrically arranged in a series-parallel configuration.

Fuel cell generator

DOEpatents

Makiel, Joseph M.

1985-01-01

A high temperature solid electrolyte fuel cell generator comprising a housing means defining a plurality of chambers including a generator chamber and a combustion products chamber, a porous barrier separating the generator and combustion product chambers, a plurality of elongated annular fuel cells each having a closed end and an open end with the open ends disposed within the combustion product chamber, the cells extending from the open end through the porous barrier and into the generator chamber, a conduit for each cell, each conduit extending into a portion of each cell disposed within the generator chamber, each conduit having means for discharging a first gaseous reactant within each fuel cell, exhaust means for exhausting the combustion product chamber, manifolding means for supplying the first gaseous reactant to the conduits with the manifolding means disposed within the combustion product chamber between the porous barrier and the exhaust means and the manifolding means further comprising support and bypass means for providing support of the manifolding means within the housing while allowing combustion products from the first and a second gaseous reactant to flow past the manifolding means to the exhaust means, and means for flowing the second gaseous reactant into the generator chamber.

Magnetic solid base catalyst CaO/CoFe2O4 for biodiesel production: Influence of basicity and wettability of the catalyst in catalytic performance

NASA Astrophysics Data System (ADS)

Zhang, Pingbo; Han, Qiuju; Fan, Mingming; Jiang, Pingping

2014-10-01

A novel magnetic solid base catalyst CaO/CoFe2O4 was successfully prepared with CoFe2O4 synthesized by hydrothermal method as the magnetic core and applied to the transesterification of soybean oil for the production of biodiesel. The magnetic solid base catalysts were characterized by a series of techniques including CO2-TPD, powder XRD, TGA, TEM and the contact angle measurement of the water droplet. It was demonstrated that CaO/CoFe2O4 has stronger magnetic strength indicating perfect utility for repeated use and better basic strength. Compared with CaO/ZnFe2O4 and CaO/MnFe2O4, solid base catalyst CaO/CoFe2O4 has better catalytic performance, weaker hydroscopicity and stronger wettability, demonstrating that catalytic performance was relative to both basicity of catalyst and the full contact between the catalyst and the reactants, but the latter was a main factor in the catalytic system.

Mathematical Modeling and Optimization Studies on Development of Fuel Cells for Multifarious Applications

DTIC Science & Technology

2010-05-12

multicomponent steady-state model for liquid -feed solid polymer electrolyte DBFCs. These fuel cells use sodium borohydride (NaBH4) in alkaline media...layers, diffusion layers and the polymer electrolyte membrane for a liquid feed DBFC. Diffusion of reactants within and between the pores is accounted...projected for futuristic portable applications. In this project we developed a three- dimensional, multicomponent steady-state model for liquid -feed solid

A new chemical route to a hybrid nanostructure: room-temperature solid-state reaction synthesis of Ag@AgCl with efficient photocatalysis.

PubMed

Hu, Pengfei; Cao, Yali

2012-08-07

The room-temperature solid-state chemical reaction technique has been used to synthesize the silver nanoparticle-loaded semiconductor silver@silver chloride for the first time. It has the advantages of convenient operation, lower cost, less pollution, and mass production. This simple technique created a wide array of nanosized silver particles which had a strong surface plasmon resonance effect in the visible region, and built up an excellent composite structure of silver@silver chloride hybrid which exhibited high photocatalytic activity and stability towards decomposition of organic methyl orange under visible-light illumination. Moreover, this work achieved the control of composition of the silver@silver chloride composite simply by adjusting the feed ratio of reactants. It offers an alternative method for synthesising metal@semiconductor composites.

Chemical stability of amorphous materials: specific and general media effects in the role of water in the degradation of freeze-dried zoniporide.

PubMed

Luthra, Suman A; Shalaev, Evgenyi Y; Medek, Ales; Hong, Jinyang; Pikal, Michael J

2012-09-01

The objective of the present work was to determine whether hydrolysis in a model lyophile was influenced by general media effects with water-changing properties of the medium or via a specific mechanism of water as a reactant. Four formulations of zoniporide and sucrose (1:10) were prepared with variable amounts of sorbitol [0%-25% (w/v) of total solids). These formulations were then equilibrated at 6% and 11% relative humidity using saturated salt solutions. The lyophile cakes were analyzed by differential scanning calorimetery (DSC), (isothermal microcalorimetry (IMC), solid- state nuclear magnetic resonance (ssNMR) spectroscopy, and ultraviolet-visible diffuse reflectance (DFR) spectroscopy. DSC and IMC were used to assess the global molecular mobility. ssNMR relaxation times were measured to access local mobility. The DFR was used to determine the solid-state acidity expressed as the Hammett acidity function. Stability of samples was evaluated at 40°C by monitoring potency and purity by high-performance liquid chromatography (HPLC). Results were interpreted in terms of the various roles of water: media effect, plasticization, polarity, and reactant. The kinetics of hydrolysis was observed to be correlated with either/both specific "chemical" effects, that is, water reactant as well as media effect, specifically global molecular mobility of the matrix. Increase in reaction rate with increase in water content is not linear and is a weaker dependence than in some hydrolytic reactions in organic solvents. A moderate amount of an inert plasticizer, sorbitol, conferred additional stabilization, possibly by restricting the amplitude and frequency of fast motions that are on a small length scale. Copyright © 2012 Wiley Periodicals, Inc.

PhreeqcRM: A reaction module for transport simulators based on the geochemical model PHREEQC

USGS Publications Warehouse

Parkhurst, David L.; Wissmeier, Laurin

2015-01-01

PhreeqcRM is a geochemical reaction module designed specifically to perform equilibrium and kinetic reaction calculations for reactive transport simulators that use an operator-splitting approach. The basic function of the reaction module is to take component concentrations from the model cells of the transport simulator, run geochemical reactions, and return updated component concentrations to the transport simulator. If multicomponent diffusion is modeled (e.g., Nernst–Planck equation), then aqueous species concentrations can be used instead of component concentrations. The reaction capabilities are a complete implementation of the reaction capabilities of PHREEQC. In each cell, the reaction module maintains the composition of all of the reactants, which may include minerals, exchangers, surface complexers, gas phases, solid solutions, and user-defined kinetic reactants.PhreeqcRM assigns initial and boundary conditions for model cells based on standard PHREEQC input definitions (files or strings) of chemical compositions of solutions and reactants. Additional PhreeqcRM capabilities include methods to eliminate reaction calculations for inactive parts of a model domain, transfer concentrations and other model properties, and retrieve selected results. The module demonstrates good scalability for parallel processing by using multiprocessing with MPI (message passing interface) on distributed memory systems, and limited scalability using multithreading with OpenMP on shared memory systems. PhreeqcRM is written in C++, but interfaces allow methods to be called from C or Fortran. By using the PhreeqcRM reaction module, an existing multicomponent transport simulator can be extended to simulate a wide range of geochemical reactions. Results of the implementation of PhreeqcRM as the reaction engine for transport simulators PHAST and FEFLOW are shown by using an analytical solution and the reactive transport benchmark of MoMaS.

40 CFR 420.131 - Specialized definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

....131 Specialized definitions. As used in this subpart: (a) The term briquetting operations means a hot... gaseous (carbon monoxide-carbon dioxide, hydrogen) or solid reactants. (c) The term forging means the hot... of briquettes manufactured by hot or cold agglomeration processes. (e) For direct reduced iron (DRI...

40 CFR 420.131 - Specialized definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

....131 Specialized definitions. As used in this subpart: (a) The term briquetting operations means a hot... gaseous (carbon monoxide-carbon dioxide, hydrogen) or solid reactants. (c) The term forging means the hot... of briquettes manufactured by hot or cold agglomeration processes. (e) For direct reduced iron (DRI...

40 CFR 420.131 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

....131 Specialized definitions. As used in this subpart: (a) The term briquetting operations means a hot... gaseous (carbon monoxide-carbon dioxide, hydrogen) or solid reactants. (c) The term forging means the hot... of briquettes manufactured by hot or cold agglomeration processes. (e) For direct reduced iron (DRI...

40 CFR 420.131 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

....131 Specialized definitions. As used in this subpart: (a) The term briquetting operations means a hot... gaseous (carbon monoxide-carbon dioxide, hydrogen) or solid reactants. (c) The term forging means the hot... of briquettes manufactured by hot or cold agglomeration processes. (e) For direct reduced iron (DRI...

Fabrication of gas impervious edge seal for a bipolar gas distribution assembly for use in a fuel cell

DOEpatents

Kaufman, Arthur; Werth, John

1986-01-01

A bipolar gas reactant distribution assembly for use in a fuel cell is disclosed, the assembly having a solid edge seal to prevent leakage of gaseous reactants wherein a pair of porous plates are provided with peripheral slits generally parallel to, and spaced apart from two edges of the plate, the slit being filled with a solid, fusible, gas impervious edge sealing compound. The plates are assembled with opposite faces adjacent one another with a layer of a fusible sealant material therebetween the slits in the individual plates being approximately perpendicular to one another. The plates are bonded to each other by the simultaneous application of heat and pressure to cause a redistribution of the sealant into the pores of the adjacent plate surfaces and to cause the edge sealing compound to flow and impregnate the region of the plates adjacent the slits and comingle with the sealant layer material to form a continuous layer of sealant along the edges of the assembled plates.

Microorganism mediated liquid fuels

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

Troiano, Richard

Herein disclosed is a method for producing liquid hydrocarbon product, the method comprising disintegrating a hydrocarbon source; pretreating the disintegrated hydrocarbon source; solubilizing the disintegrated hydrocarbon source to form a slurry comprising a reactant molecule of the hydrocarbon source; admixing a biochemical liquor into the slurry, wherein the biochemical liquor comprises at least one conversion enzyme configured to facilitate bond selective photo-fragmentation of said reactant molecule of the hydrocarbon source, to form liquid hydrocarbons via enzyme assisted bond selective photo-fragmentation, wherein said conversion enzyme comprises reactive sites configured to restrict said reactant molecule such that photo-fragmentation favorably targets a preselectedmore » internal bond of said reactant molecule; separating the liquid hydrocarbons from the slurry, wherein contaminants remain in the slurry; and enriching the liquid hydrocarbons to form a liquid hydrocarbon product. Various aspects of such method/process are also discussed.« less

Catalyst for producing lower alcohols

DOEpatents

Rathke, Jerome W.; Klingler, Robert J.; Heiberger, John J.

1987-01-01

A process and system for the production of the lower alcohols such as methanol, ethanol and propanol involves the reaction of carbon monoxide and water in the presence of a lead salt and an alkali metal formate catalyst combination. The lead salt is present as solid particles such as lead titanate, lead molybdate, lead vanadate, lead zirconate, lead tantalate and lead silicates coated or in slurry within molten alkali metal formate. The reactants, carbon monoxide and steam are provided in gas form at relatively low pressures below 100 atmospheres and at temperatures of 200-400.degree. C. The resulted lower alcohols can be separated into boiling point fractions and recovered from the excess reactants by distillation.

Theoretical Insights for Practical Handling of Pressurized Fluids

ERIC Educational Resources Information Center

Aranda, Alfonso; Rodriguez, Maria del Prado

2006-01-01

The practical scenarios discussed in a chemistry or chemical engineering course that use solid or liquid reactants are presented. Important ideas to be considered when handling pressurized fluids are provided and three typical examples are described to enable students develop secondary skills such as the selective search of data, identification of…

Evaluation of modified boehm titration methods for use with biochars.

PubMed

Fidel, Rivka B; Laird, David A; Thompson, Michael L

2013-11-01

The Boehm titration, originally developed to quantify organic functional groups of carbon blacks and activated carbons in discrete pK ranges, has received growing attention for analyzing biochar. However, properties that distinguish biochar from carbon black and activated carbon, including greater carbon solubility and higher ash content, may render the original Boehm titration method unreliable for use with biochars. Here we use seven biochars and one reference carbon black to evaluate three Boehm titration methods that use (i) acidification followed by sparging (sparge method), (ii) centrifugation after treatment with BaCl (barium method), and (iii) a solid-phase extraction cartridge followed by acidification and sparging (cartridge method) to remove carbonates and dissolved organic compounds (DOC) from the Boehm extracts before titration. Our results for the various combinations of Boehm reactants and methods indicate that no one method was free of bias for all three Boehm reactants and that the cartridge method showed evidence of bias for all pK ranges. By process of elimination, we found that a combination of the sparge method for quantifying functional groups in the lowest pK range (∼5 to 6.4), and the barium method for quantifying functional groups in the higher pK ranges (∼6.4 to 10.3 and ∼10.3 to 13) to be free of evidence for bias. We caution, however, that further testing is needed and that all Boehm titration results for biochars should be considered suspect unless efforts were undertaken to remove ash and prevent interference from DOC. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Reactivating the Ni-YSZ electrode in solid oxide cells and stacks by infiltration

NASA Astrophysics Data System (ADS)

Skafte, Theis Løye; Hjelm, Johan; Blennow, Peter; Graves, Christopher

2018-02-01

The solid oxide cell (SOC) could play a vital role in energy storage when the share of intermittent electricity production is high. However, large-scale commercialization of the technology is still hindered by the limited lifetime. Here, we address this issue by examining the potential for repairing various failure and degradation mechanisms occurring in the fuel electrode, thereby extending the potential lifetime of a SOC system. We successfully infiltrated the nickel and yttria-stabilized zirconia cermet electrode in commercial cells with Gd-doped ceria after operation. By this method we fully reactivated the fuel electrode after simulated reactant starvation and after carbon formation. Furthermore, by infiltrating after 900 h of operation, the degradation of the fuel electrode was reduced by a factor of two over the course of 2300 h. Lastly, the scalability of the concept is demonstrated by reactivating an 8-cell stack based on a commercial design.

Shockwave Processing of Composite Boron and Titanium Nitride Powders

NASA Astrophysics Data System (ADS)

Beason, Matthew T.; Gunduz, I. Emre; Mukasyan, Alexander S.; Son, Steven F.

2015-06-01

Shockwave processing of powders has been shown to initiate reactions between condensed phase reactants. It has been observed that these reactions can occur at very short timescales, resulting in chemical reactions occurring at a high pressure state. These reactions have the potential to produce metastable phases. Kinetic limitations prevent gaseous reactants from being used in this type of synthesis reaction. To overcome this limitation, a solid source of gaseous reactants must be used. An example of this type of reaction is the nitrogen exchange reaction (e.g. B + TiN, B + Si3N4 etc.). In these reactions nitrogen is ``carried'' by a material that can be then reduced by the second reactant. This work explores the possibility of using nitrogen exchange reactions to synthesize the cubic phase of boron nitride (c-BN) through shockwave processing of ball milled mixtures of boron and titanium nitride. The heating from the passage of the shock wave (pore collapse, plastic work, etc.) combined with thermochemical energy from the reaction may provide a means to synthesize c-BN. This material is based upon work supported by the Department of Energy, National Nuclear Security Administration, under Award Number(s) DE-NA0002377. National Defense Science & Engineering Graduate Fellowship (NDSEG), 32 CFR 168a.

Solid polymer electrolyte (SPE) fuel cell technology program, phase 2/2A. [testing and evaluations

NASA Technical Reports Server (NTRS)

1976-01-01

Test evaluations were performed on a fabricated single solid polymer electrolyte cell unit. The cell operated at increased current density and at higher performance levels. This improved performance was obtained through a combination of increased temperature, increased reactant pressures, improved activation techniques and improved thermal control over the baseline cell configuration. The cell demonstrated a higher acid content membrane which resulted in increased performance. Reduced catalyst loading and low cost membrane development showed encouraging results.

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

NASA Technical Reports Server (NTRS)

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

1951-01-01

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

Modeling and experimental performance of an intermediate temperature reversible solid oxide cell for high-efficiency, distributed-scale electrical energy storage

NASA Astrophysics Data System (ADS)

Wendel, Christopher H.; Gao, Zhan; Barnett, Scott A.; Braun, Robert J.

2015-06-01

Electrical energy storage is expected to be a critical component of the future world energy system, performing load-leveling operations to enable increased penetration of renewable and distributed generation. Reversible solid oxide cells, operating sequentially between power-producing fuel cell mode and fuel-producing electrolysis mode, have the capability to provide highly efficient, scalable electricity storage. However, challenges ranging from cell performance and durability to system integration must be addressed before widespread adoption. One central challenge of the system design is establishing effective thermal management in the two distinct operating modes. This work leverages an operating strategy to use carbonaceous reactant species and operate at intermediate stack temperature (650 °C) to promote exothermic fuel-synthesis reactions that thermally self-sustain the electrolysis process. We present performance of a doped lanthanum-gallate (LSGM) electrolyte solid oxide cell that shows high efficiency in both operating modes at 650 °C. A physically based electrochemical model is calibrated to represent the cell performance and used to simulate roundtrip operation for conditions unique to these reversible systems. Design decisions related to system operation are evaluated using the cell model including current density, fuel and oxidant reactant compositions, and flow configuration. The analysis reveals tradeoffs between electrical efficiency, thermal management, energy density, and durability.

Carbon dioxide-soluble polymers and swellable polymers for carbon dioxide applications

DOEpatents

DeSimone, Joseph M.; Birnbaum, Eva; Carbonell, Ruben G.; Crette, Stephanie; McClain, James B.; McCleskey, T. Mark; Powell, Kimberly R.; Romack, Timothy J.; Tumas, William

2004-06-08

A method for carrying out a catalysis reaction in carbon dioxide comprising contacting a fluid mixture with a catalyst bound to a polymer, the fluid mixture comprising at least one reactant and carbon dioxide, wherein the reactant interacts with the catalyst to form a reaction product. A composition of matter comprises carbon dioxide and a polymer and a reactant present in the carbon dioxide. The polymer has bound thereto a catalyst at a plurality of chains along the length of the polymer, and wherein the reactant interacts with the catalyst to form a reaction product.

A Conceptual Approach to Limiting-Reagent Problems

ERIC Educational Resources Information Center

Sostarecz, Michael C.; Sostarecz, Audra Goach

2012-01-01

A solid foundation of chemistry principles is only gained through a true comprehension of the material as opposed to pure memorization. One of the most fundamental concepts in chemistry is that of determining the amount of product formed in a chemical reaction when one of the reactants is limiting. To increase students' comprehension of this…

40 CFR 420.131 - Specialized definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... gaseous (carbon monoxide-carbon dioxide, hydrogen) or solid reactants. (c) The term forging means the hot... commercially (as opposed to fines that may be reprocessed on site). (f) For forging, the term product means the tons of finished steel forgings produced by hot working steel shapes. (g) The term O&G (as HEM) means...

Mechanochemical Synthesis of Two Polymorphs of the Tetrathiafulvalene-Chloranil Charge Transfer Salt: An Experiment for Organic Chemistry

ERIC Educational Resources Information Center

Wixtrom, Alex; Buhler, Jessica; Abdel-Fattah, Tarek

2014-01-01

Mechanochemical syntheses avoid or considerably reduce the use of reaction solvents, thus providing green chemistry synthetic alternatives that are both environmentally friendly and economically advantageous. The increased solid-state reactivity generated by mechanical energy imparted to the reactants by grinding or milling can offer alternative…

Air-Independent Solid Oxide Fuel Cells for NASA's LOX-CH4 Landers

NASA Technical Reports Server (NTRS)

Ryan, Abigail C.; Araghi, Koorosh R.; Farmer, Serene C.

2013-01-01

Gemini, Apollo, and Space Shuttle used fuel cells as main power source for vehicle and water source for life support and thermal PEM (Gemini) and Alkaline (Apollo, Shuttle) fuel cells were used Ideal for short (less than 3 weeks) missions when the required O2 and H2 can be launched with the vehicle. New missions that might require long-duration stays in orbit or at a habitat, cannot rely on the availability of pure reactants but should also aim to be sun-independent - a problem for which Solid Oxide Fuel Cells might be the answer. Recently, NASA has investigated & developed LOX/CH4-propelled landers (Altair, MORPHEUS). In order to preserve mission flexibility, fuel cells are being studied as a potential power source. Much of NASA's fuel cell development has been focused on creating a dead-headed, non-flow through PEM fuel cells which would weigh less and be more reliable than the existing Alkaline and PEM technology; however, LOX/CH4 as a propellant introduces SOFCs as a power option due to their ability to accept those reactants without much reforming.

Method for reacting nongaseous material with a gaseous reactant

DOEpatents

Lumpkin, Robert E.; Duraiswamy, Kandaswamy

1979-03-27

This invention relates to a new and novel method and apparatus for reacting nongaseous material with a gaseous reactant comprising introducing a first stream containing a nongaseous material into a reaction zone; simultaneously introducing a second stream containing a gaseous reactant into the reaction zone such that the gaseous reactant immediately contacts and reacts with the first stream thereby producing a gaseous product; forming a spiralling vortex within the reaction zone to cause substantial separation of gases, including the gaseous product, from the nongaseous material; forming and removing a third stream from the reaction zone containing the gaseous product which is substantially free of the nongaseous material before a major portion of the gaseous product can react with the nongaseous material; and forming and removing a fourth stream containing the nongaseous material from the reaction zone.

Moving bed reactor setup to study complex gas-solid reactions.

PubMed

Gupta, Puneet; Velazquez-Vargas, Luis G; Valentine, Charles; Fan, Liang-Shih

2007-08-01

A moving bed scale reactor setup for studying complex gas-solid reactions has been designed in order to obtain kinetic data for scale-up purpose. In this bench scale reactor setup, gas and solid reactants can be contacted in a cocurrent and countercurrent manner at high temperatures. Gas and solid sampling can be performed through the reactor bed with their composition profiles determined at steady state. The reactor setup can be used to evaluate and corroborate model parameters accounting for intrinsic reaction rates in both simple and complex gas-solid reaction systems. The moving bed design allows experimentation over a variety of gas and solid compositions in a single experiment unlike differential bed reactors where the gas composition is usually fixed. The data obtained from the reactor can also be used for direct scale-up of designs for moving bed reactors.

PROCESS FOR PRODUCING URANIUM HALIDES

DOEpatents

Murphree, E.V.

1957-10-29

A process amd associated apparatus for producing UF/sub 4/ from U/sub 3/ O/sub 8/ by a fluidized'' technique are reported. The U/sub 3/O/sub 8/ is first reduced to UO/sub 2/ by reaction with hydrogen, and the lower oxide of uranium is then reacted with gaseous HF to produce UF/sub 4/. In each case the reactant gas is used, alone or in combination with inert gases, to fluidize'' the finely divided reactant solid. The complete setup of the plant equipment including bins, reactor and the associated piping and valving, is described. An auxiliary fluorination reactor allows for the direct production of UF/sub 6/ from UF/sub 4/ and fluorine gas, or if desired, UF/sub 4/ may be collected as the product.

Power recovery system for coal liquefaction process

DOEpatents

Horton, Joel R.

1985-01-01

Method and apparatus for minimizing energy required to inject reactant such as coal-oil slurry into a reaction vessel, using high pressure effluent from the latter to displace the reactant from a containment vessel into the reaction vessel with assistance of low pressure pump. Effluent is degassed in the containment vessel, and a heel of the degassed effluent is maintained between incoming effluent and reactant in the containment vessel.

Method for predicting enzyme-catalyzed reactions

DOEpatents

Hlavacek, William S.; Unkefer, Clifford J.; Mu, Fangping; Unkefer, Pat J.

2013-03-19

The reactivity of given metabolites is assessed using selected empirical atomic properties in the potential reaction center. Metabolic reactions are represented as biotransformation rules. These rules are generalized from the patterns in reactions. These patterns are not unique to reactants but are widely distributed among metabolites. Using a metabolite database, potential substructures are identified in the metabolites for a given biotransformation. These substructures are divided into reactants or non-reactants, depending on whether they participate in the biotransformation or not. Each potential substructure is then modeled using descriptors of the topological and electronic properties of atoms in the potential reaction center; molecular properties can also be used. A Support Vector Machine (SVM) or classifier is trained to classify a potential reactant as a true or false reactant using these properties.

Electrochemistry in an acoustically levitated drop.

PubMed

Chainani, Edward T; Ngo, Khanh T; Scheeline, Alexander

2013-02-19

Levitated drops show potential as microreactors, especially when radicals are present as reactants or products. Solid/liquid interfaces are absent or minimized, avoiding adsorption and interfacial reaction of conventional microfluidics. We report amperometric detection in an acoustically levitated drop with simultaneous ballistic addition of reactant. A gold microelectrode sensor was fabricated with a lithographic process; active electrode area was defined by a photosensitive polyimide mask. The microdisk gold working electrode of radius 19 μm was characterized using ferrocenemethanol in aqueous buffer. Using cyclic voltammetry, the electrochemically active surface area was estimated by combining a recessed microdisk electrode model with the Randles-Sevcik equation. Computer-controlled ballistic introduction of reactant droplets into the levitated drop was developed. Chronoamperometric measurements of ferrocyanide added ballistically demonstrate electrochemical monitoring using the microfabricated electrode in a levitated drop. Although concentration increases with time due to drop evaporation, the extent of concentration is predictable with a linear evaporation model. Comparison of diffusion-limited currents in pendant and levitated drops show that convection arising from acoustic levitation causes an enhancement of diffusion-limited current on the order of 16%.

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.

Gradient isolator for flow field of fuel cell assembly

DOEpatents

Ernst, W.D.

1999-06-15

Isolator(s) include isolating material and optionally gasketing material strategically positioned within a fuel cell assembly. The isolating material is disposed between a solid electrolyte and a metal flow field plate. Reactant fluid carried by flow field plate channel(s) forms a generally transverse electrochemical gradient. The isolator(s) serve to isolate electrochemically a portion of the flow field plate, for example, transversely outward from the channel(s), from the electrochemical gradient. Further, the isolator(s) serve to protect a portion of the solid electrolyte from metallic ions. 4 figs.

Gradient isolator for flow field of fuel cell assembly

DOEpatents

Ernst, William D.

1999-01-01

Isolator(s) include isolating material and optionally gasketing material strategically positioned within a fuel cell assembly. The isolating material is disposed between a solid electrolyte and a metal flow field plate. Reactant fluid carried by flow field plate channel(s) forms a generally transverse electrochemical gradient. The isolator(s) serve to isolate electrochemically a portion of the flow field plate, for example, transversely outward from the channel(s), from the electrochemical gradient. Further, the isolator(s) serve to protect a portion of the solid electrolyte from metallic ions.

Hydrogen generation systems and methods utilizing sodium silicide and sodium silica gel materials

DOEpatents

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

2015-08-11

Systems, devices, and methods combine thermally stable reactant materials and aqueous solutions to generate hydrogen and a non-toxic liquid by-product. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Springs and other pressurization mechanisms pressurize and deliver an aqueous solution to the reaction. A check valve and other pressure regulation mechanisms regulate the pressure of the aqueous solution delivered to the reactant fuel material in the reactor based upon characteristics of the pressurization mechanisms and can regulate the pressure of the delivered aqueous solution as a steady decay associated with the pressurization force. The pressure regulation mechanism can also prevent hydrogen gas from deflecting the pressure regulation mechanism.

Probing solid catalysts under operating conditions: electrons or X-rays?

PubMed

Thomas, John Meurig; Hernandez-Garrido, Juan-Carlos

2009-01-01

Seeing is believing: In light of recent advances, the pros and cons of using electrons and X-rays for in situ studies of catalysts are analyzed: by using X-rays the structure of bound reactants at steady state are obtained from extended X-ray adsorption fine structure spectroscopy (EXAFS) data (see graph), thereby affording mechanistic insights.

CATALYST-FREE REACTIONS UNDER SOLVENT-FEE CONDITIONS: MICROWAVE-ASSISTED SYNTHESIS OF HETEROCYCLIC HYDRAZONES BELOW THE MELTING POINT OF NEAT REACTANTS

EPA Science Inventory

The reaction of neat 5- or 8-oxobenzopyran-2(1H)-ones with a variety of aromatic and heteroaromatic hydrazines are remarkable accelerated upon irradiation in a household microwave oven in the absence of any catalyst, solid support or solvent thus providing an environmentally frie...

Nanowire membrane-based nanothermite: towards processable and tunable interfacial diffusion for solid state reactions.

PubMed

Yang, Yong; Wang, Peng-peng; Zhang, Zhi-cheng; Liu, Hui-ling; Zhang, Jingchao; Zhuang, Jing; Wang, Xun

2013-01-01

Interfacial diffusion is of great importance in determining the performance of solid-state reactions. For nanometer sized particles, some solid-state reactions can be triggered accidently by mechanical stress owing to their large surface-to-volume ratio compared with the bulk ones. Therefore, a great challenge is the control of interfacial diffusion for solid state reactions, especially for energetic materials. Here we demonstrate, through the example of nanowire-based thermite membrane, that the thermite solid-state reaction can be easily tuned via the introduction of low-surface-energy coating layer. Moreover, this silicon-coated thermite membrane exhibit controlled wetting behavior ranging from superhydrophilic to superhydrophobic and, simultaneously, to significantly reduce the friction sensitivity of thermite membrane. This effect enables to increase interfacial resistance by increasing the amount of coating material. Indeed, our results described here make it possible to tune the solid-state reactions through the manipulation of interfacial diffusion between the reactants.

Nanowire Membrane-based Nanothermite: towards Processable and Tunable Interfacial Diffusion for Solid State Reactions

NASA Astrophysics Data System (ADS)

Yang, Yong; Wang, Peng-Peng; Zhang, Zhi-Cheng; Liu, Hui-Ling; Zhang, Jingchao; Zhuang, Jing; Wang, Xun

2013-04-01

Interfacial diffusion is of great importance in determining the performance of solid-state reactions. For nanometer sized particles, some solid-state reactions can be triggered accidently by mechanical stress owing to their large surface-to-volume ratio compared with the bulk ones. Therefore, a great challenge is the control of interfacial diffusion for solid state reactions, especially for energetic materials. Here we demonstrate, through the example of nanowire-based thermite membrane, that the thermite solid-state reaction can be easily tuned via the introduction of low-surface-energy coating layer. Moreover, this silicon-coated thermite membrane exhibit controlled wetting behavior ranging from superhydrophilic to superhydrophobic and, simultaneously, to significantly reduce the friction sensitivity of thermite membrane. This effect enables to increase interfacial resistance by increasing the amount of coating material. Indeed, our results described here make it possible to tune the solid-state reactions through the manipulation of interfacial diffusion between the reactants.

Combustion synthesis of advanced materials. [using in-situ infiltration technique

NASA Technical Reports Server (NTRS)

Moore, J. J.; Feng, H. J.; Perkins, N.; Readey, D. W.

1992-01-01

The combustion synthesis of ceramic-metal composites using an in-situ liquid infiltration technique is described. The effect of varying the reactants and their stoichiometry to provide a range of reactant and product species i.e. solids, liquids and gases, with varying physical properties e.g. thermal conductivity, on the microstructure and morphology of synthesized products is also described. Alternatively, conducting the combustion synthesis reaction in a reactive gas environment is also discussed, in which advantages can be gained from the synergistic effects of combustion synthesis and vapor phase transport. In each case, the effect of the presence or absence of gravity (density) driven fluid flow and vapor transport is discussed as is the potential for producing new and perhaps unique materials by conducting these SHS reactions under microgravity conditions.

Reactant conversion in homogeneous turbulence - Mathematical modeling, computational validations, and practical applications

NASA Technical Reports Server (NTRS)

Madnia, C. K.; Frankel, S. H.; Givi, P.

1992-01-01

The presently obtained closed-form analytical expressions, which predict the limiting rate of mean reactant conversion in homogeneous turbulent flows under the influence of a binary reaction, are derived via the single-point pdf method based on amplitude mapping closure. With this model, the maximum rate of the mean reactant's decay can be conveniently expressed in terms of definite integrals of the parabolic cylinder functions. The results obtained are shown to be in good agreement with data generated by direct numerical simulations.

METHOD FOR PRODUCING ISOTOPIC METHANES FROM LITHIUM CARBONATE AND LITHIUM HYDRIDE

DOEpatents

Frazer, J.W.

1959-10-27

A process is descrlbed for the production of methane and for the production of methane containing isotopes of hydrogen and/or carbon. Finely divided lithium hydrlde and litldum carbonate reactants are mixed in intimate contact and subsequently compacted under pressures of from 5000 to 60,000 psl. The compacted lithium hydride and lithium carbenate reactunts are dispised in a gas collecting apparatus. Subsequently, the compact is heated to a temperature in the range 350 to 400 deg C whereupon a solid-solid reaction takes place and gaseous methane is evolved. The evolved methane is contaminated with gaseous hydrogen and a very small amount of CO/sub 2/; however, the desired methane product is separated from sald impurities by well known chemical processes, e.g., condensation in a cold trap. The product methane contalns isotopes of carbon and hydrogen, the Isotopic composition being determined by the carbon isotopes originally present In the lithium carbonate and the hydrogen isotopes originally present in the lithium hydride.

Catalytic reforming methods

DOEpatents

Tadd, Andrew R; Schwank, Johannes

2013-05-14

A catalytic reforming method is disclosed herein. The method includes sequentially supplying a plurality of feedstocks of variable compositions to a reformer. The method further includes adding a respective predetermined co-reactant to each of the plurality of feedstocks to obtain a substantially constant output from the reformer for the plurality of feedstocks. The respective predetermined co-reactant is based on a C/H/O atomic composition for a respective one of the plurality of feedstocks and a predetermined C/H/O atomic composition for the substantially constant output.

A complete two-phase model of a porous cathode of a PEM fuel cell

NASA Astrophysics Data System (ADS)

Hwang, J. J.

This paper has developed a complete two-phase model of a proton exchange membrane (PEM) fuel cell by considering fluid flow, heat transfer and current simultaneously. In fluid flow, two momentum equations governing separately the gaseous-mixture velocity (u g) and the liquid-water velocity (u w) illustrate the behaviors of the two-phase flow in a porous electrode. Correlations for the capillary pressure and the saturation level connect the above two-fluid transports. In heat transfer, a local thermal non-equilibrium (LTNE) model accounting for intrinsic heat transfer between the reactant fluids and the solid matrices depicts the interactions between the reactant-fluid temperature (T f) and the solid-matrix temperature (T s). The irreversibility heating due to electrochemical reactions, Joule heating arising from Ohmic resistance, and latent heat of water condensation/evaporation are considered in the present non-isothermal model. In current, Ohm's law is applied to yield the conservations in ionic current (i m) and electronic current (i s) in the catalyst layer. The Butler-Volmer correlation describes the relation of the potential difference (overpotential) and the transfer current between the electrolyte (such as Nafion™) and the catalyst (such as Pt/C).

Computational modeling of chemical reactions and interstitial growth and remodeling involving charged solutes and solid-bound molecules

PubMed Central

Nims, Robert J.; Maas, Steve; Weiss, Jeffrey A.

2014-01-01

Mechanobiological processes are rooted in mechanics and chemistry, and such processes may be modeled in a framework that couples their governing equations starting from fundamental principles. In many biological applications, the reactants and products of chemical reactions may be electrically charged, and these charge effects may produce driving forces and constraints that significantly influence outcomes. In this study, a novel formulation and computational implementation are presented for modeling chemical reactions in biological tissues that involve charged solutes and solid-bound molecules within a deformable porous hydrated solid matrix, coupling mechanics with chemistry while accounting for electric charges. The deposition or removal of solid-bound molecules contributes to the growth and remodeling of the solid matrix; in particular, volumetric growth may be driven by Donnan osmotic swelling, resulting from charged molecular species fixed to the solid matrix. This formulation incorporates the state of strain as a state variable in the production rate of chemical reactions, explicitly tying chemistry with mechanics for the purpose of modeling mechanobiology. To achieve these objectives, this treatment identifies the specific theoretical and computational challenges faced in modeling complex systems of interacting neutral and charged constituents while accommodating any number of simultaneous reactions where reactants and products may be modeled explicitly or implicitly. Several finite element verification problems are shown to agree with closed-form analytical solutions. An illustrative tissue engineering analysis demonstrates tissue growth and swelling resulting from the deposition of chondroitin sulfate, a charged solid-bound molecular species. This implementation is released in the open-source program FEBio (www.febio.org). The availability of this framework may be particularly beneficial to optimizing tissue engineering culture systems by examining the influence of nutrient availability on the evolution of inhomogeneous tissue composition and mechanical properties, the evolution of construct dimensions with growth, the influence of solute and solid matrix electric charge on the transport of cytokines, the influence of binding kinetics on transport, the influence of loading on binding kinetics, and the differential growth response to dynamically loaded versus free-swelling culture conditions. PMID:24558059

Computational modeling of chemical reactions and interstitial growth and remodeling involving charged solutes and solid-bound molecules.

PubMed

Ateshian, Gerard A; Nims, Robert J; Maas, Steve; Weiss, Jeffrey A

2014-10-01

Mechanobiological processes are rooted in mechanics and chemistry, and such processes may be modeled in a framework that couples their governing equations starting from fundamental principles. In many biological applications, the reactants and products of chemical reactions may be electrically charged, and these charge effects may produce driving forces and constraints that significantly influence outcomes. In this study, a novel formulation and computational implementation are presented for modeling chemical reactions in biological tissues that involve charged solutes and solid-bound molecules within a deformable porous hydrated solid matrix, coupling mechanics with chemistry while accounting for electric charges. The deposition or removal of solid-bound molecules contributes to the growth and remodeling of the solid matrix; in particular, volumetric growth may be driven by Donnan osmotic swelling, resulting from charged molecular species fixed to the solid matrix. This formulation incorporates the state of strain as a state variable in the production rate of chemical reactions, explicitly tying chemistry with mechanics for the purpose of modeling mechanobiology. To achieve these objectives, this treatment identifies the specific theoretical and computational challenges faced in modeling complex systems of interacting neutral and charged constituents while accommodating any number of simultaneous reactions where reactants and products may be modeled explicitly or implicitly. Several finite element verification problems are shown to agree with closed-form analytical solutions. An illustrative tissue engineering analysis demonstrates tissue growth and swelling resulting from the deposition of chondroitin sulfate, a charged solid-bound molecular species. This implementation is released in the open-source program FEBio ( www.febio.org ). The availability of this framework may be particularly beneficial to optimizing tissue engineering culture systems by examining the influence of nutrient availability on the evolution of inhomogeneous tissue composition and mechanical properties, the evolution of construct dimensions with growth, the influence of solute and solid matrix electric charge on the transport of cytokines, the influence of binding kinetics on transport, the influence of loading on binding kinetics, and the differential growth response to dynamically loaded versus free-swelling culture conditions.

Fuel-Cell Power Source Based on Onboard Rocket Propellants

NASA Technical Reports Server (NTRS)

Ganapathi, Gani; Narayan, Sri

2010-01-01

The use of onboard rocket propellants (dense liquids at room temperature) in place of conventional cryogenic fuel-cell reactants (hydrogen and oxygen) eliminates the mass penalties associated with cryocooling and boil-off. The high energy content and density of the rocket propellants will also require no additional chemical processing. For a 30-day mission on the Moon that requires a continuous 100 watts of power, the reactant mass and volume would be reduced by 15 and 50 percent, respectively, even without accounting for boiloff losses. The savings increase further with increasing transit times. A high-temperature, solid oxide, electrolyte-based fuel-cell configuration, that can rapidly combine rocket propellants - both monopropellant system with hydrazine and bi-propellant systems such as monomethyl hydrazine/ unsymmetrical dimethyl hydrazine (MMH/UDMH) and nitrogen tetroxide (NTO) to produce electrical energy - overcomes the severe drawbacks of earlier attempts in 1963-1967 of using fuel reforming and aqueous media. The electrical energy available from such a fuel cell operating at 60-percent efficiency is estimated to be 1,500 Wh/kg of reactants. The proposed use of zirconia-based oxide electrolyte at 800-1,000 C will permit continuous operation, very high power densities, and substantially increased efficiency of conversion over any of the earlier attempts. The solid oxide fuel cell is also tolerant to a wide range of environmental temperatures. Such a system is built for easy refueling for exploration missions and for the ability to turn on after several years of transit. Specific examples of future missions are in-situ landers on Europa and Titan that will face extreme radiation and temperature environments, flyby missions to Saturn, and landed missions on the Moon with 14 day/night cycles.

High temperature solid oxide regenerative fuel cell for solar photovoltaic energy storage

NASA Technical Reports Server (NTRS)

Bents, David J.

1987-01-01

A hydrogen-oxygen regenerative fuel cell energy storage system based on high temperature solid oxide fuel cell technology is discussed which has application to darkside energy storage for solar photovoltaics. The forward and reverse operating cycles are described, and heat flow, mass, and energy balance data are presented to characterize the system's performance and the variation of performance with changing reactant storage pressure. The present system weighs less than nickel hydrogen battery systems after 0.7 darkside operation, and it maintains a specific weight advantage over radioisotope generators for discharge periods up to 72 hours.

Mathematical modeling of solid oxide fuel cells

NASA Technical Reports Server (NTRS)

Lu, Cheng-Yi; Maloney, Thomas M.

1988-01-01

Development of predictive techniques, with regard to cell behavior, under various operating conditions is needed to improve cell performance, increase energy density, reduce manufacturing cost, and to broaden utilization of various fuels. Such technology would be especially beneficial for the solid oxide fuel cells (SOFC) at it early demonstration stage. The development of computer models to calculate the temperature, CD, reactant distributions in the tubular and monolithic SOFCs. Results indicate that problems of nonuniform heat generation and fuel gas depletion in the tubular cell module, and of size limitions in the monolithic (MOD 0) design may be encountered during FC operation.

High temperature solid oxide regenerative fuel cell for solar photovoltaic energy storage

NASA Astrophysics Data System (ADS)

Bents, David J.

A hydrogen-oxygen regenerative fuel cell energy storage system based on high temperature solid oxide fuel cell technology is discussed which has application to darkside energy storage for solar photovoltaics. The forward and reverse operating cycles are described, and heat flow, mass, and energy balance data are presented to characterize the system's performance and the variation of performance with changing reactant storage pressure. The present system weighs less than nickel hydrogen battery systems after 0.7 darkside operation, and it maintains a specific weight advantage over radioisotope generators for discharge periods up to 72 hours.

Method for forming synthesis gas using a plasma-catalyzed fuel reformer

DOEpatents

Hartvigsen, Joseph J; Elangovan, S; Czernichowski, Piotr; Hollist, Michele

2015-04-28

A method of forming a synthesis gas utilizing a reformer is disclosed. The method utilizes a reformer that includes a plasma zone to receive a pre-heated mixture of reactants and ionize the reactants by applying an electrical potential thereto. A first thermally conductive surface surrounds the plasma zone and is configured to transfer heat from an external heat source into the plasma zone. The reformer further includes a reaction zone to chemically transform the ionized reactants into synthesis gas comprising hydrogen and carbon monoxide. A second thermally conductive surface surrounds the reaction zone and is configured to transfer heat from the external heat source into the reaction zone. The first thermally conductive surface and second thermally conductive surface are both directly exposed to the external heat source. A corresponding apparatus and system are also disclosed herein.

Laser-driven fusion etching process

DOEpatents

Ashby, C.I.H.; Brannon, P.J.; Gerardo, J.B.

1987-08-25

The surfaces of solids are etched by a radiation-driven chemical reaction. The process involves exposing a substrate coated with a layer of a reactant material on its surface to radiation, e.g., a laser, to induce localized melting of the substrate which results in the occurrence of a fusion reaction between the substrate and coating material. The resultant reaction product and excess reactant salt are then removed from the surface of the substrate with a solvent which is relatively inert towards the substrate. The laser-driven chemical etching process is especially suitable for etching ionic substrates, e.g., LiNbO/sub 3/, such as used in electro-optical/acousto-optic devices. It is also suitable for applications wherein the etching process is required to produce an etched ionic substrate having a smooth surface morphology or when a very rapid etching rate is desired.

Method for synthesizing ultrafine powder materials

DOEpatents

Buss, Richard J.; Ho, Pauline

1988-01-01

A method for synthesizing ultrafine powder materials, for example, ceramic and metal powders, comprises admitting gaseous reactants from which the powder material is to be formed into a vacuum reaction chamber maintained at a pressure less than atmospheric and at a temperature less than about 400.degree. K. (127.degree.C.). The gaseous reactants are directed through a glow discharge provided in the vacuum reaction chamber to form the ultrafine powder material.

Apparatus for rendering at least a portion of a device inoperable and related methods

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

Daniels, Michael A.; Steffler, Eric D.; Hartenstein, Steven D.

2016-11-08

Apparatus for rendering at least a portion of a device inoperable may include a containment structure having a first compartment that is configured to receive a device therein and a movable member configured to receive a cartridge having reactant material therein. The movable member is configured to be inserted into the first compartment of the containment structure and to ignite the reactant material within the cartridge. Methods of rendering at least a portion of a device inoperable may include disposing the device into the first compartment of the containment structure, inserting the movable member into the first compartment of themore » containment structure, igniting the reactant material in the cartridge, and expelling molten metal onto the device.« less

Stagnation point reverse flow combustor

NASA Technical Reports Server (NTRS)

Zinn, Ben T. (Inventor); Neumeier, Yedidia (Inventor); Seitzman, Jerry M. (Inventor); Jagoda, Jechiel (Inventor); Weksler, Yoav (Inventor)

2008-01-01

A method for combusting a combustible fuel includes providing a vessel having an opening near a proximate end and a closed distal end defining a combustion chamber. A combustible reactants mixture is presented into the combustion chamber. The combustible reactants mixture is ignited creating a flame and combustion products. The closed end of the combustion chamber is utilized for directing combustion products toward the opening of the combustion chamber creating a reverse flow of combustion products within the combustion chamber. The reverse flow of combustion products is intermixed with combustible reactants mixture to maintain the flame.

Putting Cocrystal Stoichiometry to Work: A Reactive Hydrogen-Bonded "Superassembly" Enables Nanoscale Enlargement of a Metal-Organic Rhomboid via a Solid-State Photocycloaddition.

PubMed

Chu, Qianli; Duncan, Andrew J E; Papaefstathiou, Giannis S; Hamilton, Tamara D; Atkinson, Manza B J; Mariappan, S V Santhana; MacGillivray, Leonard R

2018-04-11

Enlargement of a self-assembled metal-organic rhomboid is achieved via the organic solid state. The solid-state synthesis of an elongated organic ligand was achieved by a template directed [2 + 2] photodimerization in a cocrystal. Initial cocrystals obtained of resorcinol template and reactant alkene afforded a 1:2 cocrystal with the alkene in a stacked yet photostable geometry. Cocrystallization performed in the presence of excess template resulted in a 3:2 cocrystal composed of novel discrete 10-component hydrogen-bonded "superassemblies" wherein the alkenes undergo a head-to-head [2 + 2] photodimerization. Isolation and reaction of elongated photoproduct with Cu(II) ions afforded a metal-organic rhomboid of nanoscale dimensions that hosts small molecules in the solid state as guests.

Original Synthetic Route To Obtain a SrAl2O4 Phosphor by the Molten Salt Method: Insights into the Reaction Mechanism and Enhancement of the Persistent Luminescence.

PubMed

Rojas-Hernandez, Rocío Estefanía; Rubio-Marcos, Fernando; Gonçalves, Ricardo Henrique; Rodriguez, Miguel Ángel; Véron, Emmanuel; Allix, Mathieu; Bessada, Catherine; Fernandez, José Francisco

2015-10-19

SrAl2O4:Eu(2+), Dy(3+) has been extensively studied for industrial applications in the luminescent materials field, because of its excellent persistent luminescence properties and chemical stability. Traditionally, this strontium aluminate material is synthesized in bulk form and/or fine powder by the classic solid-state method. Here, we report an original synthetic route, a molten salt assisted process, to obtain highly crystalline SrAl2O4 powder with nanometer-scale crystals. The main advantages of salt addition are the increase of the reaction rate and the significant reduction of the synthesis temperature because of much higher mobility of reactants in the liquid medium than in the solid-state method. In particular, the formation mechanism of SrAl2O4, the role of the salt, and the phase's evolution have been explored as a function of temperature and time. Phosphorescent powders based on SrAl2O4:Eu(2+), Dy(3+) with high crystallinity are obtained after 1 h treatment at 900 °C. This work could promote further interest in adopting the molten salt strategy to process high-crystallinity materials with enhanced luminescence to design technologically relevant phosphors.

Nanowire Membrane-based Nanothermite: towards Processable and Tunable Interfacial Diffusion for Solid State Reactions

PubMed Central

Yang, Yong; Wang, Peng-peng; Zhang, Zhi-cheng; Liu, Hui-ling; Zhang, Jingchao; Zhuang, Jing; Wang, Xun

2013-01-01

Interfacial diffusion is of great importance in determining the performance of solid-state reactions. For nanometer sized particles, some solid-state reactions can be triggered accidently by mechanical stress owing to their large surface-to-volume ratio compared with the bulk ones. Therefore, a great challenge is the control of interfacial diffusion for solid state reactions, especially for energetic materials. Here we demonstrate, through the example of nanowire-based thermite membrane, that the thermite solid-state reaction can be easily tuned via the introduction of low-surface-energy coating layer. Moreover, this silicon-coated thermite membrane exhibit controlled wetting behavior ranging from superhydrophilic to superhydrophobic and, simultaneously, to significantly reduce the friction sensitivity of thermite membrane. This effect enables to increase interfacial resistance by increasing the amount of coating material. Indeed, our results described here make it possible to tune the solid-state reactions through the manipulation of interfacial diffusion between the reactants. PMID:23603809

Method and compositions for detecting of bloodstains using fluorescin-fluorescein reaction

DOEpatents

Di Benedetto, John; Kyle, Kevin; Boan, Terry; Marie, Charlene

2004-02-17

A method, compositions and kit are set forth for detecting blood stains. A reactant solution includes fluorescin solubilized (reduced) in acetic acid in ethanol. The solution may be buffered to a pH of approximately 9. After spraying the reactant solution on the suspected area an oxidizer is applied to promote the fluorescin to fluorescein reaction with the blood. The reacted fluorescein is then detected through luminescence for capture by photography.

Method of making sintered ductile intermetallic-bonded ceramic composites

DOEpatents

Plucknett, Kevin; Tiegs, Terry N.; Becher, Paul F.

1999-01-01

A method of making an intermetallic-bonded ceramic composite involves combining a particulate brittle intermetallic precursor with a particulate reactant metal and a particulate ceramic to form a mixture and heating the mixture in a non-oxidizing atmosphere at a sufficient temperature and for a sufficient time to react the brittle intermetallic precursor and the reactant metal to form a ductile intermetallic and sinter the mixture to form a ductile intermetallic-bonded ceramic composite.

Semipermeable polymers and method for producing same

DOEpatents

Buschmann, Wayne E [Boulder, CO

2012-04-03

A polyamide membrane comprising reaction product of an anhydrous solution comprising an anhydrous solvent, at least one polyfunctional secondary amine and a pre-polymer deposition catalyst; and an anhydrous, organic solvent solution comprising a polyfunctional aromatic amine-reactive reactant comprising one ring. A composite semipermeable membrane comprising the polyamide membrane on a porous support. A method of making a composite semipermeable membrane by coating a porous support with an anhydrous solution comprising an anhydrous solvent, a polyfunctional secondary amine and a pre-polymer deposition catalyst, to form an activated pre-polymer layer on the porous support and contacting the activated pre-polymer layer with an anhydrous, organic solvent solution comprising a polyfunctional amine-reactive reactant to interfacially condense the amine-reactive reactant with the polyfunctional secondary amine, thereby forming a cross-linked, interfacial polyamide layer on the porous support. A method of impregnating a composite semipermeable membrane with nanoparticles selected from heavy metals and/or oxides of heavy metals.

Electrochemical cell and method of assembly

DOEpatents

Shimotake, Hiroshi; Voss, Ernst C. H.; Bartholme, Louis G.

1979-01-01

A method of preparing an electrochemical cell is disclosed which permits the assembly to be accomplished in air. The cell includes a metal sulfide as the positive electrode reactant, lithium alloy as the negative electrode reactant and an alkali metal, molten salt electrolyte. Positive electrode reactant is introduced as Li.sub.2 FeS.sub.2, a single-phase compound produced by the reaction of Li.sub.2 S and FeS. The use of this compound permits introduction of lithium in an oxidized form. Additional lithium can be introduced in the negative electrode structure enclosed within an aluminum foil envelope between layers of porous aluminum. Molten salt electrolyte is added after assembly and evacuation of the cell by including an interelectrode separator that has been prewet with an organic solution of KCl.

Method of making sintered ductile intermetallic-bonded ceramic composites

DOEpatents

Plucknett, K.; Tiegs, T.N.; Becher, P.F.

1999-05-18

A method of making an intermetallic-bonded ceramic composite involves combining a particulate brittle intermetallic precursor with a particulate reactant metal and a particulate ceramic to form a mixture and heating the mixture in a non-oxidizing atmosphere at a sufficient temperature and for a sufficient time to react the brittle intermetallic precursor and the reactant metal to form a ductile intermetallic and sinter the mixture to form a ductile intermetallic-bonded ceramic composite. 2 figs.

Method to produce biomass-derived compounds using a co-solvent system containing gamma-valerolactone

DOEpatents

Dumesic, James A.; Motagamwala, Ali Hussain

2017-06-27

A method to produce an aqueous solution of carbohydrates containing C5- and/or C6-sugar-containing oligomers and/or C5- and/or C6-sugar monomers in which biomass or a biomass-derived reactant is reacted with a solvent system having an organic solvent, and organic co-solvent, and water, in the presence of an acid. The method produces the desired product, while a substantial portion of any lignin present in the reactant appears as a precipitate in the product mixture.

The Hydroxyl Radical Reaction Rate Constant and Products of Cyclohexanol

DTIC Science & Technology

2007-10-01

Analysis Samples from kinetic studies were quantitativelymon- itored using a Hewlett-Packard (HP) gas chromato- graph (GC) 5890 with a flame ionization...excluded from the reaction mixture and the COL concentration was approximately doubled (4.9–9 ppm). Product Study Analysis Reactant mixtures and standards...from product identi- fication experiments were sampled by exposing a 100% polydimethylsiloxane solid phase microextrac- tion fiber (SPME) in the

Steam Methane Reformation Testing for Air-Independent Solid Oxide Fuel Cell Systems

NASA Technical Reports Server (NTRS)

Mwara, Kamwana N.

2015-01-01

Recently, NASA has been looking into utilizing landers that can be propelled by LOX-CH (sub 4), to be used for long duration missions. Using landers that utilize such propellants, also provides the opportunity to use solid oxide fuel cells as a power option, especially since they are able to process methane into a reactant through fuel reformation. One type of reformation, called steam methane reformation, is a process to reform methane into a hydrogen-rich product by reacting methane and steam (fuel cell exhaust) over a catalyst. A steam methane reformation system could potentially use the fuel cell's own exhaust to create a reactant stream that is hydrogen-rich, and requires less internal reforming of the incoming methane. Also, steam reformation may hold some advantages over other types of reforming, such as partial oxidation (PROX) reformation. Steam reformation does not require oxygen, while up to 25 percent can be lost in PROX reformation due to unusable CO (sub 2) reformation. NASA's Johnson Space Center has conducted various phases of steam methane reformation testing, as a viable solution for in-space reformation. This has included using two different types of catalysts, developing a custom reformer, and optimizing the test system to find the optimal performance parameters and operating conditions.

Rare earth/iron fluoride and methods for making and using same

DOEpatents

Schmidt, Frederick A.; Wheelock, John T.; Peterson, David T.

1991-12-17

A particulate mixture of Fe.sub.2 O.sub.3 and RE.sub.2 O.sub.3, where RE is a rare earth element, is reacted with an excess of HF acid to form an insoluble fluoride compound (salt) comprising REF.sub.3 and FeF.sub.3 present in solid solution in the REF.sub.3 crystal lattice. The REF.sub.3 /FeF.sub.3 compound is dried to render it usable as a reactant in the thermite reduction process as well as other processes which require an REF.sub.3 /FeF.sub.3 mixture. The dried REF.sub.3 /FeF.sub.3 compound comprises about 5 weight % to about 40 weight % of FeF.sub.3 and the balance REF.sub.3 to this end.

Templated and template-free fabrication strategies for zero-dimensional hollow MOF superstructures.

PubMed

Kim, Hyehyun; Lah, Myoung Soo

2017-05-16

Various fabrication strategies for hollow metal-organic framework (MOF) superstructures are reviewed and classified using various types of external templates and their properties. Hollow MOF superstructures have also been prepared without external templates, wherein unstable intermediates obtained during reactions convert to the final hollow MOF superstructures. Many hollow MOF superstructures have been fabricated using hard templates. After the core-shell core@MOF structure was prepared using a hard template, the core was selectively etched to generate a hollow MOF superstructure. Another approach for generating hollow superstructures is to use a solid reactant as a sacrificial template; this method requires no additional etching process. Soft templates such as discontinuous liquid/emulsion droplets and gas bubbles in a continuous soft phase have also been employed to prepare hollow MOF superstructures.

Bayesian inversion analysis of nonlinear dynamics in surface heterogeneous reactions.

PubMed

Omori, Toshiaki; Kuwatani, Tatsu; Okamoto, Atsushi; Hukushima, Koji

2016-09-01

It is essential to extract nonlinear dynamics from time-series data as an inverse problem in natural sciences. We propose a Bayesian statistical framework for extracting nonlinear dynamics of surface heterogeneous reactions from sparse and noisy observable data. Surface heterogeneous reactions are chemical reactions with conjugation of multiple phases, and they have the intrinsic nonlinearity of their dynamics caused by the effect of surface-area between different phases. We adapt a belief propagation method and an expectation-maximization (EM) algorithm to partial observation problem, in order to simultaneously estimate the time course of hidden variables and the kinetic parameters underlying dynamics. The proposed belief propagation method is performed by using sequential Monte Carlo algorithm in order to estimate nonlinear dynamical system. Using our proposed method, we show that the rate constants of dissolution and precipitation reactions, which are typical examples of surface heterogeneous reactions, as well as the temporal changes of solid reactants and products, were successfully estimated only from the observable temporal changes in the concentration of the dissolved intermediate product.

Chiroplasmonic magnetic gold nanocomposites produced by one-step aqueous method using κ-carrageenan.

PubMed

Lesnichaya, Marina V; Sukhov, Boris G; Aleksandrova, Galina P; Gasilova, Ekaterina R; Vakul'skaya, Tamara I; Khutsishvili, Spartak S; Sapozhnikov, Anatoliy N; Klimenkov, Igor V; Trofimov, Boris A

2017-11-01

Novel water-soluble chiroplasmonic nanobiocomposites with directly varied gold content were synthesized by a one-step redox method in water using a biocompatible polysaccharide κ-carrageenan (industrial product from algae) as both reducing and stabilizing matrix. The influence of the reactants ratio, temperature, and pH on the reaction was studied and the optimal reaction parameters were found. The structure and the properties of composite nanomaterials were examined in solid state and aqueous solutions by using complementary physical-chemical methods X-ray diffraction analysis, transmission electron microscopy, spectroscopy of electron paramagnetic resonance, atomic absorption and optical spectroscopy, polarimetry including optical rotatory dispersion with registration of interphase-crossbred Cotton effect of a chiral polysaccharide matrix on plasmonic chromophore of gold nanoparticles, dynamic and static light scattering. The new perspective multi-purpose nanocomposites demonstrate a complex of chiroplasmonic and magnetic properties, imparted by both nanoparticles and radicals enriched chiral polysaccharide matrix. Copyright © 2017 Elsevier Ltd. All rights reserved.

Low Temperature Pulsed Plasma Deposition. Part 1. A New Technique for Thin Film Deposition with Complete Gas Dissociation.

DTIC Science & Technology

1988-04-12

Res. Minneapolis Dr P Klocek Texas Instruments, Dallas Dr D N Lewis Naval Research Lab Dr S Musikant General Electric Co, Philadelphia Dr D Perry US...by utilising only a small fraction of the available reactants. Not only is this wasteful, limiting the method to reactants that are comparatively

Precise non-steady-state characterization of solid active materials with no preliminary mechanistic assumptions

DOE PAGES

Constales, Denis; Yablonsky, Gregory S.; Wang, Lucun; ...

2017-04-25

This paper presents a straightforward and user-friendly procedure for extracting a reactivity characterization of catalytic reactions on solid materials under non-steady-state conditions, particularly in temporal analysis of products (TAP) experiments. The kinetic parameters derived by this procedure can help with the development of detailed mechanistic understanding. The procedure consists of the following two major steps: 1) Three “Laplace reactivities” are first determined based on the moments of the exit flow pulse response data; 2) Depending on a select kinetic model, kinetic constants of elementary reaction steps can then be expressed as a function of reactivities and determined accordingly. In particular,more » we distinguish two calculation methods based on the availability and reliability of reactant and product data. The theoretical results are illustrated using a reverse example with given parameters as well as an experimental example of CO oxidation over a supported Au/SiO 2 catalyst. The procedure presented here provides an efficient tool for kinetic characterization of many complex chemical reactions.« less

Reactive solid surface morphology variation via ionic diffusion.

PubMed

Sun, Zhenchao; Zhou, Qiang; Fan, Liang-Shih

2012-08-14

In gas-solid reactions, one of the most important factors that determine the overall reaction rate is the solid morphology, which can be characterized by a combination of smooth, convex and concave structures. Generally, the solid surface structure varies in the course of reactions, which is classically noted as being attributed to one or more of the following three mechanisms: mechanical interaction, molar volume change, and sintering. Here we show that if a gas-solid reaction involves the outward ionic diffusion of a solid-phase reactant then this outward ionic diffusion could eventually smooth the surface with an initial concave and/or convex structure. Specifically, the concave surface is filled via a larger outward diffusing surface pointing to the concave valley, whereas the height of the convex surface decreases via a lower outward diffusion flux in the vertical direction. A quantitative 2-D continuum diffusion model is established to analyze these two morphological variation processes, which shows consistent results with the experiments. This surface morphology variation by solid-phase ionic diffusion serves to provide a fourth mechanism that supplements the traditionally acknowledged solid morphology variation or, in general, porosity variation mechanisms in gas-solid reactions.

Method of purifying metallurgical grade silicon employing reduced pressure atmospheric control

NASA Technical Reports Server (NTRS)

Ingle, W. M.; Thompson, S. W.; Chaney, R. E. (Inventor)

1979-01-01

A method in which a quartz tube is charged with chunks of metallurgical grade silicon and/or a mixture of such chunks and high purity quartz sand, and impurities from a class including aluminum, boron, as well as certain transition metals including nickel, iron, and manganese is described. The tube is then evacuated and heated to a temperature within a range of 800 C to 1400 C. A stream of gas comprising a reactant, such as silicon tetrafluoride, is continuously delivered at low pressures through the charge for causing a metathetical reaction of impurities of the silicon and the reactant to occur for forming a volatile halide and leaving a residue of silicon of an improved purity. The reactant which included carbon monoxide gas and impurities such as iron and nickel react to form volatile carbonyls.

Optimization of polymer electrolyte membrane fuel cell flow channels using a genetic algorithm

NASA Astrophysics Data System (ADS)

Catlin, Glenn; Advani, Suresh G.; Prasad, Ajay K.

The design of the flow channels in PEM fuel cells directly impacts the transport of reactant gases to the electrodes and affects cell performance. This paper presents results from a study to optimize the geometry of the flow channels in a PEM fuel cell. The optimization process implements a genetic algorithm to rapidly converge on the channel geometry that provides the highest net power output from the cell. In addition, this work implements a method for the automatic generation of parameterized channel domains that are evaluated for performance using a commercial computational fluid dynamics package from ANSYS. The software package includes GAMBIT as the solid modeling and meshing software, the solver FLUENT, and a PEMFC Add-on Module capable of modeling the relevant physical and electrochemical mechanisms that describe PEM fuel cell operation. The result of the optimization process is a set of optimal channel geometry values for the single-serpentine channel configuration. The performance of the optimal geometry is contrasted with a sub-optimal one by comparing contour plots of current density, oxygen and hydrogen concentration. In addition, the role of convective bypass in bringing fresh reactant to the catalyst layer is examined in detail. The convergence to the optimal geometry is confirmed by a bracketing study which compares the performance of the best individual to those of its neighbors with adjacent parameter values.

Kinetics and mechanism of solid decompositions — From basic discoveries by atomic absorption spectrometry and quadrupole mass spectroscopy to thorough thermogravimetric analysis

NASA Astrophysics Data System (ADS)

L'vov, Boris V.

2008-02-01

This paper sums up the evolution of thermochemical approach to the interpretation of solid decompositions for the past 25 years. This period includes two stages related to decomposition studies by different techniques: by ET AAS and QMS in 1981-2001 and by TG in 2002-2007. As a result of ET AAS and QMS investigations, the method for determination of absolute rates of solid decompositions was developed and the mechanism of decompositions through the congruent dissociative vaporization was discovered. On this basis, in the period from 1997 to 2001, the decomposition mechanisms of several classes of reactants were interpreted and some unusual effects observed in TA were explained. However, the thermochemical approach has not received any support by other TA researchers. One of the potential reasons of this distrust was the unreliability of the E values measured by the traditional Arrhenius plot method. The theoretical analysis and comparison of metrological features of different methods used in the determinations of thermochemical quantities permitted to conclude that in comparison with the Arrhenius plot and second-law methods, the third-law method is to be very much preferred. However, this method cannot be used in the kinetic studies by the Arrhenius approach because its use suggests the measuring of the equilibrium pressures of decomposition products. On the contrary, the method of absolute rates is ideally suitable for this purpose. As a result of much higher precision of the third-law method, some quantitative conclusions that follow from the theory were confirmed, and several new effects, which were invisible in the framework of the Arrhenius approach, have been revealed. In spite of great progress reached in the development of reliable methodology, based on the third-law method, the thermochemical approach remains unclaimed as before.

Catalytic conversion of hydrocarbons to hydrogen and high-value carbon

DOEpatents

Shah, Naresh; Panjala, Devadas; Huffman, Gerald P.

2005-04-05

The present invention provides novel catalysts for accomplishing catalytic decomposition of undiluted light hydrocarbons to a hydrogen product, and methods for preparing such catalysts. In one aspect, a method is provided for preparing a catalyst by admixing an aqueous solution of an iron salt, at least one additional catalyst metal salt, and a suitable oxide substrate support, and precipitating metal oxyhydroxides onto the substrate support. An incipient wetness method, comprising addition of aqueous solutions of metal salts to a dry oxide substrate support, extruding the resulting paste to pellet form, and calcining the pellets in air is also discloses. In yet another aspect, a process is provided for producing hydrogen from an undiluted light hydrocarbon reactant, comprising contacting the hydrocarbon reactant with a catalyst as described above in a reactor, and recovering a substantially carbon monoxide-free hydrogen product stream. In still yet another aspect, a process is provided for catalytic decomposition of an undiluted light hydrocarbon reactant to obtain hydrogen and a valuable multi-walled carbon nanotube coproduct.

Improved flow cytometer measurement of binding assays

DOEpatents

Saunders, G.C.

1984-05-30

The invention relates to a method of measuring binding assays carried out with different size particles wherein the binding assay sample is run through a flow cytometer without separating the sample from the marking agent. The amount of a binding reactant present in a sample is determined by providing particles with a coating of binder and also a known quantity of smaller particles with a coating of binder reactant. The binding reactant is the same as the binding reactant present in the sample. The smaller particles also contain a fluorescent chemical. The particles are combined with the sample and the binding reaction is allowed to occur for a set length of time followed by combining the smaller particles with the mixture of the particles and the sample produced and allowing the binding reactions to proceed to equilibrium. The fluorescence and light scatter of the combined mixture is then measured as the combined mixture passes through a flow cytometer equipped with a laser to bring about fluorescence, and the number and strength of fluorescent events are compared. A similar method is also provided for determining the amount of antigen present in the sample by providing spheres with an antibody coating and some smaller spheres with an antigen coating. (LEW)

Amphiphilic phase-transforming catalysts for transesterification of triglycerides

NASA Astrophysics Data System (ADS)

Nawaratna, Gayan Ivantha

Heterogeneous catalytic reactions that involve immiscible liquid-phase reactants are challenging to conduct due to limitations associated with mass transport. Nevertheless, there are numerous reactions such as esterification, transesterification, etherification, and hydrolysis where two immiscible liquid reactants (such as polar and non-polar liquids) need to be brought into contact with a catalyst. With the intention of alleviating mass transport issues associated with such systems but affording the ability to separate the catalyst once the reaction is complete, the overall goal of this study is geared toward developing a catalyst that has emulsification properties as well as the ability to phase-transfer (from liquid-phase to solid-phase) while the reaction is ongoing and evaluating the effectiveness of such a catalytic process in a practical reaction. To elucidate this concept, the transesterification reaction was selected. Metal-alkoxides that possess acidic and basic properties (to catalyze the reaction), amphiphilic properties (to stabilize the alcohol/oil emulsion) and that can undergo condensation polymerization when heated (to separate as a solid subsequent to the completion of the reaction) were used to test the concept. Studies included elucidating the effect of metal sites and alkoxide sites and their concentration effects on transesterification reaction, effect of various metal alkoxide groups on the phase stability of the reactant system, and kinetic effects of the reaction system. The studies revealed that several transition-metal alkoxides, especially, titanium and yttrium based, responded positively to this reaction system. These alkoxides were able to be added to the reaction medium in liquid phase and were able to stabilize the alcohol/oil system. The alkoxides were selective to the transesterification reaction giving a range of ester yields (depending on the catalyst used). It was also observed that transition-metal alkoxides were able to be recovered in the form of their polymerized counterparts as a result of condensation polymerization subsequent to completion of the transesterification reaction.

Solid polymer membrane program

NASA Technical Reports Server (NTRS)

1971-01-01

The results are presented for a solid polymer electrolyte fuel cell development program. Failure mechanism was identified and resolution of the mechanism experienced in small stack testing was demonstrated. The effect included laboratory analysis and evaluation of a matrix of configurations and operational variables for effects on the degree of hydrogen fluoride released from the cell and on the degree of blistering/delamination occurring in the reactant inlet areas of the cell and to correlate these conditions with cell life capabilities. The laboratory evaluation tests were run at conditions intended to accelerate the degradation of the solid polymer electrolyte in order to obtain relative evaluations as quick as possible. Evaluation of the resolutions for the identified failure mechanism in space shuttle configuration cell assemblies was achieved with the fabrication and life testing of two small stack buildups of four cell assemblies and eight cells each.

Thermodynamic Models for Aqueous Alteration Coupled with Volume and Pressure Changes in Asteroids

NASA Technical Reports Server (NTRS)

Mironenko, M. V.; Zolotov, M. Y.

2005-01-01

All major classes of chondrites show signs of alteration on their parent bodies (asteroids). The prevalence of oxidation and hydration in alteration pathways implies that water was the major reactant. Sublimation and melting of water ice, generation of gases, formation of aqueous solutions, alteration of primary minerals and glasses and formation of secondary solids in interior parts of asteroids was likely to be driven by heat from the radioactive decay of short-lived radionuclides. Progress of alteration reactions should have affected masses and volumes of solids, and aqueous and gas phases. In turn, pressure evolution should have been controlled by changes in volumes and temperatures, escape processes, and production/ consumption of gases.

Principles and Applications of Solid Polymer Electrolyte Reactors for Electrochemical Hydrodehalogenation of Organic Pollutants

NASA Astrophysics Data System (ADS)

Cheng, Hua; Scott, Keith

The ability to re-cycle halogenated liquid wastes, based on electrochemical hydrodehalogenation (EHDH), will provide a significant economic advantage and will reduce the environmental burden in a number of processes. The use of a solid polymer electrolyte (SPE) reactor is very attractive for this purpose. Principles and features of electrochemical HDH technology and SPE EHDH reactors are described. The SPE reactor enables selective dehalogenation of halogenated organic compounds in both aqueous and non-aqueous media with high current efficiency and low energy consumption. The influence of operating conditions, including cathode material, current density, reactant concentration and temperature on the HDH process and its stability are examined.

Method of preparing a positive electrode for an electrochemical cell

DOEpatents

Tomczuk, Zygmunt

1979-01-01

A method of preparing an electrochemical cell including a metal sulfide as the positive electrode reactant and lithium alloy as the negative electrochemical reactant with an alkali metal, molten salt electrolyte is disclosed which permits the assembly to be accomplished in air. The electrode reactants are introduced in the most part as a sulfide of lithium and the positive electrode metal in a single-phase compound. For instance, Li.sub.2 FeS.sub.2 is a single-phase compound that is produced by the reaction of Li.sub.2 S and FeS. This compound is an intermediate in the positive electrode cycle from FeS.sub.2 to Fe and Li.sub.2 S. Its use minimizes volumetric changes from the assembled to the charged and discharged conditions of the electrode and minimizes electrode material interaction with air and moisture during assembly.

Hydrogen generation systems and methods utilizing sodium silicide and sodium silica gel materials

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

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

Systems, devices, and methods combine thermally stable reactant materials and aqueous solutions to generate hydrogen and a non-toxic liquid by-product. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Springs and other pressurization mechanisms pressurize and deliver an aqueous solution to the reaction. A check valve and other pressure regulation mechanisms regulate the pressure of the aqueous solution delivered to the reactantmore » fuel material in the reactor based upon characteristics of the pressurization mechanisms and can regulate the pressure of the delivered aqueous solution as a steady decay associated with the pressurization force. The pressure regulation mechanism can also prevent hydrogen gas from deflecting the pressure regulation mechanism.« less

Apparatus and method for continuous production of materials

DOEpatents

Chang, Chih-hung; Jin, Hyungdae

2014-08-12

Embodiments of a continuous-flow injection reactor and a method for continuous material synthesis are disclosed. The reactor includes a mixing zone unit and a residence time unit removably coupled to the mixing zone unit. The mixing zone unit includes at least one top inlet, a side inlet, and a bottom outlet. An injection tube, or plurality of injection tubes, is inserted through the top inlet and extends past the side inlet while terminating above the bottom outlet. A first reactant solution flows in through the side inlet, and a second reactant solution flows in through the injection tube(s). With reference to nanoparticle synthesis, the reactant solutions combine in a mixing zone and form nucleated nanoparticles. The nucleated nanoparticles flow through the residence time unit. The residence time unit may be a single conduit, or it may include an outer housing and a plurality of inner tubes within the outer housing.

Method for the catalytic conversion of organic materials into a product gas

DOEpatents

Elliott, D.C.; Sealock, L.J. Jr.; Baker, E.G.

1997-04-01

A method for converting organic material into a product gas includes: (a) providing a liquid reactant mixture containing liquid water and liquid organic material within a pressure reactor; (b) providing an effective amount of a reduced metal catalyst selected from the group consisting of ruthenium, rhodium, osmium and iridium or mixtures thereof within the pressure reactor; and (c) maintaining the liquid reactant mixture and effective amount of reduced metal catalyst in the pressure reactor at temperature and pressure conditions of from about 300 C to about 450 C; and at least 130 atmospheres for a period of time, the temperature and pressure conditions being effective to maintain the reactant mixture substantially as liquid, the effective amount of reduced metal catalyst and the period of time being sufficient to catalyze a reaction of the liquid organic material to produce a product gas composed primarily of methane, carbon dioxide and hydrogen. 5 figs.

Method for the catalytic conversion of organic materials into a product gas

DOEpatents

Elliott, Douglas C.; Sealock, Jr., L. John; Baker, Eddie G.

1997-01-01

A method for converting organic material into a product gas includes: a) providing a liquid reactant mixture containing liquid water and liquid organic material within a pressure reactor; b) providing an effective amount of a reduced metal catalyst selected from the group consisting of ruthenium, rhodium, osmium and iridium or mixtures thereof within the pressure reactor; and c) maintaining the liquid reactant mixture and effective amount of reduced metal catalyst in the pressure reactor at temperature and pressure conditions of from about 300.degree. C. to about 450.degree. C.; and at least 130 atmospheres for a period of time, the temperature and pressure conditions being effective to maintain the reactant mixture substantially as liquid, the effective amount of reduced metal catalyst and the period of time being sufficient to catalyze a reaction of the liquid organic material to produce a product gas composed primarily of methane, carbon dioxide and hydrogen.

Staged membrane oxidation reactor system

DOEpatents

Repasky, John Michael; Carolan, Michael Francis; Stein, VanEric Edward; Chen, Christopher Ming-Poh

2014-05-20

Ion transport membrane oxidation system comprising (a) two or more membrane oxidation stages, each stage comprising a reactant zone, an oxidant zone, one or more ion transport membranes separating the reactant zone from the oxidant zone, a reactant gas inlet region, a reactant gas outlet region, an oxidant gas inlet region, and an oxidant gas outlet region; (b) an interstage reactant gas flow path disposed between each pair of membrane oxidation stages and adapted to place the reactant gas outlet region of a first stage of the pair in flow communication with the reactant gas inlet region of a second stage of the pair; and (c) one or more reactant interstage feed gas lines, each line being in flow communication with any interstage reactant gas flow path or with the reactant zone of any membrane oxidation stage receiving interstage reactant gas.

Staged membrane oxidation reactor system

DOEpatents

Repasky, John Michael; Carolan, Michael Francis; Stein, VanEric Edward; Chen, Christopher Ming-Poh

2013-04-16

Ion transport membrane oxidation system comprising (a) two or more membrane oxidation stages, each stage comprising a reactant zone, an oxidant zone, one or more ion transport membranes separating the reactant zone from the oxidant zone, a reactant gas inlet region, a reactant gas outlet region, an oxidant gas inlet region, and an oxidant gas outlet region; (b) an interstage reactant gas flow path disposed between each pair of membrane oxidation stages and adapted to place the reactant gas outlet region of a first stage of the pair in flow communication with the reactant gas inlet region of a second stage of the pair; and (c) one or more reactant interstage feed gas lines, each line being in flow communication with any interstage reactant gas flow path or with the reactant zone of any membrane oxidation stage receiving interstage reactant gas.

Staged membrane oxidation reactor system

DOEpatents

Repasky, John Michael; Carolan, Michael Francis; Stein, VanEric Edward; Chen, Christopher Ming-Poh

2012-09-11

Ion transport membrane oxidation system comprising (a) two or more membrane oxidation stages, each stage comprising a reactant zone, an oxidant zone, one or more ion transport membranes separating the reactant zone from the oxidant zone, a reactant gas inlet region, a reactant gas outlet region, an oxidant gas inlet region, and an oxidant gas outlet region; (b) an interstage reactant gas flow path disposed between each pair of membrane oxidation stages and adapted to place the reactant gas outlet region of a first stage of the pair in flow communication with the reactant gas inlet region of a second stage of the pair; and (c) one or more reactant interstage feed gas lines, each line being in flow communication with any interstage reactant gas flow path or with the reactant zone of any membrane oxidation stage receiving interstage reactant gas.

La-Sr-Ni-Co-O based perovskite-type solid solutions as catalyst precursors in the CO 2 reforming of methane

NASA Astrophysics Data System (ADS)

Valderrama, Gustavo; Kiennemann, Alain; Goldwasser, Mireya R.

La 1- xSr xNi 0.4Co 0.6O 3 and La 0.8Sr 0.2Ni 1- yCo yO 3 solid solutions with perovskite-type structure were synthesized by the sol-gel resin method and used as catalytic precursors in the dry reforming of methane with CO 2 to syngas, between 873 and 1073 K at atmospheric pressure under continuous flow of reactant gases with CH 4/CO 2 = 1 ratio. These quaternary oxides were characterized by X-ray diffraction (XRD), BET specific surface area and temperature-programmed reduction (TPR) techniques. XRD analyses of the more intense diffraction peaks and cell parameter measurements showed formation of La-Sr-Ni-Co-O solid solutions with La 0.9Sr 0.1CoO 3 and/or La 0.9Sr 0.1NiO 3 as the main crystallographic phases present on the solids depending on the degree of substitution. TPR analyses showed that Sr doping decreases the temperature of reduction via formation of intermediary species producing Ni 0, Co 0 with particle sizes in the range of nanometers over the SrO and La 2O 3 phases. These metallic nano particles highly dispersed in the solid matrix are responsible for the high activity shown during the reaction and avoid carbon formation. The presence of Sr in doping quantities also promotes the secondary reactions of carbon formation and water-gas shift in a very small extension during the dry reforming reaction.

Internal voltage control of hydrogen-oxygen fuel cells: Feasibility study

NASA Technical Reports Server (NTRS)

Prokopius, P. R.

1975-01-01

An experimental study was conducted to assess the feasibility of internal voltage regulation of fuel cell systems. Two methods were tested. In one, reactant partial pressure was used as the voltage control parameter and in the other reactant total pressure was used for control. Both techniques were breadboarded and tested on a single alkaline-electrolyte fuel cell. Both methods were found to be possible forms of regulation, however, of the two the total pressure technique would be more efficient, simpler to apply and would provide better transient characteristics.

Innovative solar thermochemical water splitting.

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

Hogan, Roy E. Jr.; Siegel, Nathan P.; Evans, Lindsey R.

2008-02-01

Sandia National Laboratories (SNL) is evaluating the potential of an innovative approach for splitting water into hydrogen and oxygen using two-step thermochemical cycles. Thermochemical cycles are heat engines that utilize high-temperature heat to produce chemical work. Like their mechanical work-producing counterparts, their efficiency depends on operating temperature and on the irreversibility of their internal processes. With this in mind, we have invented innovative design concepts for two-step solar-driven thermochemical heat engines based on iron oxide and iron oxide mixed with other metal oxides (ferrites). The design concepts utilize two sets of moving beds of ferrite reactant material in close proximitymore » and moving in opposite directions to overcome a major impediment to achieving high efficiency--thermal recuperation between solids in efficient counter-current arrangements. They also provide inherent separation of the product hydrogen and oxygen and are an excellent match with high-concentration solar flux. However, they also impose unique requirements on the ferrite reactants and materials of construction as well as an understanding of the chemical and cycle thermodynamics. In this report the Counter-Rotating-Ring Receiver/Reactor/Recuperator (CR5) solar thermochemical heat engine and its basic operating principals are described. Preliminary thermal efficiency estimates are presented and discussed. Our ferrite reactant material development activities, thermodynamic studies, test results, and prototype hardware development are also presented.« less

Engine and method for operating an engine

DOEpatents

Lauper, Jr., John Christian; Willi, Martin Leo [Dunlap, IL; Thirunavukarasu, Balamurugesh [Peoria, IL; Gong, Weidong [Dunlap, IL

2008-12-23

A method of operating an engine is provided. The method may include supplying a combustible combination of reactants to a combustion chamber of the engine, which may include supplying a first hydrocarbon fuel, hydrogen fuel, and a second hydrocarbon fuel to the combustion chamber. Supplying the second hydrocarbon fuel to the combustion chamber may include at least one of supplying at least a portion of the second hydrocarbon fuel from an outlet port that discharges into an intake system of the engine and supplying at least a portion of the second hydrocarbon fuel from an outlet port that discharges into the combustion chamber. Additionally, the method may include combusting the combustible combination of reactants in the combustion chamber.

Pressure Regulator With Internal Ejector Circulation Pump, Flow and Pressure Measurement Porting, and Fuel Cell System Integration Options

NASA Technical Reports Server (NTRS)

Vasquez, Arturo

2011-01-01

An advanced reactant pressure regulator with an internal ejector reactant circulation pump has been developed to support NASA's future fuel cell power systems needs. These needs include reliable and safe operation in variable-gravity environments, and for exploration activities with both manned and un manned vehicles. This product was developed for use in Proton Exchange Membrane Fuel Cell (PEMFC) power plant reactant circulation systems, but the design could also be applied to other fuel cell system types, (e.g., solid-oxide or alkaline) or for other gas pressure regulation and circulation needs. The regulator design includes porting for measurement of flow and pressure at key points in the system, and also includes several fuel cell system integration options. NASA has recognized ejectors as a viable alternative to mechanical pumps for use in spacecraft fuel cell power systems. The ejector motive force is provided by a variable, high-pressure supply gas that travels through the ejector s jet nozzle, whereby the pressure energy of the fluid stream is converted to kinetic energy in the gas jet. The ejector can produce circulation-to-consumption-flow ratios that are relatively high (2-3 times), and this phenomenon can potentially (with proper consideration of the remainder of the fuel cell system s design) be used to provide completely for reactant pre-humidification and product water removal in a fuel cell system. Specifically, a custom pressure regulator has been developed that includes: (1) an ejector reactant circulation pump (with interchangeable jet nozzles and mixer sections, gas-tight sliding and static seals in required locations, and internal fluid porting for pressure-sensing at the regulator's control elements) and (2) internal fluid porting to allow for flow rate and system pressure measurements. The fluid porting also allows for inclusion of purge, relief, and vacuum-breaker check valves on the regulator assembly. In addition, this regulator could also be used with NASA's advanced nonflow-through fuel cell power systems by simply incorporating a jet nozzle with an appropriate nozzle diameter.

Non-equilibrium reactive flux: A unified framework for slow and fast reaction kinetics.

PubMed

Bose, Amartya; Makri, Nancy

2017-10-21

The flux formulation of reaction rate theory is recast in terms of the expectation value of the reactive flux with an initial condition that corresponds to a non-equilibrium, factorized reactant density. In the common case of slow reactive processes, the non-equilibrium expression reaches the plateau regime only slightly slower than the equilibrium flux form. When the reactants are described by a single quantum state, as in the case of electron transfer reactions, the factorized reactant density describes the true initial condition of the reactive process. In such cases, the time integral of the non-equilibrium flux expression yields the reactant population as a function of time, allowing characterization of the dynamics in cases where there is no clear separation of time scales and thus a plateau regime cannot be identified. The non-equilibrium flux offers a unified approach to the kinetics of slow and fast chemical reactions and is ideally suited to mixed quantum-classical methods.

Waste conversion into high-value ceramics: Carbothermal nitridation synthesis of titanium nitride nanoparticles using automotive shredder waste.

PubMed

Mayyas, Mohannad; Pahlevani, Farshid; Maroufi, Samane; Liu, Zhao; Sahajwalla, Veena

2017-03-01

Environmental concern about automotive shredder residue (ASR) has increased in recent years due to its harmful content of heavy metals. Although several approaches of ASR management have been suggested, these approaches remain commercially unproven. This study presents an alternative approach for ASR management where advanced materials can be generated as a by-product. In this approach, titanium nitride (TiN) has been thermally synthesized by nitriding pressed mixture of automotive shredder residue (ASR) and titanium oxide (TiO 2 ). Interactions between TiO 2 and ASR at non-isothermal conditions were primarily investigated using thermogravimetric analysis (TGA) and differential scanning calorimetry. Results indicated that TiO 2 influences and catalyses degradation reactions of ASR, and the temperature, at which reduction starts, was determined around 980 °C. The interaction between TiO 2 and ASR at isothermal conditions in the temperature range between 1200 and 1550 °C was also studied. The pressed mixture of both materials resulted in titanium nitride (TiN) ceramic at all given temperatures. Formation kinetics were extracted using several models for product layer diffusion-controlled solid-solid and solid-fluid reactions. The effect of reactants ratio and temperature on the degree of conversion and morphology was investigated. The effect of reactants ratio was found to have considerable effect on the morphology of the resulting material, while temperature had a lesser impact. Several unique structures of TiN (porous nanostructured, polycrystalline, micro-spherical and nano-sized structures) were obtained by simply tuning the ratio of TiO 2 to ASR, and a product with appreciable TiN content of around 85% was achieved after only one hour nitridation at 1550 °C. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fuel cell system blower configuration

DOEpatents

Patel, Kirtikumar H.; Saito, Kazuo

2017-11-28

An exemplary fuel cell system includes a cell stack assembly having a plurality of cathode components and a plurality of anode components. A first reactant blower has an outlet situated to provide a first reactant to the cathode components. A second reactant blower has an outlet situated to provide a second reactant to the anode components. The second reactant blower includes a fan portion that moves the second reactant through the outlet. The second reactant blower also includes a motor portion that drives the fan portion and a bearing portion associated with the fan portion and the motor portion. The motor portion has a motor coolant inlet coupled with the outlet of the first reactant blower to receive some of the first reactant for cooling the motor portion.

Surface-Activated Coupling Reactions Confined on a Surface.

PubMed

Dong, Lei; Liu, Pei Nian; Lin, Nian

2015-10-20

Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density-functional theory (DFT) transition-state calculations have been used to shed light on reaction mechanisms and to unravel the trends of different surface materials. In this Account, we discuss recent progress made in two widely studied surface-confined coupling reactions, aryl-aryl (Ullmann-type) coupling and alkyne-alkyne (Glaser-type) coupling, and focus on surface activation effects. Combined experimental and theoretical studies on the same reactions taking place on different metal surfaces have clearly demonstrated that different surfaces not only reduce the reaction barrier differently and render different reaction pathways but also control the morphology of the reaction products and, to some degree, select the reaction products. We end the Account with a list of questions to be addressed in the future. Satisfactorily answering these questions may lead to using the surface-confined coupling reactions to synthesize predefined products with high yield.

Highly efficient quenching of tris(2,2'-bipyridyl)ruthenium(II) electrochemiluminescence by ozone using formaldehyde, methylglyoxal, and glyoxalate as co-reactants and its application to ozone sensing.

PubMed

Gao, Ying; Liu, Xiaoyun; Qi, Wenjing; Gao, Wenyue; Li, Yunhui; Xu, Guobao

2015-06-21

Most electrochemiluminescence (ECL) systems require high concentrations of quencher to totally quench ECL. In this study, we found that ozone can quench tris(2,2'-bipyridyl)ruthenium(II) ECL using formaldehyde, methylglyoxal, or glyoxalate as co-reactants at a glassy carbon electrode with remarkable efficiencies even when the concentration of ozone is merely 0.25% of that of the co-reactant. The strongest quenching is observed with the tris(2,2'-bipyridyl)ruthenium(II)/formaldehyde ECL system. The tris(2,2'-bipyridyl)ruthenium(II)/formaldehyde ECL intensities decrease linearly with the ozone concentration over the range of 0.025-25 μM (r = 0.9947) with a limit of detection of 8 nM. The method is more sensitive and faster than most methods. It shows high selectivity in the presence of other ROS or oxidants and some metal ions, such as H2O2, ClO(-), Mg(2+), Ni(2+), etc. The method exhibits high recoveries for the detection of ozone in a ventilated photocopy room.

Characterizing Laminar Flame Interactions with Turbulent Fluidic Jets and Solid Obstacles for Turbulence Induction

NASA Astrophysics Data System (ADS)

Gerdts, Stephen; Chambers, Jessica; Ahmed, Kareem

2016-11-01

A detonation engine's fundamental design concept focuses on enhancing the Deflagration to Detonation Transition (DDT), the process through which subsonic flames accelerate to form a spontaneous detonation wave. Flame acceleration is driven by turbulent interactions that expand the reaction zone and induce mixing of products and reactants. Turbulence in a duct can be generated using solid obstructions, fluidic obstacles, duct angle changes, and wall skin friction. Solid obstacles have been previously explored and offer repeatable turbulence induction at the cost of pressure losses and additional system weight. Fluidic jet obstacles are a novel technique that provide advantages such as the ability to be throttled, allowing for active control of combustion modes. The scope of the present work is to expand the experimental database of varying parameters such as main flow and jet equivalence ratios, fluidic momentum ratios, and solid obstacle blockage ratios. Schlieren flow visualization and particle image velocimetry (PIV) are employed to investigate turbulent flame dynamics throughout the interaction. Optimum conditions that lead to flame acceleration for both solid and fluidic obstacles will be determined. American Chemical Society.

Solid oxide fuel cell with multi-unit construction and prismatic design

DOEpatents

McPheeters, Charles C.; Dees, Dennis W.; Myles, Kevin M.

1999-01-01

A single cell unit of a solid oxide fuel cell that is individually fabricated and sintered prior to being connected to adjacent cells to form a solid oxide fuel cell. The single cell unit is comprised of a shaped anode sheet positioned between a flat anode sheet and an anode-electrolyte-cathode (A/E/C) sheet, and a shaped cathode sheet positioned between the A/E/C sheet and a cathode-interconnect-anode (C/I/A) sheet. An alternate embodiment comprises a shaped cathode sheet positioned between an A/E/C sheet and a C/I/A sheet. The shaped sheets form channels for conducting reactant gases. Each single cell unit is individually sintered to form a finished sub-assembly. The finished sub-assemblies are connected in electrical series by interposing connective material between the end surfaces of adjacent cells, whereby individual cells may be inspected for defects and interchanged with non-defective single cell units.

Chemical Detection using Electrically Open Circuits having no Electrical Connections

NASA Technical Reports Server (NTRS)

Woodward, Stanley E.; Olgesby, Donald M.; Taylor, Bryant D.; Shams, Qamar A.

2008-01-01

This paper presents investigations to date on chemical detection using a recently developed method for designing, powering and interrogating sensors as electrically open circuits having no electrical connections. In lieu of having each sensor from a closed circuit with multiple electrically connected components, an electrically conductive geometric pattern that is powered using oscillating magnetic fields and capable of storing an electric field and a magnetic field without the need of a closed circuit or electrical connections is used. When electrically active, the patterns respond with their own magnetic field whose frequency, amplitude and bandwidth can be correlated with the magnitude of the physical quantities being measured. Preliminary experimental results of using two different detection approaches will be presented. In one method, a thin film of a reactant is deposited on the surface of the open-circuit sensor. Exposure to a specific targeted reactant shifts the resonant frequency of the sensor. In the second method, a coating of conductive material is placed on a thin non-conductive plastic sheet that is placed over the surface of the sensor. There is no physical contact between the sensor and the electrically conductive material. When the conductive material is exposed to a targeted reactant, a chemical reaction occurs that renders the material non-conductive. The change in the material s electrical resistance within the magnetic field of the sensor alters the sensor s response bandwidth and amplitude, allowing detection of the reaction without having the reactants in physical contact with the sensor.

A Chebyshev method for state-to-state reactive scattering using reactant-product decoupling: OH + H2 → H2O + H.

PubMed

Cvitaš, Marko T; Althorpe, Stuart C

2013-08-14

We extend a recently developed wave packet method for computing the state-to-state quantum dynamics of AB + CD → ABC + D reactions [M. T. Cvitaš and S. C. Althorpe, J. Phys. Chem. A 113, 4557 (2009)] to include the Chebyshev propagator. The method uses the further partitioned approach to reactant-product decoupling, which uses artificial decoupling potentials to partition the coordinate space of the reaction into separate reactant, product, and transition-state regions. Separate coordinates and basis sets can then be used that are best adapted to each region. We derive improved Chebyshev partitioning formulas which include Mandelshtam-and-Taylor-type decoupling potentials, and which are essential for the non-unitary discrete variable representations that must be used in 4-atom reactive scattering calculations. Numerical tests on the fully dimensional OH + H2 → H2O + H reaction for J = 0 show that the new version of the method is as efficient as the previously developed split-operator version. The advantages of the Chebyshev propagator (most notably the ease of parallelization for J > 0) can now be fully exploited in state-to-state reactive scattering calculations on 4-atom reactions.

Plasma-catalyzed fuel reformer

DOEpatents

Hartvigsen, Joseph J.; Elangovan, S.; Czernichowski, Piotr; Hollist, Michele

2013-06-11

A reformer is disclosed that includes a plasma zone to receive a pre-heated mixture of reactants and ionize the reactants by applying an electrical potential thereto. A first thermally conductive surface surrounds the plasma zone and is configured to transfer heat from an external heat source into the plasma zone. The reformer further includes a reaction zone to chemically transform the ionized reactants into synthesis gas comprising hydrogen and carbon monoxide. A second thermally conductive surface surrounds the reaction zone and is configured to transfer heat from the external heat source into the reaction zone. The first thermally conductive surface and second thermally conductive surface are both directly exposed to the external heat source. A corresponding method and system are also disclosed and claimed herein.

Synthesis of Sulfotyrosine-Containing Peptides by Incorporating Fluorosulfated Tyrosine Using an Fmoc-Based Solid-Phase Strategy.

PubMed

Chen, Wentao; Dong, Jiajia; Li, Suhua; Liu, Yu; Wang, Yujia; Yoon, Leonard; Wu, Peng; Sharpless, K Barry; Kelly, Jeffery W

2016-01-26

Tyrosine O-sulfation is a common protein post-translational modification that regulates many biological processes, including leukocyte adhesion and chemotaxis. Many peptides with therapeutic potential contain one or more sulfotyrosine residues. We report a one-step synthesis for Fmoc-fluorosulfated tyrosine. An efficient Fmoc-based solid-phase peptide synthetic strategy is then introduced for incorporating the fluorosulfated tyrosine residue into peptides of interest. Standard simultaneous peptide-resin cleavage and removal of the acid-labile side-chain protecting groups affords the crude peptides containing fluorosulfated tyrosine. Basic ethylene glycol, serving both as solvent and reactant, transforms the fluorosulfated tyrosine peptides into sulfotyrosine peptides in high yield. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High Temperature Advanced Structural Composites. Volume 2. Ceramic Matrix Composites, Fiber Processing and Properties, and Interfaces

DTIC Science & Technology

1993-04-02

1977) 97. 3 W. Wieswieler, E. Fitzer, G . Nagel, and H. Jager, Thin Solid Film, 148 (1987) 93. 4 T. A. Chernyshova , L. I. Kobelova, J. Mater. Scl., 20...AD-A267 023 I[E[gh ’Temperature kdvanced Structural (Composites Rensselaer Polytechnic Institute , \\ G Troy, N. Y. 12180-3590 - Final Report -- Book 2...thermodynamic data (heats of forma- ,(T p, comp.) °+p, comp.) (1) tion, absolute entropies, heat capacities) of reactants where g ’ is the chemical

Relativity and the lead-acid battery.

PubMed

Ahuja, Rajeev; Blomqvist, Andreas; Larsson, Peter; Pyykkö, Pekka; Zaleski-Ejgierd, Patryk

2011-01-07

The energies of the solid reactants in the lead-acid battery are calculated ab initio using two different basis sets at nonrelativistic, scalar-relativistic, and fully relativistic levels, and using several exchange-correlation potentials. The average calculated standard voltage is 2.13 V, compared with the experimental value of 2.11 V. All calculations agree in that 1.7-1.8 V of this standard voltage arise from relativistic effects, mainly from PbO2 but also from PbSO4.

Fabrication of Thin Electrolytes for Second-Generation Solid Oxide Fuel Cells

DTIC Science & Technology

1999-05-05

stabilized zirconia but are equally applicable to components, have been developed. Halogen com- other oxide electrolytes. pounds such as ZrCl4 and YC13...substrates. They used ZrCl4 and an oxygen source reactant. EVD is a two-step YC13 vapor mixtures as the metal compound sources process. The first step...thin zirconia layers on ited film. In this step oxygen ions formed on the porous alumina substrates. ZrCl4 and YC13 vapor water vapor side of the

Effects of different operating parameters on the particle size of silver chloride nanoparticles prepared in a spinning disk reactor

NASA Astrophysics Data System (ADS)

Dabir, Hossein; Davarpanah, Morteza; Ahmadpour, Ali

2015-07-01

The aim of this research was to present an experimental method for large-scale production of silver chloride nanoparticles using spinning disk reactor. Silver nitrate and sodium chloride were used as the reactants, and the protecting agent was gelatin. The experiments were carried out in a continuous mode by injecting the reactants onto the surface of the spinning disk, where a chemical precipitation reaction took place to form AgCl particles. The effects of various operating variables, including supersaturation, disk rotational speed, reactants flow rate, disk diameter, and excess ions, on the particle size of products were investigated. In addition, the AgCl nanoparticles were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction. According to the results, smaller AgCl particles are obtained under higher supersaturations and also higher disk rotation speeds. Moreover, in the range of our investigation, the use of lower reactants flow rates and larger disk diameter can reduce the particle size of products. The non-stoichiometric condition of reactants has a significant influence on the reduction in particle aggregation. It was also found that by optimizing the operating conditions, uniform AgCl nanoparticles with the mean size of around 37 nm can be produced.

Chemical reactions in reverse micelle systems

DOEpatents

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

1993-08-24

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

Controlled decomposition and oxidation: A treatment method for gaseous process effluents

NASA Technical Reports Server (NTRS)

Mckinley, Roger J. B., Sr.

1990-01-01

The safe disposal of effluent gases produced by the electronics industry deserves special attention. Due to the hazardous nature of many of the materials used, it is essential to control and treat the reactants and reactant by-products as they are exhausted from the process tool and prior to their release into the manufacturing facility's exhaust system and the atmosphere. Controlled decomposition and oxidation (CDO) is one method of treating effluent gases from thin film deposition processes. CDO equipment applications, field experience, and results of the use of CDO equipment and technological advances gained from the field experiences are discussed.

Method of Manufacturing Micro-Disperse Particles of Sodium Borohydride

DOEpatents

Kravitz, Stanley H.; Hecht, Andrew M.; Sylwester. Alan P.; Bell, Nelson S.

2008-09-23

A compact solid source of hydrogen gas, where the gas is generated by contacting water with micro-disperse particles of sodium borohydride in the presence of a catalyst, such as cobalt or ruthenium. The micro-disperse particles can have a substantially uniform diameter of 1-10 microns, and preferably about 3-5 microns. Ruthenium or cobalt catalytic nanoparticles can be incorporated in the micro-disperse particles of sodium borohydride, which allows a rapid and complete reaction to occur without the problems associated with caking and scaling of the surface by the reactant product sodium metaborate. A closed loop water management system can be used to recycle wastewater from a PEM fuel cell to supply water for reacting with the micro-disperse particles of sodium borohydride in a compact hydrogen gas generator. Capillary forces can wick water from a water reservoir into a packed bed of micro-disperse fuel particles, eliminating the need for using an active pump.

Method of generating hydrogen gas from sodium borohydride

DOEpatents

Kravitz, Stanley H.; Hecht, Andrew M.; Sylwester, Alan P.; Bell, Nelson S.

2007-12-11

A compact solid source of hydrogen gas, where the gas is generated by contacting water with micro-disperse particles of sodium borohydride in the presence of a catalyst, such as cobalt or ruthenium. The micro-disperse particles can have a substantially uniform diameter of 1-10 microns, and preferably about 3-5 microns. Ruthenium or cobalt catalytic nanoparticles can be incorporated in the micro-disperse particles of sodium borohydride, which allows a rapid and complete reaction to occur without the problems associated with caking and scaling of the surface by the reactant product sodium metaborate. A closed loop water management system can be used to recycle wastewater from a PEM fuel cell to supply water for reacting with the micro-disperse particles of sodium borohydride in a compact hydrogen gas generator. Capillary forces can wick water from a water reservoir into a packed bed of micro-disperse fuel particles, eliminating the need for using an active pump.

Computational analysis of species transport and electrochemical characteristics of a MOLB-type SOFC

NASA Astrophysics Data System (ADS)

Hwang, J. J.; Chen, C. K.; Lai, D. Y.

A multi-physics model coupling electrochemical kinetics with fluid dynamics has been developed to simulate the transport phenomena in mono-block-layer built (MOLB) solid oxide fuel cells (SOFC). A typical MOLB module is composed of trapezoidal flow channels, corrugated positive electrode-electrolyte-negative electrode (PEN) plates, and planar inter-connecters. The control volume-based finite difference method is employed for calculation, which is based on the conservation of mass, momentum, energy, species, and electric charge. In the porous electrodes, the flow momentum is governed by a Darcy model with constant porosity and permeability. The diffusion of reactants follows the Bruggman model. The chemistry within the plates is described via surface reactions with a fixed surface-to-volume ratio, tortuosity and average pore size. Species transports as well as the local variations of electrochemical characteristics, such as overpotential and current density distributions in the electrodes of an MOLB SOFC, are discussed in detail.

Reactor for producing large particles of materials from gases

NASA Technical Reports Server (NTRS)

Flagan, Richard C. (Inventor); Alam, Mohammed K. (Inventor)

1987-01-01

A method and apparatus is disclosed for producing large particles of material from gas, or gases, containing the material (e.g., silicon from silane) in a free-space reactor comprised of a tube (20) and controlled furnace (25). A hot gas is introduced in the center of the reactant gas through a nozzle (23) to heat a quantity of the reactant gas, or gases, to produce a controlled concentration of seed particles (24) which are entrained in the flow of reactant gas, or gases. The temperature profile (FIG. 4) of the furnace is controlled for such a slow, controlled rate of reaction that virtually all of the material released condenses on seed particles and new particles are not nucleated in the furnace. A separate reactor comprised of a tube (33) and furnace (30) may be used to form a seed aerosol which, after passing through a cooling section (34) is introduced in the main reactor tube (34) which includes a mixer (36) to mix the seed aerosol in a controlled concentration with the reactant gas or gases.

Microstructure and wear resistance of Al2O3-M7C3/Fe composite coatings produced by laser controlled reactive synthesis

NASA Astrophysics Data System (ADS)

Tan, Hui; Luo, Zhen; Li, Yang; Yan, Fuyu; Duan, Rui

2015-05-01

Based on the principle of thermite reaction of Al and Fe2O3 powders, the Al2O3 ceramic reinforced Fe-based composite coatings were fabricated on a steel substrate by laser controlled reactive synthesis and cladding. The effects of different additions of thermite reactants on the phase transition, microstructure evolution, microhardness and wear resistance of the composite coatings were investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Vickers microhardness and block-on-ring wear test, respectively. The results show that Al2O3 ceramic and M7C3 carbide are in situ synthesized via the laser controlled reactive synthesis. The Al2O3 ceramic and M7C3 carbides prefer to distribute along the γ-Fe phase boundary continuously, which separates the γ-Fe matrix and is beneficial to the grain refinement. With the increase of thermite reactants, the amount of Al2O3 ceramic and M7C3 carbide in the composite coatings increases gradually. Moreover the cladding layer changes from dendritic structure to columnar structure and martensite structure in the heat affected zone becomes coarse. The increased thermite reactants improve the microhardness and wear resistance of the in situ composite coatings obviously and enhance the hardness of the heat affected zone, which should be ascribed to the grain refinement, ceramic and carbide precipitation and solid solution strengthening.

Immobilization of Chromium from Liquid Waste of Electroplating Home-Industries by Fly Ash Geopolymerization

NASA Astrophysics Data System (ADS)

Fansuri, H.; Erviana, E.; Rosyidah, M.; Iqbal, R. M.; Utomo, W. P.; Nurlina

2018-05-01

Immobilization is one of methods that can be used to overcome the problem of water pollution by heavy metals, such as chromium, which is possibly produced in an electroplating home-industry. One method that can be used to immobilize heavy metals is by using the waste water as a reactant in a geopolymerization process. The resulting geopolymer will contain such heavy metals and keep them from being dispersed into the environment. In this research, the immobilization was carried out by geopolymerization of fly ash from PT. IPMOMI (International Power Mitsui Operation and Maintenance) in Probolinggo, Indonesia, which pass through 60 (FA 60), 100 (FA 100), and 200 (FA 200) mesh sieve and using wastewater from electroplating home-industries in Ngingas Village, Sidoarjo-Indonesia, or a solution of Cr(NO3)3.9H2O as one of its reactants. The composition of the geopolymerization follows the results of previous research, i.e using the ratio of Solid to Liquid (S/L) = 3.59, Na2O/SiO2 = 0.67, H2O/Na2O = 3.33 and SiO2/Al2O3 = 6.46. Experimental results show that the compressive strength of geopolymers without heavy metals addition increases when the particle size decreases. Geopolymer made of FA 100 has the highest compressive strength i.e 35.05 MPa. The addition of a chromium-containing wastewater in FA 100 geopolymerization produce a geopolymer with a lower compressive strength i.e 26.42 MPa while the addition of Cr(NO3)3·9H2O solution produce geopolymer with compressive strength of 24.47 MPa. The SEM-EDX photo shows that chrome was evenly dispersed in the geopolymer. Leaching test with TCLP method (Toxicity Characteristic Leaching Procedure) on the geopolymer product showed that no chrome content in the leachate was found. This suggests that chromium is immobilized by geopolymers very well.

Method for selectively preparing evoglucosenone (LGO) and other anhydrosugars from biomass in polar aprotic solvents

DOEpatents

Huber, George W.; Cao, Fei; Dumesic, James A.; Schwartz, Thomas J.

2016-06-28

A method to produce 5-hydroxymethylfurfural (HMF) is described in which a reactant including cellulose, lignocellulose, or a combination thereof, in a reaction mixture of a polar, aprotic solvent and an acid is reacted for a time, at a temperature, and at a hydrogen ion concentration wherein at least a portion of the cellulose or lignocellulose present in the reactant is converted to HMF. The reaction mixture is initially substantially devoid of water. As the reaction proceeds, dehydration of intermediates causes the water concentration in the reaction mixture to rise to no more than about 2.0 wt % water.

Method for selectively preparing 5-hydroxymethylfurfual (HMF) from biomass in polar aprotic solvents

DOEpatents

Dumesic, James A.; Huber, George W.; Weingarten, Ronen

2016-01-26

A method to produce 5-hydroxymethylfurfural (HMF) is described in which a reactant including cellulose, lignocellulose, or a combination thereof, in a reaction mixture of a polar, aprotic solvent and an acid is reacted for a time, at a temperature, and at a hydrogen ion concentration wherein at least a portion of the cellulose or lignocellulose present in the reactant is converted to HMF. The reaction mixture is initially substantially devoid of water. As the reaction proceeds, dehydration of intermediates causes the water concentration in the reaction mixture to rise to no more than about 0.2 wt % water.

Method of inducing surface ensembles on a metal catalyst

DOEpatents

Miller, Steven S.

1989-01-01

A method of inducing surface ensembles on a transition metal catalyst used in the conversion of a reactant gas or gas mixture, such as carbon monoxide and hydrogen into hydrocarbons (the Fischer-Tropsch reaction) is disclosed which comprises adding a Lewis base to the syngas (CO+H.sub.2) mixture before reaction takes place. The formation of surface ensembles in this manner restricts the number and types of reaction pathways which will be utilized, thus greatly narrowing the product distribution and maximizing the efficiency of the Fischer-Tropsch reaction. Similarly, amines may also be produced by the conversion of reactant gas or gases, such as nitrogen, hydrogen, or hydrocarbon constituents.

Method of inducing surface ensembles on a metal catalyst

DOEpatents

Miller, S.S.

1987-10-02

A method of inducing surface ensembles on a transition metal catalyst used in the conversion of a reactant gas or gas mixture, such as carbon monoxide and hydrogen into hydrocarbons (the Fischer-Tropsch reaction) is disclosed which comprises adding a Lewis base to the syngas (CO + H/sub 2/) mixture before reaction takes place. The formation of surface ensembles in this manner restricts the number and types of reaction pathways which will be utilized, thus greatly narrowing the product distribution and maximizing the efficiency of the Fischer-Tropsch reaction. Similarly, amines may also be produced by the conversion of reactant gas or gases, such as nitrogen, hydrogen, or hydrocarbon constituents.

Active control of nanolitre droplet contents with convective concentration gradients across permeable walls.

PubMed

Zeitoun, Ramsey I; Goudie, Marcus J; Zwier, Jacob; Mahawilli, David; Burns, Mark A

2011-12-07

Nanolitre droplets in microfluidic devices can be used to perform thousands of independent chemical and biological experiments while minimizing reagents, cost and time. However, the absence of simple and versatile methods capable of controlling the contents of these nanolitre chemical systems limits their scientific potential. To address this, we have developed a method that is simple to fabricate and can continuously control nanolitre chemical systems by integrating a time-resolved convective flow signal across a permeable membrane wall. With this method, we can independently control the volume and concentration of nanolitre-sized drops without ever directly contacting the fluid. Transport occurring in these systems was also analyzed and thoroughly characterized. We achieved volumetric fluid introduction and removal rates ranging from 0.23 to 4.0 pL s(-1). Furthermore, we expanded this method to perform chemical processes. We precipitated silver chloride using a flow signal of sodium chloride and silver nitrate droplets. From there, we were able to separate sodium chloride reactants with a water flow signal, and dissolve silver chloride solids with an ammonia hydroxide flow signal. Finally, we demonstrate the potential to deliver large molecules and perform physical processes like crystallization and particle packing.

Novel duplex vapor-electrochemical method for silicon solar cells

NASA Technical Reports Server (NTRS)

Kapur, V. K.; Nanis, L.; Sanjurjo, A.

1977-01-01

Silicon was produced by alternate pulse feeding of the reactants SiF4 gas and liquid sodium. The average temperature in the reactor could be controlled, by regulating the amount of reactant in each pulse. Silicon tetrafluoride gas was analyzed by mass spectrometry to determine the nature and amount of contained volatile impurities which included silicon oxyfluorides, sulfur oxyfluorides, and sulfur dioxide. Sodium metal was analyzed by emission spectrography, and it was found to contain only calcium and copper as impurities.

Fast quench reactor method

DOEpatents

Detering, B.A.; Donaldson, A.D.; Fincke, J.R.; Kong, P.C.; Berry, R.A.

1999-08-10

A fast quench reaction includes a reactor chamber having a high temperature heating means such as a plasma torch at its inlet and a means of rapidly expanding a reactant stream, such as a restrictive convergent-divergent nozzle at its outlet end. Metal halide reactants are injected into the reactor chamber. Reducing gas is added at different stages in the process to form a desired end product and prevent back reactions. The resulting heated gaseous stream is then rapidly cooled by expansion of the gaseous stream. 8 figs.

Fast quench reactor method

DOEpatents

Detering, Brent A.; Donaldson, Alan D.; Fincke, James R.; Kong, Peter C.; Berry, Ray A.

1999-01-01

A fast quench reaction includes a reactor chamber having a high temperature heating means such as a plasma torch at its inlet and a means of rapidly expanding a reactant stream, such as a restrictive convergent-divergent nozzle at its outlet end. Metal halide reactants are injected into the reactor chamber. Reducing gas is added at different stages in the process to form a desired end product and prevent back reactions. The resulting heated gaseous stream is then rapidly cooled by expansion of the gaseous stream.

Synthesis and acid catalysis of cellulose-derived carbon-based solid acid

NASA Astrophysics Data System (ADS)

Suganuma, Satoshi; Nakajima, Kiyotaka; Kitano, Masaaki; Yamaguchi, Daizo; Kato, Hideki; Hayashi, Shigenobu; Hara, Michikazu

2010-06-01

SO 3H-bearing amorphous carbon, prepared by partial carbonization of cellulose followed by sulfonation in fuming H 2SO 4, was applied as a solid catalyst for the acid-catalyzed hydrolysis of β-1,4 glucan, including cellobiose and crystalline cellulose. Structural analyses revealed that the resulting carbon material consists of graphene sheets with 1.5 mmol g -1 of SO 3H groups, 0.4 mmol g -1 of COOH, and 5.6 mmol g -1 of phenolic OH groups. The carbon catalyst showed high catalytic activity for the hydrolysis of β-1,4 glycosidic bonds in both cellobiose and crystalline cellulose. Pure crystalline cellulose was not hydrolyzed by conventional strong solid Brønsted acid catalysts such as niobic acid, Nafion ® NR-50, and Amberlyst-15, whereas the carbon catalyst efficiently hydrolyzes cellulose into water-soluble saccharides. The catalytic performance of the carbon catalyst is due to the large adsorption capacity for hydrophilic reactants and the adsorption ability of β-1,4 glucan, which is not adsorbed to other solid acids.

Carbon dioxide and water vapor high temperature electrolysis

NASA Technical Reports Server (NTRS)

Isenberg, Arnold O.; Verostko, Charles E.

1989-01-01

The design, fabrication, breadboard testing, and the data base obtained for solid oxide electrolysis systems that have applications for planetary manned missions and habitats are reviewed. The breadboard tested contains sixteen tubular cells in a closely packed bundle for the electrolysis of carbon dioxide and water vapor. The discussion covers energy requirements, volume, weight, and operational characteristics related to the measurement of the reactant and product gas compositions, temperature distribution along the electrolyzer tubular cells and through the bundle, and thermal energy losses. The reliability of individual cell performance in the bundle configuration is assessed.

Direct electrical arc ignition of hybrid rocket motors

NASA Astrophysics Data System (ADS)

Judson, Michael I., Jr.

Hybrid rockets motors provide distinct safety advantages when compared to traditional liquid or solid propellant systems, due to the inherent stability and relative inertness of the propellants prior to established combustion. As a result of this inherent propellant stability, hybrid motors have historically proven difficult to ignite. State of the art hybrid igniter designs continue to require solid or liquid reactants distinct from the main propellants. These ignition methods however, reintroduce to the hybrid propulsion system the safety and complexity disadvantages associated with traditional liquid or solid propellants. The results of this study demonstrate the feasibility of a novel direct electrostatic arc ignition method for hybrid motors. A series of small prototype stand-alone thrusters demonstrating this technology were successfully designed and tested using Acrylonitrile Butadiene Styrene (ABS) plastic and Gaseous Oxygen (GOX) as propellants. Measurements of input voltage and current demonstrated that arc-ignition will occur using as little as 10 watts peak power and less than 5 joules total energy. The motor developed for the stand-alone small thruster was adapted as a gas generator to ignite a medium-scale hybrid rocket motor using nitrous oxide /and HTPB as propellants. Multiple consecutive ignitions were performed. A large data set as well as a collection of development `lessons learned' were compiled to guide future development and research. Since the completion of this original groundwork research, the concept has been developed into a reliable, operational igniter system for a 75mm hybrid motor using both gaseous oxygen and liquid nitrous oxide as oxidizers. A development map of the direct spark ignition concept is presented showing the flow of key lessons learned between this original work and later follow on development.

Solid oxide fuel cell with multi-unit construction and prismatic design

DOEpatents

McPheeters, C.C.; Dees, D.W.; Myles, K.M.

1999-03-16

A single cell unit of a solid oxide fuel cell is described that is individually fabricated and sintered prior to being connected to adjacent cells to form a solid oxide fuel cell. The single cell unit is comprised of a shaped anode sheet positioned between a flat anode sheet and an anode-electrolyte-cathode (A/E/C) sheet, and a shaped cathode sheet positioned between the A/E/C sheet and a cathode-interconnect-anode (C/I/A) sheet. An alternate embodiment comprises a shaped cathode sheet positioned between an A/E/C sheet and a C/I/A sheet. The shaped sheets form channels for conducting reactant gases. Each single cell unit is individually sintered to form a finished sub-assembly. The finished sub-assemblies are connected in electrical series by interposing connective material between the end surfaces of adjacent cells, whereby individual cells may be inspected for defects and interchanged with non-defective single cell units. 7 figs.

Synthesis of biodiesel from a model waste oil feedstock using a carbon-based solid acid catalyst: reaction and separation.

PubMed

Shu, Qing; Nawaz, Zeeshan; Gao, Jixian; Liao, Yuhui; Zhang, Qiang; Wang, Dezheng; Wang, Jinfu

2010-07-01

A solid acid catalyst that can keep high activity and stability is necessary when low cost feedstocks are utilized for biodiesel synthesis because the reaction medium contains a large amount of water. Three solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt. The structure of these catalysts was characterized by a variety of techniques. A new process that used the coupling of the reaction and separation was employed, which greatly improved the conversion of cottonseed oil (triglyceride) and free fatty acids (FFA) when a model waste oil feedstock was used. The vegetable oil asphalt-based catalyst showed the highest catalytic activity. This was due to the high density and stability of its acid sites, its loose irregular network, its hydrophobicity that prevented the hydration of -OH species, and large pores that provided more acid sites for the reactants. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Evidence for Symmetry Reduction in Ti3(Al1-δCuδ)C2 MAX Phase Solid Solutions.

PubMed

Nechiche, Mustapha; Cabioc'h, Thierry; Caspi, Elad N; Rivin, Oleg; Hoser, Andreas; Gauthier-Brunet, Véronique; Chartier, Patrick; Dubois, Sylvain

2017-12-04

Ti 3 [Al 1-δ Cu δ ]C 2 MAX phase solid solutions have been synthesized by sintering compacted Ti 3 AlC 2 -Cu composites produced by mechanical milling. Using X-ray and neutron diffraction techniques, it is demonstrated that the Cu mixing into the Al site is accompanied by lattice distortion, which leads to symmetry reduction from a hexagonal to a monoclinic structure. Such symmetry reduction likely results from this mixing through deviation of the A-site position from the special (0, 0, 1 / 4 ) position within the P6 3 /mmc space group of the original Ti 3 AlC 2 structure. Moreover, it is demonstrated that the Cu admixture into the A site can be adjusted from the composition of the reactant mixture. The lattice parameter variation of the solid solution compounds, with 10-50 atom % Cu in the A site, is found to be consistent with Vegard's law.

Efficient Application of Continuous Fractional Component Monte Carlo in the Reaction Ensemble

PubMed Central

2017-01-01

A new formulation of the Reaction Ensemble Monte Carlo technique (RxMC) combined with the Continuous Fractional Component Monte Carlo method is presented. This method is denoted by serial Rx/CFC. The key ingredient is that fractional molecules of either reactants or reaction products are present and that chemical reactions always involve fractional molecules. Serial Rx/CFC has the following advantages compared to other approaches: (1) One directly obtains chemical potentials of all reactants and reaction products. Obtained chemical potentials can be used directly as an independent check to ensure that chemical equilibrium is achieved. (2) Independent biasing is applied to the fractional molecules of reactants and reaction products. Therefore, the efficiency of the algorithm is significantly increased, compared to the other approaches. (3) Changes in the maximum scaling parameter of intermolecular interactions can be chosen differently for reactants and reaction products. (4) The number of fractional molecules is reduced. As a proof of principle, our method is tested for Lennard-Jones systems at various pressures and for various chemical reactions. Excellent agreement was found both for average densities and equilibrium mixture compositions computed using serial Rx/CFC, RxMC/CFCMC previously introduced by Rosch and Maginn (Journal of Chemical Theory and Computation, 2011, 7, 269–279), and the conventional RxMC approach. The serial Rx/CFC approach is also tested for the reaction of ammonia synthesis at various temperatures and pressures. Excellent agreement was found between results obtained from serial Rx/CFC, experimental results from literature, and thermodynamic modeling using the Peng–Robinson equation of state. The efficiency of reaction trial moves is improved by a factor of 2 to 3 (depending on the system) compared to the RxMC/CFCMC formulation by Rosch and Maginn. PMID:28737933

Ice Melting to Release Reactants in Solution Syntheses.

PubMed

Wei, Hehe; Huang, Kai; Zhang, Le; Ge, Binghui; Wang, Dong; Lang, Jialiang; Ma, Jingyuan; Wang, Da; Zhang, Shuai; Li, Qunyang; Zhang, Ruoyu; Hussain, Naveed; Lei, Ming; Liu, Li-Min; Wu, Hui

2018-03-19

Aqueous solution syntheses are mostly based on mixing two solutions with different reactants. It is shown that freezing one solution and melting it in another solution provides a new interesting strategy to mix chemicals and to significantly change the reaction kinetics and thermodynamics. For example, a precursor solution containing a certain concentration of AgNO 3 was frozen and dropped into a reductive NaBH 4 solution at about 0 °C. The ultra-slow release of reactants was successfully achieved. An ice-melting process can be used to synthesize atomically dispersed metals, including cobalt, nickel, copper, rhodium, ruthenium, palladium, silver, osmium, iridium, platinum, and gold, which can be easily extended to other solution syntheses (such as precipitation, hydrolysis, and displacement reactions) and provide a generalized method to redesign the interphase reaction kinetics and ion diffusion in wet chemistry. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of titanium ester on synthesizing NH2-MIL-125(Ti): Morphology changes from circular plate to octahedron and rhombic dodecahedron

NASA Astrophysics Data System (ADS)

Hu, Shen; Liu, Min; Guo, Xinwen; Kuang, Zhichong; Li, Keyan; Song, Chunshan; Zhang, Guoliang

2018-06-01

Titanium based MOF materials NH2-MIL-125 was synthesized through solvothermal method. By increasing the concentration of the reactants, the morphology of NH2-MIL-125 can be controlled from circular plate to special polyhedron. Meanwhile, the polyhedron can be modulated from octahedron to rhombic dodecahedron through changing the titanium ester of the reactants from tetraethyl titanate to tetrabutyl titanate. This is the first time to obtain NH2-MIL-125 with rhombic dodecahedron morphology. The test of acetic acid as additive on morphology changes shows that the adsorption of additives on special facets shows a more significant impact on the morphology formation. The morphology control of NH2-MIL-125 based on the modulation of the type of titanium ester, reactants concentration, and the added acetic acid concentration were detailed exhibited and explained.

Consistent Estimation of Gibbs Energy Using Component Contributions

PubMed Central

Milo, Ron; Fleming, Ronan M. T.

2013-01-01

Standard Gibbs energies of reactions are increasingly being used in metabolic modeling for applying thermodynamic constraints on reaction rates, metabolite concentrations and kinetic parameters. The increasing scope and diversity of metabolic models has led scientists to look for genome-scale solutions that can estimate the standard Gibbs energy of all the reactions in metabolism. Group contribution methods greatly increase coverage, albeit at the price of decreased precision. We present here a way to combine the estimations of group contribution with the more accurate reactant contributions by decomposing each reaction into two parts and applying one of the methods on each of them. This method gives priority to the reactant contributions over group contributions while guaranteeing that all estimations will be consistent, i.e. will not violate the first law of thermodynamics. We show that there is a significant increase in the accuracy of our estimations compared to standard group contribution. Specifically, our cross-validation results show an 80% reduction in the median absolute residual for reactions that can be derived by reactant contributions only. We provide the full framework and source code for deriving estimates of standard reaction Gibbs energy, as well as confidence intervals, and believe this will facilitate the wide use of thermodynamic data for a better understanding of metabolism. PMID:23874165

Solar thermochemical processing system and method

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

Wegeng, Robert S.; Humble, Paul H.; Krishnan, Shankar

A solar thermochemical processing system is disclosed. The system includes a first unit operation for receiving concentrated solar energy. Heat from the solar energy is used to drive the first unit operation. The first unit operation also receives a first set of reactants and produces a first set of products. A second unit operation receives the first set of products from the first unit operation and produces a second set of products. A third unit operation receives heat from the second unit operation to produce a portion of the first set of reactants.

Particle size studies to reveal crystallization mechanisms of the metal organic framework HKUST-1 during sonochemical synthesis.

PubMed

Armstrong, Mitchell R; Senthilnathan, Sethuraman; Balzer, Christopher J; Shan, Bohan; Chen, Liang; Mu, Bin

2017-01-01

Systematic studies of key operating parameters for the sonochemical synthesis of the metal organic framework (MOF) HKUST-1(also called CuBTC) were performed including reaction time, reactor volume, sonication amplitude, sonication tip size, solvent composition, and reactant concentrations analyzed through SEM particle size analysis. Trends in the particle size and size distributions show reproducible control of average particle sizes between 1 and 4μm. These results along with complementary studies in sonofragmentation and temperature control were conducted to compare these results to kinetic crystal growth models found in literature to develop a plausible hypothetical mechanism for ultrasound-assisted growth of metal-organic-frameworks composed of a competitive mechanism including constructive solid-on-solid (SOS) crystal growth and a deconstructive sonofragmentation. Copyright © 2016 Elsevier B.V. All rights reserved.

A Hands-On Activity Incorporating the Threefold Representation on Limiting Reactant

ERIC Educational Resources Information Center

Gonza´lez-Sa´nchez, Ange´lica M.; Ortiz-Nieves, Edgardo L.; Medina, Zuleikra

2014-01-01

Many students share the common belief that the limiting reactant in a chemical reaction is the reactant in the smallest quantity of material. To help students overcome this difficulty a hands-on activity for the limiting reactant concept was developed. The activity incorporates the three levels of representation (macroscopic, submicroscopic, and…

Aromatic polyimides containing a dimethylsilane-linked dianhydride

NASA Technical Reports Server (NTRS)

St.clair, Anne K. (Inventor); St.clair, Terry L. (Inventor); Pratt, J. Richard (Inventor)

1989-01-01

A high-temperature stable, optically transparent, low dielectric aromatic polyimide is prepared by chemically combining equimolar quantities of an aromatic dianhydride reactant and an aromatic diamine reactant, which are selected so that one reactant contains at least one Si(CH3)2 group in its molecular structure, and the other reactant contains at least one -CF3 group in its molecular structure. The reactants are chemically combined in a solvent medium to form a solution of a high molecular weight polyamic acid, which is then converted to the corresponding polyimide.

Aromatic polyimides containing a dimethylsilane-linked dianhydride

NASA Technical Reports Server (NTRS)

St. Clair, Anne K. (Inventor); St. Clair, Terry L. (Inventor); Pratt, J. Richard (Inventor)

1992-01-01

A high-temperature stable, optically transparent, low dielectric aromatic polyimide is prepared by chemically combining equimolar quantities of an aromatic dianhydride reactant and an aromatic diamine reactant, which are selected so that one reactant contains at least one Si(CH.sub.3).sub.2 group in its molecular structure, and the other reactant contains at least one --CH.sub.3 group in its molecular structure. The reactants are chemically combined in a solvent medium to form a solution of a high molecular weight polyamic acid, which is then converted to the corresponding polyimide.

Wave packet and statistical quantum calculations for the He + NeH⁺ → HeH⁺ + Ne reaction on the ground electronic state.

PubMed

Koner, Debasish; Barrios, Lizandra; González-Lezana, Tomás; Panda, Aditya N

2014-09-21

A real wave packet based time-dependent method and a statistical quantum method have been used to study the He + NeH(+) (v, j) reaction with the reactant in various ro-vibrational states, on a recently calculated ab initio ground state potential energy surface. Both the wave packet and statistical quantum calculations were carried out within the centrifugal sudden approximation as well as using the exact Hamiltonian. Quantum reaction probabilities exhibit dense oscillatory pattern for smaller total angular momentum values, which is a signature of resonances in a complex forming mechanism for the title reaction. Significant differences, found between exact and approximate quantum reaction cross sections, highlight the importance of inclusion of Coriolis coupling in the calculations. Statistical results are in fairly good agreement with the exact quantum results, for ground ro-vibrational states of the reactant. Vibrational excitation greatly enhances the reaction cross sections, whereas rotational excitation has relatively small effect on the reaction. The nature of the reaction cross section curves is dependent on the initial vibrational state of the reactant and is typical of a late barrier type potential energy profile.

Chemical modification of nanocrystal surfaces

DOEpatents

Alivisatos, A. Paul; Owen, Jonathan

2013-05-07

A method is disclosed. The method includes obtaining a precursor nanoparticle comprising a base material and a first ligand attached to the base material, and reacting the precursor nanoparticle with a reactant comprising a silicon bond, thereby removing the first ligand.

A Raman spectroscopic determination of the kinetics of decomposition of ammonium chromate (NH 4) 2CrO 4

NASA Astrophysics Data System (ADS)

De Waal, D.; Heyns, A. M.; Range, K.-J.

1989-06-01

Raman spectroscopy was used as a method in the kinetic investigation of the thermal decomposition of solid (NH 4) 2CrO 4. Time-dependent measurements of the intensity of the totally symmetric stretching CrO mode of (NH 4) 2CrO 4 have been made between 343 and 363 K. A short initial acceleratory period is observed at lower temperatures and the decomposition reaction decelerates after the maximum decomposition rate has been reached at all temperatures. These results can be interpreted in terms of the Avrami-Erofe'ev law 1 - (χ r) {1}/{2} = kt , where χr is the fraction of reactant at time t. At 358 K, k is equal to 1.76 ± 0.01 × 10 -3 sec -1 for microcrystals and for powdered samples. Activation energies of 97 ± 10 and 49 ± 0.9 kJ mole -1 have been calculated for microcrystalline and powdered samples, respectively.

Synthesis and growth mechanism of Zn0.5Cd0.5S nanohexagon dendrite

NASA Astrophysics Data System (ADS)

Yu, Wen; Fang, Pengfei; Wang, Shaojie

2014-12-01

Hierarchical Zn0.5Cd0.5S nanohexagon dendrites were synthesized by a one-step hydrothermal method. The Zn0.5Cd0.5S nanohexagon dendrites were made up of nanohexagons with a side length of about 90 nm. The nanohexagons were regularly arranged forming as embranchments which were parallel to each other along certain hexagonal directions. Furthermore, these embranchments made up primary trunks shaping as dendrites. The growth mechanism of Zn0.5Cd0.5S nanohexagon dendrites was proposed in which molecular soft template and lowest energy principle played key roles. By adjusting the composition of the reactants, a series of ZnxCd1-xS solid solutions could be obtained. The morphology of the synthesized ZnxCd1-xS depended much on the x value. The UV-vis spectra absorb edges of the ZnxCd1-xS samples continuously shifted indicating the changes of the band gap.

LEAP into the Pfizer Global Virtual Library (PGVL) space: creation of readily synthesizable design ideas automatically.

PubMed

Hu, Qiyue; Peng, Zhengwei; Kostrowicki, Jaroslav; Kuki, Atsuo

2011-01-01

Pfizer Global Virtual Library (PGVL) of 10(13) readily synthesizable molecules offers a tremendous opportunity for lead optimization and scaffold hopping in drug discovery projects. However, mining into a chemical space of this size presents a challenge for the concomitant design informatics due to the fact that standard molecular similarity searches against a collection of explicit molecules cannot be utilized, since no chemical information system could create and manage more than 10(8) explicit molecules. Nevertheless, by accepting a tolerable level of false negatives in search results, we were able to bypass the need for full 10(13) enumeration and enabled the efficient similarity search and retrieval into this huge chemical space for practical usage by medicinal chemists. In this report, two search methods (LEAP1 and LEAP2) are presented. The first method uses PGVL reaction knowledge to disassemble the incoming search query molecule into a set of reactants and then uses reactant-level similarities into actual available starting materials to focus on a much smaller sub-region of the full virtual library compound space. This sub-region is then explicitly enumerated and searched via a standard similarity method using the original query molecule. The second method uses a fuzzy mapping onto candidate reactions and does not require exact disassembly of the incoming query molecule. Instead Basis Products (or capped reactants) are mapped into the query molecule and the resultant asymmetric similarity scores are used to prioritize the corresponding reactions and reactant sets. All sets of Basis Products are inherently indexed to specific reactions and specific starting materials. This again allows focusing on a much smaller sub-region for explicit enumeration and subsequent standard product-level similarity search. A set of validation studies were conducted. The results have shown that the level of false negatives for the disassembly-based method is acceptable when the query molecule can be recognized for exact disassembly, and the fuzzy reaction mapping method based on Basis Products has an even better performance in terms of lower false-negative rate because it is not limited by the requirement that the query molecule needs to be recognized by any disassembly algorithm. Both search methods have been implemented and accessed through a powerful desktop molecular design tool (see ref. (33) for details). The chapter will end with a comparison of published search methods against large virtual chemical space.

Curable liquid hydrocarbon prepolymers containing hydroxyl groups and process for producing same

NASA Technical Reports Server (NTRS)

Rhein, R. A.; Ingham, J. D. (Inventor)

1978-01-01

Production of hydroxyl containing curable liquid hydrocarbon prepolymers by ozonizing a high molecular weight saturated hydrocarbon polymer such as polyisobutylene or ethylene propylene rubber is discussed. The ozonized material is reduced using reducing agents, preferably diisobutyl aluminum hydride, to form the hydroxyl containing liquid prepolymers having a substantially lower molecular weight than the parent polymer. The resulting curable liquid hydroxyl containing prepolymers can be poured into a mold and readily cured, with reactants such as toluene diisocyanate, to produce highly stable elastomers having a variety of uses such as binders for solid propellants.

Monitoring structural transformations in crystals. 7. 1-Chloroanthracene and its photodimer.

PubMed

Turowska-Tyrk, Ilona; Grześniak, Karolina

2004-02-01

Crystals of the 1-chloroanthracene photodimer, viz. trans-bi(1-chloro-9,10-dihydro-9,10-anthracenediyl), C(28)H(18)Cl(2), were obtained from the solid-state [4+4]-photodimerization of the monomer, C(14)H(9)Cl, followed by recrystallization. The symmetry of the product molecules is defined by the orientation of the reactant molecules in the crystal. The mutual orientation parameters calculated for adjacent monomers explain the reactivity of the compound. The molecules in the crystal of the monomer and the recrystallized photodimer pack differently and the photodimer has crystallographically imposed inversion symmetry.

Effect of thermal expansion on the stability of two-reactant flames

NASA Technical Reports Server (NTRS)

Jackson, T. L.

1986-01-01

The full problem of flame stability for the two-reactant model, which takes into account thermal expansion effects for all disturbance wave lengths, is examined. It is found that the stability problem for the class of two-reactant flames is equivalent to the stability problem for the class of one-reactant flames with an appropriate interpretation of Lewis numbers.

Interfacial microstructure in a B{sub 4}C/Al composite fabricated by pressureless infiltration.

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

Luo, Z.; Song, Y.; Zhang, S.

In this work, B{sub 4}C particulate-reinforced Al composite was fabricated by a pressureless infiltration technique, and its interfacial microstructure was studied in detail by X-ray diffraction as well as by scanning and transmission electron microscopy. The B{sub 4}C phase was unstable in Al melt during the infiltration process, forming AlB{sub 10}-type AlB{sub 24}C{sub 4} or Al{sub 2.1}B{sub 51}C{sub 8} as a major reactant phase. The Al matrix was large grains (over 10 {micro}m), which had no definite orientation relationships (ORs) with the randomly orientated B{sub 4}C or its reactant particles, except for possible nucleation sites with {l_brace}011{r_brace}{sub B{sub 4}C} almostmore » parallel to {l_brace}111{r_brace}{sub Al} at a deviation angle of 1.5 deg. Both B{sub 4}C-Al and reactant-Al interfaces are semicoherent and free of other phases. A comparison was made with the SiC/Al composite fabricated similarly by the pressureless infiltration. It was suggested that the lack of ORs between the Al matrix and reinforced particles, except for possible nucleation sites, is the common feature of the composites prepared by the infiltration method.« less

Gas-Phase Combustion Synthesis of Aluminum Nitride Powder

NASA Technical Reports Server (NTRS)

Axelbaum, R. L.; Lottes, C. R.; Huertas, J. I.; Rosen, L. J.

1996-01-01

Due to its combined properties of high electrical resistivity and high thermal conductivity aluminum nitride (AlN) is a highly desirable material for electronics applications. Methods are being sought for synthesis of unagglomerated, nanometer-sized powders of this material, prepared in such a way that they can be consolidated into solid compacts having minimal oxygen content. A procedure for synthesizing these powders through gas-phase combustion is described. This novel approach involves reacting AlCl3, NH3, and Na vapors. Equilibrium thermodynamic calculations show that 100% yields can be obtained for these reactants with the products being AlN, NaCl, and H2. The NaCl by-product is used to coat the AlN particles in situ. The coating allows for control of AlN agglomeration and protects the powders from hydrolysis during post-flame handling. On the basis of thermodynamic and kinetic considerations, two different approaches were employed to produce the powder, in co-flow diffusion flame configurations. In the first approach, the three reactants were supplied in separate streams. In the second, the AlCl3 and NH3 were premixed with HCl and then reacted with Na vapor. X-ray diffraction (XRD) spectra of as-produced powders show only NaCl for the first case and NaCl and AlN for the second. After annealing at 775 C tinder dynamic vacuum, the salt was removed and XRD spectra of powders from both approaches show only AlN. Aluminum metal was also produced in the co-flow flame by reacting AlCl3 with Na. XRD spectra of as-produced powders show the products to be only NaCl and elemental aluminum.

Solar-induced chemical vapor deposition of diamond-type carbon films

DOEpatents

Pitts, J.R.; Tracy, C.E.; King, D.E.; Stanley, J.T.

1994-09-13

An improved chemical vapor deposition method for depositing transparent continuous coatings of sp[sup 3]-bonded diamond-type carbon films, comprises: (a) providing a volatile hydrocarbon gas/H[sub 2] reactant mixture in a cold wall vacuum/chemical vapor deposition chamber containing a suitable substrate for said films, at pressure of about 1 to 50 Torr; and (b) directing a concentrated solar flux of from about 40 to about 60 watts/cm[sup 2] through said reactant mixture to produce substrate temperatures of about 750 C to about 950 C to activate deposition of the film on said substrate. 11 figs.

Solar-induced chemical vapor deposition of diamond-type carbon films

DOEpatents

Pitts, J. Roland; Tracy, C. Edwin; King, David E.; Stanley, James T.

1994-01-01

An improved chemical vapor deposition method for depositing transparent continuous coatings of sp.sup.3 -bonded diamond-type carbon films, comprising: a) providing a volatile hydrocarbon gas/H.sub.2 reactant mixture in a cold wall vacuum/chemical vapor deposition chamber containing a suitable substrate for said films, at pressure of about 1 to 50 Torr; and b) directing a concentrated solar flux of from about 40 to about 60 watts/cm.sup.2 through said reactant mixture to produce substrate temperatures of about 750.degree. C. to about 950.degree. C. to activate deposition of the film on said substrate.

Methods and electrolytes for electrodeposition of smooth films

DOEpatents

Zhang, Jiguang; Xu, Wu; Graff, Gordon L; Chen, Xilin; Ding, Fei; Shao, Yuyan

2015-03-17

Electrodeposition involving an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and/or film surface. For electrodeposition of a first conductive material (C1) on a substrate from one or more reactants in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second conductive material (C2), wherein cations of C2 have an effective electrochemical reduction potential in the solution lower than that of the reactants.

Simplified Production of Organic Compounds Containing High Enantiomer Excesses

NASA Technical Reports Server (NTRS)

Cooper, George W. (Inventor)

2015-01-01

The present invention is directed to a method for making an enantiomeric organic compound having a high amount of enantiomer excesses including the steps of a) providing an aqueous solution including an initial reactant and a catalyst; and b) subjecting said aqueous solution simultaneously to a magnetic field and photolysis radiation such that said photolysis radiation produces light rays that run substantially parallel or anti-parallel to the magnetic field passing through said aqueous solution, wherein said catalyst reacts with said initial reactant to form the enantiomeric organic compound having a high amount of enantiomer excesses.

Method of producing silicon. [gas phase reactor multiple injector liquid feed system

NASA Technical Reports Server (NTRS)

Wolf, C. B.; Meyer, T. N. (Inventor)

1980-01-01

A liquid reactant injector assembly suited for the injection of liquid reactant into a high temperature metal reductant vapor and carrier gas stream for the production of metal is presented. The assembly is especially adapted for the continuous production of high purity silicon by the reduction of SiCl4 with sodium. The assembly includes a refractory-lined, hollow metal shell having ten equally-spaced, concentric, radially directed ports provided in the shell and wall. A hydraulic, atomizing type spray nozzle is mounted in each of the ports recessed from the inner wall surface.

Synthesis and characterisation of the uranium pyrochlore betafite [(Ca,U)₂(Ti,Nb,Ta)₂O₇].

PubMed

McMaster, Scott A; Ram, Rahul; Charalambous, Fiona; Pownceby, Mark I; Tardio, James; Bhargava, Suresh K

2014-09-15

Betafite of composition [(Ca,U)2(Ti,Nb,Ta)2O7] was prepared via a solid state synthesis route. The synthesis was shown to be sensitive to initial reactant ratios, the atmosphere used (oxidising, neutral, reducing) and time. The optimum conditions for the synthesis of betafite were found to be heating the reactants required at 1150°C for 48 h under an inert gas atmosphere. XRD characterisation revealed that the synthesised betafite contained minor impurities. EPMA analysis of a sectioned surface showed very small regions of Ca-free betafite on grain boundaries as well as minor rutile impurities. Some heterogeneity between the Nb:Ta ratio was observed by quantitative EPMA but was generally within the nomenclature requirements stated for betafite. SEM analysis revealed the synthesised betafite was comprised mostly of hexaoctohedral crystals of ∼ 3 μm in diameter. XPS analysis of the sample showed that the uranium in the synthesised betafite was predominately present in the U(5+) oxidation state. A minor amount of U(6+) was also detected which was possibly due to surface oxidation. Copyright © 2014 Elsevier B.V. All rights reserved.

The dynamics of Al/Pt reactive multilayer ignition via pulsed-laser irradiation

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

Murphy, Ryan D.; Reeves, Robert V.; Yarrington, Cole D.

2015-12-07

Reactive multilayers consisting of alternating layers of Al and Pt were irradiated by single laser pulses ranging from 100 μs to 100 ms in duration, resulting in the initiation of rapid, self-propagating reactions. The threshold intensities for ignition vary with the focused laser beam diameter, bilayer thickness, and pulse length and are affected by solid state reactions and conduction of heat away from the irradiated regions. High-speed photography was used to observe ignition dynamics during irradiation and elucidate the effects of heat transfer into a multilayer foil. For an increasing laser pulse length, the ignition process transitioned from a more uniform tomore » a less uniform temperature profile within the laser-heated zone. A more uniform temperature profile is attributed to rapid heating rates and heat localization for shorter laser pulses, and a less uniform temperature profile is due to slower heating of reactants and conduction during irradiation by longer laser pulses. Finite element simulations of laser heating using measured threshold intensities indicate that micron-scale ignition of Al/Pt occurs at low temperatures, below the melting point of both reactants.« less

The dynamics of Al/Pt reactive multilayer ignition via pulsed-laser irradiation

DOE PAGES

Murphy, Ryan D.; Reeves, Robert V.; Yarrington, Cole D.; ...

2015-12-07

Reactive multilayers consisting of alternating layers of Al and Pt were irradiated by single laser pulses ranging from 100 μs to 100 ms in duration, resulting in the initiation of rapid, self-propagating reactions. The threshold intensities for ignition vary with the focused laser beam diameter, bilayer thickness, and pulse length and are affected by solid state reactions and conduction of heat away from the irradiated regions. We used high-speed photography to observe ignition dynamics during irradiation and elucidate the effects of heat transfer into a multilayer foil. For an increasing laser pulse length, the ignition process transitioned from a moremore » uniform to a less uniform temperature profile within the laser-heated zone. A more uniform temperature profile is attributed to rapid heating rates and heat localization for shorter laser pulses, and a less uniform temperature profile is due to slower heating of reactants and conduction during irradiation by longer laser pulses. Lastly, finite element simulations of laser heating using measured threshold intensities indicate that micron-scale ignition of Al/Pt occurs at low temperatures, below the melting point of both reactants.« less

Synthesis of nanosized sodium titanates

DOEpatents

Hobbs, David T.; Taylor-Pashow, Kathryn M. L.; Elvington, Mark C.

2015-09-29

Methods directed to the synthesis and peroxide-modification of nanosized monosodium titanate are described. Methods include combination of reactants at a low concentration to a solution including a nonionic surfactant. The nanosized monosodium titanate can exhibit high selectivity for sorbing various metallic ions.

Compact solid source of hydrogen gas

DOEpatents

Kravitz, Stanley H.; Hecht, Andrew M.; Sylwester, Alan P.; Bell, Nelson S.

2004-06-08

A compact solid source of hydrogen gas, where the gas is generated by contacting water with micro-disperse particles of sodium borohydride in the presence of a catalyst, such as cobalt or ruthenium. The micro-disperse particles can have a substantially uniform diameter of 1-10 microns, and preferably about 3-5 microns. Ruthenium or cobalt catalytic nanoparticles can be incorporated in the micro-disperse particles of sodium borohydride, which allows a rapid and complete reaction to occur without the problems associated with caking and scaling of the surface by the reactant product sodium metaborate. A closed loop water management system can be used to recycle wastewater from a PEM fuel cell to supply water for reacting with the micro-disperse particles of sodium borohydride in a compact hydrogen gas generator. Capillary forces can wick water from a water reservoir into a packed bed of micro-disperse fuel particles, eliminating the need for using an active pump.

All-solid electrodes with mixed conductor matrix

DOEpatents

Huggins, Robert A.; Boukamp, Bernard A.

1984-01-01

Alkali metal based electrochemical cells offer a great deal of promise for applications in many areas such as electric vehicles and load leveling purposes in stationary power plants. Lithium is an attractive candidate as the electroactive species in such cells since lithium is very electropositive, abundant and light weight. One type of lithium-based cell utilizes a molten salt electrolyte and normally is operated at elevated temperatures. The subject invention provides an electrochemical cell in one embodiment of which lithium is the electroactive species. The cell comprises an electrolyte, a positive electrode, and a negative electrode, either or both of which is an all-solid, composite microstructural electrode containing both a reactant phase and a mixed ionic-electronic conducting phase. The cells of the subject invention exhibit improved kinetic features, current and power densities. Repeated charging and discharging of these cells can be accomplished without appreciable loss of capacity.

Simulating Dynamic Equilibria: A Class Experiment

NASA Astrophysics Data System (ADS)

Harrison, John A.; Buckley, Paul D.

2000-08-01

A first-order reversible reaction is simulated on an overhead projector using small coins or discs. A simulation is carried out in which initially there are 24 discs representing reactant A and none representing reactant B. At the end of each minute half of the reactant A discs get converted to reactant B, and one quarter of the reactant B discs get converted to reactant A discs. Equilibrium is established with 8 A discs and 16 B discs, and no further net change is observed as the simulation continues. Another simulation beginning with 48 A discs and 0 B discs leads at equilibrium to 16 A discs and 32 B discs. These results illustrate how dynamic equilibria are established and allow the introduction of the concept of an equilibrium constant. Le Châtelier's principle is illustrated by further simulations.

Methods of producing sulfate salts of cations from heteroatomic compounds and dialkyl sulfates and uses thereof

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

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2015-09-29

Methods of preparing sulfate salts of heteroatomic compounds using dialkyl sulfates as a primary reactant are disclosed. Also disclosed are methods of making ionic liquids from the sulfate salts of the heteroatomic compound, and electrochemical cells comprising the ionic liquids.

Effect of the calcium to phosphorus ratio on the setting properties of calcium phosphate bone cements.

PubMed

Vlad, M D; Gómez, S; Barracó, M; López, J; Fernández, E

2012-09-01

α-Tricalcium phosphate (α-TCP) has become the main reactant of most experimental and commercial ceramic bone cements. It has calcium-to-phosphorus (Ca/P) ratio of 1.50. The present study expands and reports on the microstructures and mechanical properties of calcium phosphate (CP) cements containing sintered monolithic reactants obtained in the interval 1.29 < Ca/P < 1.77. The study focuses on their cement setting and hardening properties as well as on their microstructure and crystal phase evolution. The results showed that: (a) CP-cements made with reactants with Ca/P ratio other than 1.50 have longer setting and lower hardening properties; (b) CP-cements reactivity was clearly affected by the Ca/P ratio of the starting reactant; (c) reactants with Ca/P < 1.50 were composed of several phases, calcium pyrophosphate and α- and β-TCP. Similarly, reactants with Ca/P > 1.50 were composed of α-TCP, tetracalcium phosphate and hydroxyapatite; (d) only the reactant with Ca/P = 1.50 was monophasic and was made of α-TCP, which transformed during the setting into calcium deficient hydroxyapatite; (e) CP-cements developed different crystal microstructures with specific features depending on the Ca/P ratio of the starting reactant.

Size- and morphology-controllable synthesis of MIL-96 (Al) by hydrolysis and coordination modulation of dual aluminium source and ligand systems.

PubMed

Liu, Dandan; Liu, Yunqi; Dai, Fangna; Zhao, Jinchong; Yang, Kang; Liu, Chenguang

2015-10-07

In this paper, an efficient method to fabricate Al-based metal organic framework (Al-MOF) MIL-96 crystals with controllable size and morphology, by mixing other forms of reactants to replace the coordination modulators or capping agents, is presented. The size and morphology of the MIL-96 crystals can be selectively varied by simply altering the ratio of dual reactants via their hydrolysis reaction. All the samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and nitrogen sorption. Then based on the BFDH theory, a mechanism for the impact of hydrolysis of reactants on the crystal size and morphology is presented and discussed. We also evaluated the performance of these MOFs as sorbents for capturing CO2, and they all show enhanced adsorption properties compared with the bulk material, displaying high adsorption capacities on CO2 at atmospheric pressure and ambient temperature.

Evaluation of selected chemical processes for production of low-cost silicon, phases 1 and 2

NASA Technical Reports Server (NTRS)

Blocher, J. M.; Browning, M. F.

1978-01-01

A miniplant, consisting of a 5 cm-diameter fluidized-bed reactor and associated equipment was used to study the deposition parameters, temperature, reactant composition, seed particle size, bed depth, reactant throughput, and methods of reactant introduction. It was confirmed that the permissible range of fluidized-bed temperature was limited at the lower end by zinc condensation (918 C) and at higher temperatures by rapidly decreasing conversion efficiency. Use of a graded bed temperature was shown to increase the conversion efficiency over that obtained in an isothermal bed. Other aspects of the process such as the condensation and fused-salt electrolysis of the ZnCl2 by-product for recycle of zinc and chlorine were studied to provide information required for design of a 50 MT/year experimental facility. In view of the favorable technical and economic indications obtained, it was recommended that construction and operation of the 50 MT/year experimental facility be implemented.

The kinetics and mechanism of nanoconfined molten salt reactions: trimerization of potassium and rubidium dicyanamide.

PubMed

Yancey, Benjamin; Vyazovkin, Sergey

2015-04-21

This study highlights the effect of the aggregate state of a reactant on the reaction kinetics under the conditions of nanoconfinement. Our previous work (Phys. Chem. Chem. Phys., 2014, 16, 11409) has demonstrated considerable deceleration of the solid state trimerization of sodium dicyanamide in organically modified silica nanopores. In the present study we use FTIR, NMR, pXRD, TGA and DSC to analyze the kinetics and mechanism of the liquid state trimerization of potassium and rubidium dicyanamide under similar conditions of nanoconfinement. It is found that nanoconfinement accelerates dramatically the kinetics of the liquid state trimerization, whereas it does not appear to affect the reaction mechanism. Kinetic analysis indicates that the acceleration is associated with an increase in the preexponential factor. Although nanoconfinement has the opposite effects on the respective kinetics of solid and liquid state trimerization, both effects are linked to a change in the preexponential factor. The results obtained are consistent with our hypothesis that the effects differ because nanoconfinement may promote disordering of the solid and ordering of the liquid reaction media.

Method and apparatus for the control of fluid dynamic mixing in pulse combustors

DOEpatents

Bramlette, T.T.; Keller, J.O.

1992-06-02

In a method and apparatus for controlling total ignition delay time in a pulse combustor, and thus controlling the mixing characteristics of the combustion reactants and the combustion products in the combustor, the total ignition delay time is controlled by adjusting the inlet geometry of the inlet to the combustion chamber. The inlet geometry may be fixed or variable for controlling the mixing characteristics. A feedback loop may be employed to sense actual combustion characteristics, and, in response to the sensed combustion characteristics, the inlet geometry may be varied to obtain the total ignition delay time necessary to achieve the desired combustion characteristics. Various embodiments relate to the varying of the mass flow rate of reactants while holding the radius/velocity ratio constant. 10 figs.

Method and apparatus for the control of fluid dynamic mixing in pulse combustors

DOEpatents

Bramlette, T. Tazwell; Keller, Jay O.

1992-06-02

In a method and apparatus for controlling total ignition delay time in a pulse combustor, and thus controlling the mixing characteristics of the combustion reactants and the combustion products in the combustor, the total ignition delay time is controlled by adjusting the inlet geometry of the inlet to the combustion chamber. The inlet geometry may be fixed or variable for controlling the mixing characteristics. A feedback loop may be employed to sense actual combustion characteristics, and, in response to the sensed combustion characteristics, the inlet geometry may be varied to obtain the total ignition delay time necessary to achieve the desired combustion characteristics. Various embodiments relate to the varying of the mass flow rate of reactants while holding the radius/velocity ratio constant.

Isochoric Burn, an Internally Consistent Method for the Reactant to Product Transformation in Reactive Flow

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

Reaugh, J E; Lee, E L

2002-07-01

Mixture rules for partially reacted explosives differ amongst various models. For instance, JWL++ uses a partial pressure addition to compute an average zonal pressure, Ignition and Growth requires pressure equilibration and thermal equilibration of temperature dependent JWL EOSs, CHEETAH In Line RF also assumes temperature and pressure equilibration. It has been suggested in the past that a more realistic equilibration scheme should comprise isentropic pressure equilibration of the separate reacted and unreacted phases. This turns out not to be a proper path for equilibration. Rather, we find that the only internally consistent method is the evaluation of the equilibrium pressuremore » that satisfies the particular conditions of reactant and product resulting from deflagration in a fixed volume.« less

User's guide to PHREEQC (Version 2) : a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, David L.; Appelo, C.A.J.

1999-01-01

PHREEQC version 2 is a computer program written in the C programming language that is designed to perform a wide variety of low-temperature aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations; (2) batch-reaction and one-dimensional (1D) transport calculations involving reversible reactions, which include aqueous, mineral, gas, solid-solution, surface-complexation, and ion-exchange equilibria, and irreversible reactions, which include specified mole transfers of reactants, kinetically controlled reactions, mixing of solutions, and temperature changes; and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for differences in composition between waters, within specified compositional uncertainty limits.New features in PHREEQC version 2 relative to version 1 include capabilities to simulate dispersion (or diffusion) and stagnant zones in 1D-transport calculations, to model kinetic reactions with user-defined rate expressions, to model the formation or dissolution of ideal, multicomponent or nonideal, binary solid solutions, to model fixed-volume gas phases in addition to fixed-pressure gas phases, to allow the number of surface or exchange sites to vary with the dissolution or precipitation of minerals or kinetic reactants, to include isotope mole balances in inverse modeling calculations, to automatically use multiple sets of convergence parameters, to print user-defined quantities to the primary output file and (or) to a file suitable for importation into a spreadsheet, and to define solution compositions in a format more compatible with spreadsheet programs. This report presents the equations that are the basis for chemical equilibrium, kinetic, transport, and inverse-modeling calculations in PHREEQC; describes the input for the program; and presents examples that demonstrate most of the program's capabilities.

Polymer useful for an ion exchange membrane

DOEpatents

Liang, Siwei; Lynd, Nathaniel A.

2017-03-14

The present invention provides for a polymer formed by reacting a first reactant polymer, or a mixture of first reactant polymers comprising different chemical structures, comprising a substituent comprising two or more nitrogen atoms (or a functional group/sidechain comprising a two or more nitrogen atoms) with a second reactant polymer, or a mixture of second reactant polymers comprising different chemical structures, comprising a halogen substituent (or a functional group/sidechain comprising a halogen).

General theory of multistage geminate reactions of isolated pairs of reactants. I. Kinetic equations.

PubMed

Doktorov, Alexander B; Kipriyanov, Alexey A

2014-05-14

General matrix approach to the consideration of multistage geminate reactions of isolated pairs of reactants depending on reactant mobility is formulated on the basis of the concept of "effective" particles. Various elementary reactions (stages of multistage reaction including physicochemical processes of internal quantum state changes) proceeding with the participation of isolated pairs of reactants (or isolated reactants) are taken into account. Investigation has been made in terms of kinetic approach implying the derivation of general (matrix) kinetic equations for local and mean probabilities of finding any of the reaction species in the sample under study (or for local and mean concentrations). The recipes for the calculation of kinetic coefficients of the equations for mean quantities in terms of relative coordinates of reactants have been formulated in the general case of inhomogeneous reacting systems. Important specific case of homogeneous reacting systems is considered.

The effect of varying the introduction mode of reactants on electrical, physical and thermal stability properties of polypyrrole synthesized with CTAB

NASA Astrophysics Data System (ADS)

Vahidi, K.; Jalili, Y. Seyed; Salar Elahi, A.

2017-10-01

Electrical and physical properties of conducting polymers are generally enhanced via modifications in the chemical structure of the final product, there appears to be a void in facile physical means to improve the materials' properties without utilizing additives which remain in the final product as impurity. In this research, we presented the effect of altering the introduction method of reactants in emulsion polymerization of PPy with CTAB on the electrical, physical and stability properties of the final product. Three samples were prepared: one via a conventional non-emulsion polymerization method as a reference sample, the second in which the reactants were added simultaneously and the goal sample in which the monomer/surfactant mixture was allowed to be stirred separately then it was added dropwise to the oxidant solution. UV-vis, FTIR, 4-point Van Derr Paw probe, FESEM and contact angle measurements were used to investigate optical, electrical, physical, heat stability and solubility properties of the samples. The results indicate that since in the final sample a higher portion of the reaction occurred on the hydrophobic interior of the micelles, the final material had a lower number of structural and chemical defects which leads to higher conjugation lengths and thus higher properties such as a 9-fold difference in conductivity and improved solubility and thermal stability. The novelty of this work lies in the simplicity of the alterations that have been made, both in terms of optimization of the synthetic route which had been thoroughly investigated and also in terms of the differences that our work poses compared to that of the others; namely: the parameters have been thoroughly studied and analyzed but not the method of addition as in our experiments the sequence of addition and the method of addition of the reactants were altered to observe their effect on the physical and the electronic properties which has led to the conclusion that in case of drop-wise addition, a larger portion of the reaction occurs inside the micelles hence giving rise to inhibition of the defect-producing chemical bonds which is supported by the analysis in our investigations.

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

Vorotilin, V. P., E-mail: VPVorotilin@yandex.ru

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

Cyclodextrin based polymer sorbents for micro-solid phase extraction followed by liquid chromatography tandem mass spectrometry in determination of endogenous steroids.

PubMed

Manaf, Normaliza Abdul; Saad, Bahruddin; Mohamed, Mohamed H; Wilson, Lee D; Latiff, Aishah A

2018-03-30

Sorbents were prepared by cross-linking β-cyclodextrin (β-CD) using two different types of cross-linker units at variable reactant mole ratios. The resulting polymers containing β-CD were evaluated as sorbents in micro-solid phase extraction (μ-SPE) format for the extraction of the endogenous steroids testosterone (T), epitestosterone (E), androsterone (A), etiocholanolone (Etio), 5α-androstane-3α,17β-diol (5αAdiol) and 5β-androstane-3α,17β-diol (5βAdiol). The best sorbent (C1; cyclodextrin polymer) showed superior extraction characteristics compared with commercial sorbents (C18 and Bond Elut Plexa). Parameters influencing the extraction efficiency of the C1 sorbent such as extraction and desorption times, desorption solvent and volume of sample were investigated. The extracts were separated using a Hypersil Gold column (50 × 2.1 mm, 1.9 μm) under gradient elution coupled to a LC-MS/MS. The compounds were successfully separated within 8 min. The method offers good repeatability (RSD < 10%) and linearity (r 2  > 0.995) were within the range of 1-200 ng mL -1 for T and E, 250-4000 ng mL -1 for A and Etio and 25-500 ng mL -1 for 5αAdiol and 5βAdiol, respectively. The method was applied for the determination of steroid profile of urine from volunteers. Copyright © 2018 Elsevier B.V. All rights reserved.

Closed end regeneration method

DOEpatents

Yang, Arthur Jing-Min; Zhang, Yuehua

2006-06-27

A nanoporous reactive adsorbent incorporates a relatively small number of relatively larger reactant, e.g. metal, enzyme, etc. particles (10) forming a discontinuous or continuous phase interspersed among and surrounded by a continuous phase of smaller adsorbent particles (12) and connected interstitial pores (14) therebetween. The reactive adsorbent can effectively remove inorganic or organic impurities in a liquid by causing the liquid to flow through the adsorbent. For example, silver ions may be adsorbed by the adsorbent particles (12) and reduced to metallic silver by reducing metal, such as irons, as the reactant particles (10). The column can be regenerated by backwashing with the liquid effluent containing, for example, acetic acid.

The general theory of multistage geminate reactions of isolated pairs of reactants. III. Two-stage reversible dissociation in geminate reaction A + A ↔ C ↔ B + B.

PubMed

Kipriyanov, Alexey A; Kipriyanov, Alexander A; Doktorov, Alexander B

2016-04-14

Specific two-stage reversible reaction A + A ↔ C ↔ B + B of the decay of species C reactants by two independent transition channels is considered on the basis of the general theory of multistage reactions of isolated pairs of reactants. It is assumed that at the initial instant of time, the reacting system contains only reactants C. The employed general approach has made it possible to consider, in the general case, the inhomogeneous initial distribution of reactants, and avoid application of model concepts of a reaction system structure (i.e., of the structure of reactants and their molecular mobility). Slowing of multistage reaction kinetics as compared to the kinetics of elementary stages is established and physically interpreted. To test approximations (point approximation) used to develop a universal kinetic law, a widely employed specific model of spherical particles with isotropic reactivity diffusing in solution is applied. With this particular model as an example, ultimate kinetics of chemical conversion of reactants is investigated. The question concerning the depths of chemical transformation at which long-term asymptotes are reached is studied.

The general theory of multistage geminate reactions of isolated pairs of reactants. III. Two-stage reversible dissociation in geminate reaction A + A↔C↔B + B

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

Kipriyanov, Alexey A.; Kipriyanov, Alexander A.; Doktorov, Alexander B.

2016-04-14

Specific two-stage reversible reaction A + A↔C↔B + B of the decay of species C reactants by two independent transition channels is considered on the basis of the general theory of multistage reactions of isolated pairs of reactants. It is assumed that at the initial instant of time, the reacting system contains only reactants C. The employed general approach has made it possible to consider, in the general case, the inhomogeneous initial distribution of reactants, and avoid application of model concepts of a reaction system structure (i.e., of the structure of reactants and their molecular mobility). Slowing of multistage reactionmore » kinetics as compared to the kinetics of elementary stages is established and physically interpreted. To test approximations (point approximation) used to develop a universal kinetic law, a widely employed specific model of spherical particles with isotropic reactivity diffusing in solution is applied. With this particular model as an example, ultimate kinetics of chemical conversion of reactants is investigated. The question concerning the depths of chemical transformation at which long-term asymptotes are reached is studied.« less

Engineering the Interfaces of Superadsorbing Graphene-Based Electrodes with Gas and Electrolyte to Boost Gas Evolution and Activation Reactions.

PubMed

Zhang, Jun-Jun; Lv, Li-Bing; Zhao, Tian-Jian; Lin, Yun-Xiao; Yu, Qiu-Ying; Su, Juan; Hirano, Shin-Ichi; Li, Xin-Hao; Chen, Jie-Sheng

2018-05-30

Electrochemical gas evolution and activation reactions are complicated processes, involving not only active electrocatalysts but also the interaction among solid electrodes, electrolyte, and gas-phase products and reactants. In this study, multiphase interfaces of superadsorbing graphene-based electrodes were controlled without changing the active centers to significantly facilitate mass diffusion kinetics for superior performance. The achieved in-depth understanding of how to regulate the interfacial properties to promote the electrochemical performance could provide valuable clues for electrode manufacture and for the design of more active electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Plasma synthesis of lithium based intercalation powders for solid polymer electrolyte batteries

DOEpatents

Kong, Peter C [Idaho Falls, ID; Pink, Robert J [Pocatello, ID; Nelson, Lee O [Idaho Falls, ID

2005-01-04

The invention relates to a process for preparing lithium intercalation compounds by plasma reaction comprising the steps of: forming a feed solution by mixing lithium nitrate or lithium hydroxide or lithium oxide and the required metal nitrate or metal hydroxide or metal oxide and between 10-50% alcohol by weight; mixing the feed solution with O.sub.2 gas wherein the O.sub.2 gas atomizes the feed solution into fine reactant droplets, inserting the atomized feed solution into a plasma reactor to form an intercalation powder; and if desired, heating the resulting powder to from a very pure single phase product.

The kinetics of ulvoespinel reduction - Synthetic study and applications to lunar rocks.

NASA Technical Reports Server (NTRS)

Mccallister, R. H.; Taylor, L. A.

1973-01-01

The kinetics of Fe2TiO4 reduction to FeTiO3 + Fe were studied using CO-CO2 gas mixtures with fO2 measured by a solid ceramic (calcia-zirconia) oxygen electrolyte cell. Isothermal rate studies at 900 C suggest that the mechanism of Fe2TiO4 reduction is one of nucleation and growth, where the growth stage may be controlled by the diffusion of the reactant through the product layer or volume diffusion. The activation energy for the growth stage of the process was determined to be 46 plus or minus 4 kcal/mole.

To Model Chemical Reactivity in Heterogeneous Emulsions, Think Homogeneous Microemulsions.

PubMed

Bravo-Díaz, Carlos; Romsted, Laurence Stuart; Liu, Changyao; Losada-Barreiro, Sonia; Pastoriza-Gallego, Maria José; Gao, Xiang; Gu, Qing; Krishnan, Gunaseelan; Sánchez-Paz, Verónica; Zhang, Yongliang; Dar, Aijaz Ahmad

2015-08-25

Two important and unsolved problems in the food industry and also fundamental questions in colloid chemistry are how to measure molecular distributions, especially antioxidants (AOs), and how to model chemical reactivity, including AO efficiency in opaque emulsions. The key to understanding reactivity in organized surfactant media is that reaction mechanisms are consistent with a discrete structures-separate continuous regions duality. Aggregate structures in emulsions are determined by highly cooperative but weak organizing forces that allow reactants to diffuse at rates approaching their diffusion-controlled limit. Reactant distributions for slow thermal bimolecular reactions are in dynamic equilibrium, and their distributions are proportional to their relative solubilities in the oil, interfacial, and aqueous regions. Our chemical kinetic method is grounded in thermodynamics and combines a pseudophase model with methods for monitoring the reactions of AOs with a hydrophobic arenediazonium ion probe in opaque emulsions. We introduce (a) the logic and basic assumptions of the pseudophase model used to define the distributions of AOs among the oil, interfacial, and aqueous regions in microemulsions and emulsions and (b) the dye derivatization and linear sweep voltammetry methods for monitoring the rates of reaction in opaque emulsions. Our results show that this approach provides a unique, versatile, and robust method for obtaining quantitative estimates of AO partition coefficients or partition constants and distributions and interfacial rate constants in emulsions. The examples provided illustrate the effects of various emulsion properties on AO distributions such as oil hydrophobicity, emulsifier structure and HLB, temperature, droplet size, surfactant charge, and acidity on reactant distributions. Finally, we show that the chemical kinetic method provides a natural explanation for the cut-off effect, a maximum followed by a sharp reduction in AO efficiency with increasing alkyl chain length of a particular AO. We conclude with perspectives and prospects.

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

Simmons, F.; Kuntamukkula, M.; Alnajjar, M.

Pyrophoric reagents represent an important class of reactants because they can participate in many different types of reactions. They are very useful in organic synthesis and in industrial applications. The Occupational Safety and Health Administration (OSHA) and the National Fire Protection Association (NFPA) define Pyrophorics as substances that will self-ignite in air at temperatures of 130 F (54.4 C) or less. However, the U.S. Department of Transportation (DOT) uses criteria different from the auto-ignition temperature criterion. The DOT defines a pyrophoric material as a liquid or solid that, even in small quantities and without an external ignition source, can ignitemore » within five minutes after coming in contact with air when tested according to the United Nations Manual of Tests and Criteria. The Environmental Protection Agency has adopted the DOT definition. Regardless of which definition is used, oxidation of the pyrophoric reagents by oxygen or exothermic reactions with moisture in the air (resulting in the generation of a flammable gas such as hydrogen) is so rapid that ignition occurs spontaneously. Due to the inherent nature of pyrophoric substances to ignite spontaneously upon exposure to air, special precautions must be taken to ensure their safe handling and use. Pyrophoric gases (such as diborane, dichloroborane, phosphine, etc.) are typically the easiest class of pyrophoric substances to handle since the gas can be plumbed directly to the application and used remotely. Pyrophoric solids and liquids, however, require the user to physically manipulate them when transferring them from one container to another. Failure to follow proper safety precautions could result in serious injury or unintended consequences to laboratory personnel. Because of this danger, pyrophorics should be handled only by experienced personnel. Users with limited experience must be trained on how to handle pyrophoric reagents and consult with a knowledgeable staff member prior to performing the experimental task. The purpose of this article is three fold: (1) to provide guidelines and general safety precautions to avoid accidents, (2) describe proper techniques on how to successfully handle, store, and dispose of pyrophoric liquids and solids, and (3) illustrate best practices for working with this class of reactants in a laboratory environment.« less

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.

Interaction of pesticides with natural and synthetic solids. Evaluation in dynamic and equilibrium conditions.

PubMed

Otalvaro, Julián Ortiz; Brigante, Maximiliano

2018-03-01

Interactions between pesticides (paraquat, glyphosate, 2,4-D, atrazine, and metsulfuron methyl) and soil organic and inorganic components have been studied in batch experiments by performing adsorption, dissolution, and chemical and photochemical degradation under different conditions. The obtained results confirm that the affinity of a pesticide to the solid surface depends on the nature of both and shows that each reactant strongly affects the mobility of the other one, e.g., anionic pesticides promote the dissolution of the solid humic acid but if this last is retained into the inorganic matrix enhances the adsorption of a cationic pesticide. Adsorption also seems to protect the bonded specie to be chemical degraded, such as shown in two pesticide/clay systems at constant pH. The use of mesoporous silicas could result in a good alternative for pesticide remediation. In fact, the solid shows high adsorption capacity towards paraquat and its modification with TiO 2 nanoparticles increases not only the pesticide adsorption but also seems to catalyze its degradation under UV light to less-toxic metabolites. UV-VIS spectroscopy was relevant and novel in such sense. Electrostatic interactions, hydrogen and coordinative bonds formations, surface complexations and hydrophobic associations play a key role in the fate of mentioned pesticides on soil and ground/surface water environments.

Liquid Water Transport in the Reactant Channels of Proton Exchange Membrane Fuel Cells

NASA Astrophysics Data System (ADS)

Banerjee, Rupak

Water management has been identified as a critical issue in the development of PEM fuel cells for automotive applications. Water is present inside the PEM fuel cell in three phases, i.e. liquid phase, vapor phase and mist phase. Liquid water in the reactant channels causes flooding of the cell and blocks the transport of reactants to the reaction sites at the catalyst layer. Understanding the behavior of liquid water in the reactant channels would allow us to devise improved strategies for removing liquid water from the reactant channels. In situ fuel cell tests have been performed to identify and diagnose operating conditions which result in the flooding of the fuel cell. A relationship has been identified between the liquid water present in the reactant channels and the cell performance. A novel diagnostic technique has been established which utilizes the pressure drop multiplier in the reactant channels to predict the flooding of the cell or the drying-out of the membrane. An ex-situ study has been undertaken to quantify the liquid water present in the reactant channels. A new parameter, the Area Coverage Ratio (ACR), has been defined to identify the interfacial area of the reactant channel which is blocked for reactant transport by the presence of liquid water. A parametric study has been conducted to study the effect of changing temperature and the inlet relative humidity on the ACR. The ACR decreases with increase in current density as the gas flow rates increase, removing water more efficiently. With increase in temperature, the ACR decreases rapidly, such that by 60°C, there is no significant ACR to be reported. Inlet relative humidity of the gases does change the saturation of the gases in the channel, but did not show any significant effect on the ACR. Automotive powertrains, which is the target for this work, are continuously faced with transient changes. Water management under transient operating conditions is significantly more challenging and has not been investigated in detail. This study begins to investigate the effects of changing operating conditions on liquid water transport through the reactant channels. It has been identified that rapidly increasing temperature leads to the dry-out of the membrane and rapidly cooling the cell below 55°C results in the start of cell flooding. In changing the operating load of the PEMFC, overshoot in the pressure drop in the reactant channel has been identified for the first time as part of this investigation. A parametric study has been conducted to identify the factors which influence this overshoot behavior.

Synthesis of hetero compounds using dialkylcarbonate quaternation

DOEpatents

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2017-10-17

Methods of preparing hetero ionic complexes, and ionic liquids from bisulfate salts of heteroatomic compounds using dialkylcarbonates as a primary quaternizing reactant are disclosed. Also disclosed are methods of making electrochemical cells comprising the ionic liquids, and an electrochemical cell comprising an alkaline electrolyte and a hetero ionic complex additive.

Synthesis of hetero ionic compounds using dialkylcarbonate quaternization

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

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2017-09-19

Methods of preparing hetero ionic complexes, and ionic liquids from bisulfate salts of heteroatomic compounds using dialkylcarbonates as a primary quaternizing reactant are disclosed. Also disclosed are methods of making electrochemical cells comprising the ionic liquids, and an electrochemical cell comprising an alkaline electrolyte and a hetero ionic complex additive.

Synthesis of hetero ionic compounds using dialkylcarbonate quaternization

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

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2018-04-03

Methods of preparing hetero ionic complexes, and ionic liquids from bisulfate salts of heteroatomic compounds using dialkylcarbonates as a primary quaternizing reactant are disclosed. Also disclosed are methods of making electrochemical cells comprising the ionic liquids, and an electrochemical cell comprising an alkaline electrolyte and a hetero ionic complex additive.

Chemical approach for controlling nadimide cure temperature and rate

NASA Technical Reports Server (NTRS)

Lauver, R. W. (Inventor)

1985-01-01

Polyimide resins suitable for use as composite matrix materials are formed by copolymerization of maleic and norbornenyl end-capped monomers and oligomers. The copolymers can be cured at temperatures under about 300 C. by controlling the available concentration of the maleic end-capped reactant. This control can be achieved by adding sufficient amounts of said maleic reactant, or by chemical modification of either copolymer, to increase Diels-Alder retrogression of the norbornenyl-capped reactant and/or holding initiation and polymerization to a rate compatible with the availability of the maleic-capped reactant.

Chemical approach for controlling nadimide cure temperature and rate

NASA Technical Reports Server (NTRS)

Lauver, R. W. (Inventor)

1984-01-01

Polyimide resins suitable for use as composite matrix materials are formed by copolymerization of maleic and norbornenyl endcapped monomers and oligomers. The copolymers can be cured at temperatures under about 300 C by controlling the available concentration of the maleic capped reactant. This control can be achieved by adding sufficient amounts of said maleic reactant, or by chemical modification of either copolymer, so as to either increase Diels-Alder retrogression of the norbornenyl capped reactant and/or holding initiation and polymerization to a rate compatible with the availability of the maleic capped reactant.

Chemical approach for controlling nadimide cure temperature and rate

NASA Technical Reports Server (NTRS)

Lauver, R. W. (Inventor)

1985-01-01

Polyimide resins suitable for use as composite matrix materials are formed by copolymerization of maleic and norbornenyl endcapped monomers and oligomers. The copolymers can be cured at temperatures under about 300 C by controlling the available concentration of the maleic endcapped reactant. This control is achieved by adding sufficient amounts of said maleic reactant or by chemical modification of either copolymer, to either increase Diels-Alder retrogression of the norbornenyl capped reactant and/or hold initiation and polymerization to a rate compatible with the availability of the maleic capped reactant.

Mechanism of Gaseous Detonation Propagation Through Reactant Layers Bounded by Inert Gas

NASA Astrophysics Data System (ADS)

Houim, Ryan

2017-11-01

Vapor cloud explosions and rotating detonation engines involve the propagation of gaseous detonations through a layer of reactants that is bounded by inert gas. Mechanistic understanding of how detonations propagate stably or fail in these scenarios is incomplete. Numerical simulations were used to investigate mechanisms of gaseous detonation propagation through reactant layers bounded by inert gas. The reactant layer was a stoichiometric mixture of C2H4/O2 at 1 atm and 300K and is 4 detonation cells in height. Cases where the inert gas temperature was 300, 1500, and 3500 K will be discussed. The detonation failed for the 300 K case and propagated marginally for the 1500 K case. Surprisingly, the detonation propagated stably for the 3500 K case. A shock structure forms that involves a detached shock in the inert gas and a series of oblique shocks in the reactants. A small local explosion is triggered when the Mach stem of a detonation cell interacts with the compressed reactants behind one of these oblique shocks. The resulting pressure wave produces a new Mach stem and a new triple point that leads to a stable detonation. Preliminary results on the influence of a deflagration at the inert/reactant interface on the stability of a layered detonation will be discussed.

Taking the plunge: chemical reaction dynamics in liquids.

PubMed

Orr-Ewing, Andrew J

2017-12-11

The dynamics of chemical reactions in liquid solutions are now amenable to direct study using ultrafast laser spectroscopy techniques and advances in computer simulation methods. The surrounding solvent affects the chemical reaction dynamics in numerous ways, which include: (i) formation of complexes between reactants and solvent molecules; (ii) modifications to transition state energies and structures relative to the reactants and products; (iii) coupling between the motions of the reacting molecules and the solvent modes, and exchange of energy; (iv) solvent caging of reactants and products; and (v) structural changes to the solvation shells in response to the changing chemical identity of the solutes, on timescales which may be slower than the reactive events. This article reviews progress in the study of bimolecular chemical reaction dynamics in solution, concentrating on reactions which occur on ground electronic states. It illustrates this progress with reference to recent experimental and computational studies, and considers how the various ways in which a solvent affects the chemical reaction dynamics can be unravelled. Implications are considered for research in fields such as mechanistic synthetic chemistry.

Theoretical models for the combustion of alloyable materials

NASA Astrophysics Data System (ADS)

Armstrong, Robert

1992-09-01

The purpose of this work is to extend a theoretical model of layered (laminar) media for SHS combustion presented in an earlier article [1] to explore possible mechanisms for after-burning in SHS ( i.e., gasless) combustion. As before, our particular interest is how the microscopic geometry of the solid reactants is reflected in the combustion wave and in the reaction product. The model is constructed from alternating lamina of two pure reactants that interdiffuse exothermically to form a product. Here, the laminar model is extended to contain layers of differing thicknesses. Using asymptotic theory, it was found that under certain conditions, the combustion wave can become “detached,” and an initial thin flame propagates through the media, leaving a slower, thicker flame following behind ( i.e., afterburning). Thin laminae are consumed in the initial flame and are thick in the secondary. The thin flame has a width determined by the inverse of the activation energy of diffusion, as found previously. The width of the afterburning zone, however, is determined by the absolute time of diffusion for the thicker laminae. Naturally, when the laminae are all the same thickness, there is only one thin flame. The condition for the appearance of afterburning is found to be contingent on the square of the ratio of smallestto-largest thicknesses being considerably less than unity.

Core-shell-structured nanothermites synthesized by atomic layer deposition

NASA Astrophysics Data System (ADS)

Qin, Lijun; Gong, Ting; Hao, Haixia; Wang, Keyong; Feng, Hao

2013-12-01

Thermite materials feature very exothermic solid-state redox reactions. However, the energy release rates of traditional thermite mixtures are limited by the reactant diffusion velocities. In this work, atomic layer deposition (ALD) is utilized to synthesize thermite materials with greatly enhanced reaction rates. By depositing certain types of metal oxides (oxidizers) onto a commercial Al nanopowder, core-shell-structured nanothermites can be produced. The average film deposition rate on the Al nanopowder is 0.17 nm/cycle for ZnO and 0.031 nm/cycle for SnO2. The thickness of the oxidizer layer can be precisely controlled by adjusting the ALD cycle number. The compositions, morphologies, and structures of the ALD nanothermites are characterized by X-ray photoelectron spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy. The characterization results reveal nearly perfect coverage of the Al nanoparticles by uniform ALD oxidizer layers and confirm the formation of core-shell nanoparticles. Combustion properties of the nanothermites are probed by laser ignition technique. Reactions of the core-shell-structured nanothermites are several times faster than the mixture of nanopowders. The promoted reaction rate is mostly attributed to the uniform distribution of reactants on the nanometer scale. These core-shell-structured nanothermites provide a potential pathway to control and enhance thermite reactions.

In-ground operation of Geothermic Fuel Cells for unconventional oil and gas recovery

NASA Astrophysics Data System (ADS)

Sullivan, Neal; Anyenya, Gladys; Haun, Buddy; Daubenspeck, Mark; Bonadies, Joseph; Kerr, Rick; Fischer, Bernhard; Wright, Adam; Jones, Gerald; Li, Robert; Wall, Mark; Forbes, Alan; Savage, Marshall

2016-01-01

This paper presents operating and performance characteristics of a nine-stack solid-oxide fuel cell combined-heat-and-power system. Integrated with a natural-gas fuel processor, air compressor, reactant-gas preheater, and diagnostics and control equipment, the system is designed for use in unconventional oil-and-gas processing. Termed a ;Geothermic Fuel Cell; (GFC), the heat liberated by the fuel cell during electricity generation is harnessed to process oil shale into high-quality crude oil and natural gas. The 1.5-kWe SOFC stacks are packaged within three-stack GFC modules. Three GFC modules are mechanically and electrically coupled to a reactant-gas preheater and installed within the earth. During operation, significant heat is conducted from the Geothermic Fuel Cell to the surrounding geology. The complete system was continuously operated on hydrogen and natural-gas fuels for ∼600 h. A quasi-steady operating point was established to favor heat generation (29.1 kWth) over electricity production (4.4 kWe). Thermodynamic analysis reveals a combined-heat-and-power efficiency of 55% at this condition. Heat flux to the geology averaged 3.2 kW m-1 across the 9-m length of the Geothermic Fuel Cell-preheater assembly. System performance is reviewed; some suggestions for improvement are proposed.

Synthesis of Ca(BH4)2 from Synthetic Colemanite Used in Hydrogen Storage by Mechanochemical Reaction

NASA Astrophysics Data System (ADS)

Karabulut, Ahmet F.; Guru, Metin; Boynueğri, Tuğba A.; Aydin, Mustafa Yasir

2016-08-01

In this study, synthesis of Ca(BH4)2 has been carried out with a solid phase reaction in which synthetic colemanite has been used as a raw material. Three dimensional high energy spex collider was selected for this mechanochemical reaction. Calcium borohydride is one of the most valuable metal borohydrides. In order to produce calcium borohydride economically, anhydrous colemanite mineral has been used as reactant. Calcium borohydride has been directly manufactured from anhydrous colemanite in spex-type ball milling without the need for any intermediate product. Thus, the advantages of this method over wet chemical procedure (such as having no intermediate product, no azeotropic limitations and no need of regaining product from solution after production by using evaporation, crystallization and drying processes) have made it possible to achieve the desired economical gains. Parametric experiments were conducted to determine the best conditions for the highest yield of solid phase reaction in the spex-type ball milling. Best results have been determined by using areas of related peaks in spectra of Fourier transform infrared spectroscopy (FT-IR). In order to use peaks area for determining Ca(BH4)2 concentration, a calibration graph of FT-IR absorbance peak areas has been created by using samples with known different concentrations of commercial Ca(BH4)2. Optimum amounts of calcium hydride and synthesis reaction time were found to be 2.1 times the stoichiometric ratio and 2500 min, respectively. As a result of these optimizations, the maximum yield of the solid phase reaction carried out by the spex-type ball milling has been determined as 93%.

Cryogenic reactant storage for lunar base regenerative fuel cells

NASA Technical Reports Server (NTRS)

Kohout, Lisa L.

1989-01-01

There are major advantages to be gained by integrating a cryogenic reactant storage system with a hydrogen-oxygen regenerative fuel cell (RFC) to provide on-site electrical power during the lunar night. Although applicable to any power system using hydrogen-oxygen RFC's for energy storage, cryogenic reactant storage offers a significant benefit whenever the sun/shade cycle and energy storage period approach hundreds of hours. For solar power installations on the moon, cryogenic reactant storage reduces overall specific mass and meteoroid vulnerability of the system. In addition, it offers synergistic benefits to on-site users, such as availability of primary fuel cell reactants for surface rover vehicles and cryogenic propellants for OTV's. The integration involves processing and storing the RFC reactant streams as cryogenic liquids rather than pressurized gases, so that reactant containment (tankage per unit mass of reactants) can be greatly reduced. Hydrogen-oxygen alkaline RFC's, GaAs photovoltaic (PV) arrays, and space cryogenic processing/refrigeration technologies are assumed to be available for the conceptual system design. Advantages are demonstrated by comparing the characteristics of two power system concepts: a conventional lunar surface PV/RFC power system using pressurized gas storage in SOA filament wound pressure vessels and, that same system with gas liquefaction and storage replacing the pressurized storage. Comparisons are made at 20 and 250 kWe. Although cryogenic storage adds a processing plant (drying and liquefaction) to the system plus 30 percent more solar array to provide processing power, the approximate order of magnitude reduction in tankage mass, confirmed by this analysis, results in a reduction in overall total system mass of approximately 50 percent.

Thermal device and method for production of carbon monoxide and hydrogen by thermal dissociation of hydrocarbon gases

DOEpatents

Detering, Brent A.; Kong, Peter C.

2001-01-01

Carbon monoxide is produced in a fast quench reactor. The production of carbon monoxide includes injecting carbon dioxide and some air into a reactor chamber having a high temperature at its inlet and a rapidly expanding a reactant stream, such as a restrictive convergent-divergent nozzle at its outlet end. Carbon dioxide and other reactants such as methane and other low molecular weight hydrocarbons are injected into the reactor chamber. Other gas may be added at different stages in the process to form a desired end product and prevent back reactions. The resulting heated gaseous stream is then rapidly cooled by expansion of the gaseous stream.

Contact structure for use in catalytic distillation

DOEpatents

Jones, Jr., Edward M.

1984-01-01

A method for conducting catalytic chemical reactions and fractionation of the reaction mixture comprising feeding reactants into a distillation column reactor contracting said reactant in liquid phase with a fixed bed catalyst in the form of a contact catalyst structure consisting of closed porous containers containing the catatlyst for the reaction and a clip means to hold and support said containers, which are disposed above, i.e., on the distillation trays in the tower. The trays have weir means to provide a liquid level on the trays to substantially cover the containers. In other words, the trays function in their ordinary manner with the addition thereto of the catalyst. The reaction mixture is concurrently fractionated in the column.

Vial OrganicTM-Organic Chemistry Labs for High School and Junior College

NASA Astrophysics Data System (ADS)

Russo, Thomas J.; Meszaros, Mark

1999-01-01

Vial Organic is the most economical, safe, and time-effective method of performing organic chemistry experiments. Activities are carried out in low-cost, sealed vials. Vial Organic is extremely safe because only micro quantities of reactants are used, reactants are contained in tightly sealed vials, and only water baths are used for temperature control. Vial Organic laboratory activities are easily performed within one 50-minute class period. When heat is required, a simple hot-water bath is prepared from a beaker of water and an inexpensive immersion heater. The low cost, ease of use, and relatively short time requirement will allow organic chemistry to be experienced by more students with less confusion and intimidation.

Influence of the reactant carbon-hydrogen-oxygen composition on the key products of the direct gasification of dewatered sewage sludge in supercritical water.

PubMed

Gong, Miao; Zhu, Wei; Fan, Yujie; Zhang, Huiwen; Su, Ying

2016-05-01

The supercritical water gasification of ten different types of dewatered sewage sludges was investigated to understand the relationship between sludge properties and gasification products. Experiments were performed in a high-pressure autoclave at 400°C for 60 min. Results showed that gasification of sewage sludge in supercritical water consists mainly of a gasification reaction, a carbonization reaction and a persistent organic pollutants synthesis reaction. Changes in the reactant C/H/O composition have significant effects on the key gasification products. Total gas production increased with increasing C/H2O of the reactant. The char/coke content increased with increasing C/H ratio of the reactant. A decrease in the C/O ratio of the reactant led to a reduction in polycyclic aromatic hydrocarbon formation. This means that we can adjust the reactant C/H/O composition by adding carbon-, hydrogen-, and oxygen-containing substances such as coal, algae and H2O2 to optimize hydrogen production and to inhibit an undesired by-product formation. Copyright © 2016 Elsevier Ltd. All rights reserved.

The effects of gas diffusion layers structure on water transportation using X-ray computed tomography based Lattice Boltzmann method

NASA Astrophysics Data System (ADS)

Jinuntuya, Fontip; Whiteley, Michael; Chen, Rui; Fly, Ashley

2018-02-01

The Gas Diffusion Layer (GDL) of a Polymer Electrolyte Membrane Fuel Cell (PEMFC) plays a crucial role in overall cell performance. It is responsible for the dissemination of reactant gasses from the gas supply channels to the reactant sites at the Catalyst Layer (CL), and the adequate removal of product water from reactant sites back to the gas channels. Existing research into water transport in GDLs has been simplified to 2D estimations of GDL structures or use virtual stochastic models. This work uses X-ray computed tomography (XCT) to reconstruct three types of GDL in a model. These models are then analysed via Lattice Boltzmann methods to understand the water transport behaviours under differing contact angles and pressure differences. In this study, the three GDL samples were tested over the contact angles of 60°, 80°, 90°, 100°, 120° and 140° under applied pressure differences of 5 kPa, 10 kPa and 15 kPa. By varying the contact angle and pressure difference, it was found that the transition between stable displacement and capillary fingering is not a gradual process. Hydrophilic contact angles in the region of 60°<θ < 90° showed stable displacement properties, whereas contact angles in the region of 100°<θ < 140° displayed capillary fingering characteristics.

40 CFR 720.45 - Information that must be included in the notice form.

Code of Federal Regulations, 2010 CFR

2010-07-01

... required in theory to account for the actual weight of monomer or other reactant molecules or fragments... one of the following two methods to develop or obtain the specified chemical identity information...

Catalytic and reactive polypeptides and methods for their preparation and use

DOEpatents

Schultz, Peter

1993-01-01

Catalytic and reactive polypeptides include a binding site specific for a reactant or reactive intermediate involved in a chemical reaction of interest. The polypeptides further include at least one active functionality proximate the bi.

Bicanonical ab Initio Molecular Dynamics for Open Systems.

PubMed

Frenzel, Johannes; Meyer, Bernd; Marx, Dominik

2017-08-08

Performing ab initio molecular dynamics simulations of open systems, where the chemical potential rather than the number of both nuclei and electrons is fixed, still is a challenge. Here, drawing on bicanonical sampling ideas introduced two decades ago by Swope and Andersen [ J. Chem. Phys. 1995 , 102 , 2851 - 2863 ] to calculate chemical potentials of liquids and solids, an ab initio simulation technique is devised, which introduces a fictitious dynamics of two superimposed but otherwise independent periodic systems including full electronic structure, such that either the chemical potential or the average fractional particle number of a specific chemical species can be kept constant. As proof of concept, we demonstrate that solvation free energies can be computed from these bicanonical ab initio simulations upon directly superimposing pure bulk water and the respective aqueous solution being the two limiting systems. The method is useful in many circumstances, for instance for studying heterogeneous catalytic processes taking place on surfaces where the chemical potential of reactants rather than their number is controlled and opens a pathway toward ab initio simulations at constant electrochemical potential.

In situ microcalorimetric investigation on the formation of cadmium-organic framework based on 5-mercaptoisophthalic acid

NASA Astrophysics Data System (ADS)

Cen, Huoshi; Liu, Wenlong; Nan, Zhaodong

In situ microcalorimetry was first used to study the crystal formation processes of porous metal-organic frameworks (MOF), [((CH3)2NH2)Cd(MIPA)]4ṡ×G, where H3MIPA is 5-Mercaptoisophthalic acid, G represents guest of DMA and H2O. An endothermic process occurred firstly, which is corresponding to the chemical reaction among the reactants. Exothermic processes followed the endothermal process are corresponding to crystal nucleation and growth. The experimental results demonstrate that a solid sample was first obtained at 150∘C for 24h. X-ray powder diffraction (XRD) peaks of the samples enhanced with the experimental time increasing from 24 to 60h (as 24, 35, 48 and 60h). The adsorption properties of the crystal obtained at 150∘C for 60h are more excellent than those reported and the same MOF synthesized at 150∘C for 72h. This study may give a method for investigation on MOFs formation mechanism and help to synthesize this kind of functional materials.

Reflections on the value of electron microscopy in the study of heterogeneous catalysts

PubMed Central

2017-01-01

Electron microscopy (EM) is arguably the single most powerful method of characterizing heterogeneous catalysts. Irrespective of whether they are bulk and multiphasic, or monophasic and monocrystalline, or nanocluster and even single-atom and on a support, their structures in atomic detail can be visualized in two or three dimensions, thanks to high-resolution instruments, with sub-Ångstrom spatial resolutions. Their topography, tomography, phase-purity, composition, as well as the bonding, and valence-states of their constituent atoms and ions and, in favourable circumstances, the short-range and long-range atomic order and dynamics of the catalytically active sites, can all be retrieved by the panoply of variants of modern EM. The latter embrace electron crystallography, rotation and precession electron diffraction, X-ray emission and high-resolution electron energy-loss spectra (EELS). Aberration-corrected (AC) transmission (TEM) and scanning transmission electron microscopy (STEM) have led to a revolution in structure determination. Environmental EM is already playing an increasing role in catalyst characterization, and new advances, involving special cells for the study of solid catalysts in contact with liquid reactants, have recently been deployed. PMID:28265196

Catalytic distillation process

DOEpatents

Smith, Jr., Lawrence A.

1982-01-01

A method for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C.sub.4 feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

Catalytic distillation process

DOEpatents

Smith, L.A. Jr.

1982-06-22

A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

Facile synthesis of Li2S-P2S5 glass-ceramics electrolyte with micron range particles for all-solid-state batteries via a low-temperature solution technique (LTST)

NASA Astrophysics Data System (ADS)

Choi, Sunho; Lee, Sewook; Park, Jongyeop; Nichols, William T.; Shin, Dongwook

2018-06-01

A lithium ion conductive 75Li2Sṡ25P2S5 glass-ceramics electrolyte is, for the first time, successfully synthesized via a new low-temperature solution technique (LTST) and compared to the conventional mechanical-milling technique. Both samples are composed of the highly lithium ion conductive thio-LISICON III analog phase. Due to the uniform dispersion of reactants in an organic liquid, the use of LTST produced significantly smaller and more uniform particle sizes (2.2 ± 1.68 μm) resulting in a 6.5 times higher specific surface area compared to the mechanically-milled sample. A pronounced enhancement of both the rate capability and cyclability is demonstrated for the LTST solid electrolyte sample due to the more intimate contact with the LiCoO2 active material. Furthermore, the LTST sample shows excellent electrochemical stability throughout the potential range of -1 to 5 V. These results suggest that the proposed technique using the optimized LTST process is promising for the preparation of 75Li2Sṡ25P2S5 solid electrolytes for use in advanced Li-ion batteries.

Process for forming a homogeneous oxide solid phase of catalytically active material

DOEpatents

Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

1995-01-01

A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

The effects of CO2 on the negative reactant ions of IMS

NASA Technical Reports Server (NTRS)

Spangler, Glenn E.

1995-01-01

In the presence of CO2, the negative reactant ions of ion mobility spectrometry (IMS) are ion clusters of CO4(-) and CO3(-). Methyl salicylate is ionized by the CO4(-)(H2O(n))(N2(m)) reactant ions, but not by the CO3(-)(H2O(n))(N2(m)) reactant ions. While the CO4(-) ions are formed by direct association, the CO3(-) ions require additional energy to be formed. The additional energy is provided by either excited neutral gas molecules in a metastable state or UV (ultraviolet) radiation.

Mechanochemical Synthesis of Carbon Nanothread Single Crystals.

PubMed

Li, Xiang; Baldini, Maria; Wang, Tao; Chen, Bo; Xu, En-Shi; Vermilyea, Brian; Crespi, Vincent H; Hoffmann, Roald; Molaison, Jamie J; Tulk, Christopher A; Guthrie, Malcolm; Sinogeikin, Stanislav; Badding, John V

2017-11-15

Synthesis of well-ordered reduced dimensional carbon solids with extended bonding remains a challenge. For example, few single-crystal organic monomers react under topochemical control to produce single-crystal extended solids. We report a mechanochemical synthesis in which slow compression at room temperature under uniaxial stress can convert polycrystalline or single-crystal benzene monomer into single-crystalline packings of carbon nanothreads, a one-dimensional sp 3 carbon nanomaterial. The long-range order over hundreds of microns of these crystals allows them to readily exfoliate into fibers. The mechanochemical reaction produces macroscopic single crystals despite large dimensional changes caused by the formation of multiple strong, covalent C-C bonds to each monomer and a lack of reactant single-crystal order. Therefore, it appears not to follow a topochemical pathway, but rather one guided by uniaxial stress, to which the nanothreads consistently align. Slow-compression room-temperature synthesis may allow diverse molecular monomers to form single-crystalline packings of polymers, threads, and higher dimensional carbon networks.

Molecular sieve catalysts for the regioselective and shape- selective oxyfunctionalization of alkanes in air.

PubMed

Thomas, J M; Raja, R; Sankar, G; Bell, R G

2001-03-01

Framework-substituted, molecular-sieve, aluminophosphate, microporous solids are the centerpieces of a new approach to the aerobic oxyfunctionalization of saturated hydrocarbons. The sieves, and the few percent of the Al(III) sites within them that are replaced by catalytically active, transition-metal ions in high oxidation states (Co(III), Mn(III), Fe(III)), are designed so as to allow free access of oxygen in to and out of the interior of these high-area solids. Certain metal-substituted, molecular sieves permit only end-on approach of linear alkanes to the active centers, thereby favoring enhanced reactivity of the terminal methyl groups. By optimizing cage dimension, with respect to that of the hydrocarbon reactant, as well as adjusting the average separation of active centers within a cage, and by choosing the sieve with the appropriate pore aperture, highly selective conversions such as n-hexane to hexanoic acid or adipic acid, and cyclohexane to cyclohexanol, cyclohexanone, or adipic acid, may be effected at low temperature, heterogeneously in air.

Method of operating a thermal engine powered by a chemical reaction

DOEpatents

Ross, John; Escher, Claus

1988-01-01

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

Method of operating a thermal engine powered by a chemical reaction

DOEpatents

Ross, J.; Escher, C.

1988-06-07

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

A KDE-Based Random Walk Method for Modeling Reactive Transport With Complex Kinetics in Porous Media

NASA Astrophysics Data System (ADS)

Sole-Mari, Guillem; Fernà ndez-Garcia, Daniel; Rodríguez-Escales, Paula; Sanchez-Vila, Xavier

2017-11-01

In recent years, a large body of the literature has been devoted to study reactive transport of solutes in porous media based on pure Lagrangian formulations. Such approaches have also been extended to accommodate second-order bimolecular reactions, in which the reaction rate is proportional to the concentrations of the reactants. Rather, in some cases, chemical reactions involving two reactants follow more complicated rate laws. Some examples are (1) reaction rate laws written in terms of powers of concentrations, (2) redox reactions incorporating a limiting term (e.g., Michaelis-Menten), or (3) any reaction where the activity coefficients vary with the concentration of the reactants, just to name a few. We provide a methodology to account for complex kinetic bimolecular reactions in a fully Lagrangian framework where each particle represents a fraction of the total mass of a specific solute. The method, built as an extension to the second-order case, is based on the concept of optimal Kernel Density Estimator, which allows the concentrations to be written in terms of particle locations, hence transferring the concept of reaction rate to that of particle location distribution. By doing so, we can update the probability of particles reacting without the need to fully reconstruct the concentration maps. The performance and convergence of the method is tested for several illustrative examples that simulate the Advection-Dispersion-Reaction Equation in a 1-D homogeneous column. Finally, a 2-D application example is presented evaluating the need of fully describing non-bilinear chemical kinetics in a randomly heterogeneous porous medium.

Conductive polymer layers to limit transfer of fuel reactants to catalysts of fuel cells to reduce reactant crossover

DOEpatents

Stanis, Ronald J.; Lambert, Timothy N.

2016-12-06

An apparatus of an aspect includes a fuel cell catalyst layer. The fuel cell catalyst layer is operable to catalyze a reaction involving a fuel reactant. A fuel cell gas diffusion layer is coupled with the fuel cell catalyst layer. The fuel cell gas diffusion layer includes a porous electrically conductive material. The porous electrically conductive material is operable to allow the fuel reactant to transfer through the fuel cell gas diffusion layer to reach the fuel cell catalyst layer. The porous electrically conductive material is also operable to conduct electrons associated with the reaction through the fuel cell gas diffusion layer. An electrically conductive polymer material is coupled with the fuel cell gas diffusion layer. The electrically conductive polymer material is operable to limit transfer of the fuel reactant to the fuel cell catalyst layer.

Unitized regenerative fuel cell system

NASA Technical Reports Server (NTRS)

Burke, Kenneth A. (Inventor)

2008-01-01

A Unitized Regenerative Fuel Cell system uses heat pipes to convey waste heat from the fuel cell stack to the reactant storage tanks. The storage tanks act as heat sinks/sources and as passive radiators of the waste heat from the fuel cell stack. During charge up, i.e., the electrolytic process, gases are conveyed to the reactant storage tanks by way of tubes that include dryers. Reactant gases moving through the dryers give up energy to the cold tanks, causing water vapor in with the gases to condense and freeze on the internal surfaces of the dryer. During operation in its fuel cell mode, the heat pipes convey waste heat from the fuel cell stack to the respective reactant storage tanks, thereby heating them such that the reactant gases, as they pass though the respective dryers on their way to the fuel cell stacks retrieve the water previously removed.

An integrative top-down and bottom-up qualitative model construction framework for exploration of biochemical systems.

PubMed

Wu, Zujian; Pang, Wei; Coghill, George M

Computational modelling of biochemical systems based on top-down and bottom-up approaches has been well studied over the last decade. In this research, after illustrating how to generate atomic components by a set of given reactants and two user pre-defined component patterns, we propose an integrative top-down and bottom-up modelling approach for stepwise qualitative exploration of interactions among reactants in biochemical systems. Evolution strategy is applied to the top-down modelling approach to compose models, and simulated annealing is employed in the bottom-up modelling approach to explore potential interactions based on models constructed from the top-down modelling process. Both the top-down and bottom-up approaches support stepwise modular addition or subtraction for the model evolution. Experimental results indicate that our modelling approach is feasible to learn the relationships among biochemical reactants qualitatively. In addition, hidden reactants of the target biochemical system can be obtained by generating complex reactants in corresponding composed models. Moreover, qualitatively learned models with inferred reactants and alternative topologies can be used for further web-lab experimental investigations by biologists of interest, which may result in a better understanding of the system.

Small Portable PEM Fuel Cell Systems for NASA Exploration Missions

NASA Technical Reports Server (NTRS)

Burke, Kenneth A.

2005-01-01

Oxygen-Hydrogen PEM-based fuel cell systems are being examined as a portable power source alternative in addition to advanced battery technology. Fuel cell power systems have been used by the Gemini, Apollo, and Space Shuttle programs. These systems have not been portable, but have been integral parts of their spacecraft, and have used reactants from a separate cryogenic supply. These systems typically have been higher in power. They also have had significant ancillary equipment sections that perform the pumping of reactants and coolant through the fuel cell stack and the separation of the product water from the unused reactant streams. The design of small portable fuel cell systems will be a significant departure from these previous designs. These smaller designs will have very limited ancillary equipment, relying on passive techniques for reactant and thermal management, and the reactant storage will be an integral part of the fuel cell system. An analysis of the mass and volume for small portable fuel cell systems was done to evaluate and quantify areas of technological improvement. A review of current fuel cell technology as well as reactant storage and management technology was completed to validate the analysis and to identify technology challenges

High-Performance Reactive Particle Tracking with Adaptive Representation

NASA Astrophysics Data System (ADS)

Schmidt, M.; Benson, D. A.; Pankavich, S.

2017-12-01

Lagrangian particle tracking algorithms have been shown to be effective tools for modeling chemical reactions in imperfectly-mixed media. One disadvantage of these algorithms is the possible need to employ large numbers of particles in simulations, depending on the concentration covariance structure, and these large particle numbers can lead to long computation times. Two distinct approaches have recently arisen to overcome this. One method employs spatial kernels that are related to a specified, reduced particle number; however, over-wide kernels, dictated by a very low particle number, lead to an excess of reaction calculations and cause a reduction in performance. Another formulation involves hybrid particles that carry multiple species of reactant, wherein each particle is treated as its own well-mixed volume, obviating the need for large numbers of particles for each species but still requiring a fixed number of hybrid particles. Here, we combine these two approaches and demonstrate an improved method for simulating a given system in a computationally efficient manner. Additionally, the independent nature of transport and reaction calculations in this approach allows for significant gains via parallelization in an MPI or OpenMP context. For benchmarking, we choose a CO2 injection simulation with dissolution and precipitation of calcite and dolomite, allowing us to derive the proper treatment of interaction between solid and aqueous phases.

Synthesis and Characterization of AlCl3 Impregnated Molybdenum Oxide as Heterogeneous Nano-Catalyst for the Friedel-Crafts Acylation Reaction in Ambient Condition.

PubMed

Jadhav, Arvind H; Chinnappan, Amutha; Hiremath, Vishwanath; Seo, Jeong Gil

2015-10-01

Aluminum trichloride (AlCl3) impregnated molybdenum oxide heterogeneous nano-catalyst was prepared by using simple impregnation method. The prepared heterogeneous catalyst was characterized by powder X-ray diffraction, FT-IR spectroscopy, solid-state NMR spectroscopy, SEM imaging, and EDX mapping. The catalytic activity of this protocol was evaluated as heterogeneous catalyst for the Friedel-Crafts acylation reaction at room temperature. The impregnated MoO4(AlCl2)2 catalyst showed tremendous catalytic activity in Friedel-Crafts acylation reaction under solvent-free and mild reaction condition. As a result, 84.0% yield of acyl product with 100% consumption of reactants in 18 h reaction time at room temperature was achieved. The effects of different solvents system with MoO4(AlCl2)2 catalyst in acylation reaction was also investigated. By using optimized reaction condition various acylated derivatives were prepared. In addition, the catalyst was separated by simple filtration process after the reaction and reused several times. Therefore, heterogeneous MoO4(AlCl2)2 catalyst was found environmentally benign catalyst, very convenient, high yielding, and clean method for the Friedel-Crafts acylation reaction under solvent-free and ambient reaction condition.

Method to convert biomass to 5-(hydroxymethyl)-furfural (HMF) and furfural using lactones, furans, and pyrans as solvents

DOEpatents

Dumesic, James A.; Ribeiro Gallo, Jean Marcel; Alonso, David

2014-07-08

Described is a process to produce hydroxymethyl furfural (HMF) from biomass-derived sugars. The process includes the steps of reacting a C5 and/or C6 sugar-containing reactant derived from biomass in a monophasic or biphasic reaction solution comprising water and a co-solvent. The co-solvent can be beta-, gamma-, and/or delta-lactones derived from biomass, tetrahydrofuran (THF) derived from biomass, and/or methyltetrahydrofuran (MTHF) derived from biomass. The reaction takes place in the presence of an acid catalyst and a dehydration catalyst for a time and under conditions such that at least a portion of glucose or fructose present in the reactant is converted to HMF.

Method to produce furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF)

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

Dumesic, James A.; Motagamwala, Ali Hussain

A process to produce furandicarboxylic acid (FDCA). The process includes the steps of reacting a C6 sugar-containing reactant in a reaction solution comprising a first organic solvent selected from the group consisting of beta-, gamma-, and delta-lactones, hydrofurans, hydropyrans, and combinations thereof, in the presence of an acid catalyst for a time and under conditions wherein at least a portion of the C6 sugar present in the reactant is converted to 5-(hydroxymethyl)furfural (HMF); oxidizing the HMF into FDCA with or without separating the HMF from the reaction solution; and extracting the FDCA by adding an aprotic organic solvent having amore » dipole moment of about 1.0 D or less to the reaction solution.« less

Probing the type of anomalous diffusion with single-particle tracking.

PubMed

Ernst, Dominique; Köhler, Jürgen; Weiss, Matthias

2014-05-07

Many reactions in complex fluids, e.g. signaling cascades in the cytoplasm of living cells, are governed by a diffusion-driven encounter of reactants. Yet, diffusion in complex fluids often exhibits an anomalous characteristic ('subdiffusion'). Since different types of subdiffusion have distinct effects on timing and equilibria of chemical reactions, a thorough determination of the reactants' type of random walk is key to a quantitative understanding of reactions in complex fluids. Here we introduce a straightforward and simple approach for determining the type of subdiffusion from single-particle tracking data. Unlike previous approaches, our method also is sensitive to transient subdiffusion phenomena, e.g. obstructed diffusion below the percolation threshold. We validate our strategy with data from experiment and simulation.

Contact structure for use in catalytic distillation

DOEpatents

Jones, E.M. Jr.

1984-03-27

A method is described for conducting catalytic chemical reactions and fractionation of the reaction mixture comprising feeding reactants into a distillation column reactor, contracting said reactant in liquid phase with a fixed bed catalyst in the form of a contact catalyst structure consisting of closed porous containers containing the catalyst for the reaction and a clip means to hold and support said containers, which are disposed above, i.e., on the distillation trays in the tower. The trays have weir means to provide a liquid level on the trays to substantially cover the containers. In other words, the trays function in their ordinary manner with the addition thereto of the catalyst. The reaction mixture is concurrently fractionated in the column. 7 figs.

Contact structure for use in catalytic distillation

DOEpatents

Jones, Jr., Edward M.

1985-01-01

A method and apparatus for conducting catalytic chemical reactions and fractionation of the reaction mixture, comprising and feeding reactants into a distillation column reactor contracting said reactant in a liquid phase with a fixed bed catalyst in the form of a contact catalyst structure, consisting of closed porous containers containing the catalyst for the reaction and a clip means to hold and support said containers, which are disposed above, i.e., on the distillation trays in the tower. The trays have weir means to provide a liquid level on the trays to substantially cover the containers. In other words, the trays function in their ordinary manner with the addition thereto of the catalyst. The reaction mixture is concurrently fractionated in the column.

Contact structure for use in catalytic distillation

DOEpatents

Jones, E.M. Jr.

1985-08-20

A method and apparatus are disclosed for conducting catalytic chemical reactions and fractionation of the reaction mixture, comprising and feeding reactants into a distillation column reactor contracting said reactant in a liquid phase with a fixed bed catalyst in the form of a contact catalyst structure, consisting of closed porous containers containing the catalyst for the reaction and a clip means to hold and support said containers, which are disposed above, i.e., on the distillation trays in the tower. The trays have weir means to provide a liquid level on the trays to substantially cover the containers. In other words, the trays function in their ordinary manner with the addition thereto of the catalyst. The reaction mixture is concurrently fractionated in the column. 7 figs.

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

Gschneidner, Jr., Karl A.; Schmidt, Frederick A.

A carbothermic reduction method is provided for reducing a La-, Ce-, MM-, and/or Y-containing oxide in the presence of carbon and a source of a reactant element comprising Si, Ge, Sn, Pb, As, Sb, Bi, and/or P to form an intermediate alloy material including a majority of La, Ce, MM, and/or Y and a minor amount of the reactant element. The intermediate material is useful as a master alloy for in making negative electrode materials for a metal hydride battery, as hydrogen storage alloys, as master alloy additive for addition to a melt of commercial Mg and Al alloys, steels,more » cast irons, and superalloys; or in reducing Sm.sub.2O.sub.3 to Sm metal for use in Sm--Co permanent magnets.« less

Effects of reactant rotation on the dynamics of the OH + CH4 → H2O + CH3 reaction: a six-dimensional study.

PubMed

Song, Hongwei; Li, Jun; Jiang, Bin; Yang, Minghui; Lu, Yunpeng; Guo, Hua

2014-02-28

The dynamics of the hydrogen abstraction reaction between methane and hydroxyl radical is investigated using an initial state selected time-dependent wave packet method within a six-dimensional model. The ab initio calibrated global potential energy surface of Espinosa-García and Corchado was used. Integral cross sections from several low-lying rotational states of both reactants have been obtained using the centrifugal sudden and J-shifting approximations. On the empirical potential energy surface, the rotational excitation of methane has little effect on the reaction cross section, but excited rotational states of OH inhibit the reactivity slightly. These results are rationalized with the newly proposed sudden vector projection model.

Amplified solid-state electrochemiluminescence detection of cholesterol in near-infrared range based on CdTe quantum dots decorated multiwalled carbon nanotubes@reduced graphene oxide nanoribbons.

PubMed

Huan, Juan; Liu, Qian; Fei, Airong; Qian, Jing; Dong, Xiaoya; Qiu, Baijing; Mao, Hanping; Wang, Kun

2015-11-15

An amplified solid-state electrochemiluminescence (ECL) biosensor for detection of cholesterol in near-infrared (NIR) range was constructed based on CdTe quantum dots (QDs) decorated multiwalled carbon nanotubes@reduced graphene nanoribbons (CdTe-MWCNTs@rGONRs), which were prepared by electrostatic interactions. The CdTe QDs decorated on the MWCNTs@rGONRs resulted in the amplified ECL intensity by ~4.5 fold and decreased onset potential by ~100 mV. By immobilization of the cholesterol oxidase (ChOx) and NIR CdTe-MWCNTs@rGONRs on the electrode surface, a solid-state ECL biosensor for cholesterol detection was constructed. When cholesterol was added to the detection solution, the immobilized ChOx catalyzed the oxidation of cholesterol to generate H2O2, which could be used as the co-reactant in the ECL system of CdTe-MWCNTs@rGONRs. The as-prepared biosensor exhibited good performance for cholesterol detection including good reproducibility, selectivity, and acceptable linear range from 1 μM to 1mM with a relative low detection limit of 0.33 μM (S/N=3). The biosensor was successfully applied to the determination of cholesterol in biological fluid and food sample, which would open a new possibility for development of solid-state ECL biosensors with NIR emitters. Copyright © 2015 Elsevier B.V. All rights reserved.

Sulfonated mesoporous silica-carbon composites and their use as solid acid catalysts

NASA Astrophysics Data System (ADS)

Valle-Vigón, Patricia; Sevilla, Marta; Fuertes, Antonio B.

2012-11-01

The synthesis of highly functionalized porous silica-carbon composites made up of sulfonic groups attached to a carbon layer coating the pores of three types of mesostructured silica (i.e. SBA-15, KIT-6 and mesocellular silica) is presented. The synthesis procedure involves the following steps: (a) removal of the surfactant, (b) impregnation of the silica pores with a carbon precursor, (c) carbonization and (d) sulfonation. The resulting silica-carbon composites contain ˜30 wt % of carbonaceous matter with a high density of acidic groups attached to the deposited carbon (i.e.sbnd SO3H, sbnd COOH and sbnd OH). The structural characteristics of the parent silica are retained in the composite materials, which exhibit a high surface area, a large pore volume and a well-ordered porosity made up uniform mesopores. The high density of the sulfonic groups in combination with the mesoporous structure of the composites ensures that a large number of active sites are easily accessible to reactants. These sulfonated silica-carbon composites behave as eco-friendly, active, selective, water tolerant and recyclable solid acids. In this study we demonstrate the usefulness of these composites as solid acid catalysts for the esterification of maleic anhydride, succinic acid and oleic acid with ethanol. These composites exhibit a superior intrinsic catalytic activity to other commercial solid acids such as Amberlyst-15.

Method for enriching a middle isotope using vibration-vibration pumping

DOEpatents

Rich, Joseph W.; Homicz, Gregory F.; Bergman, Richard C.

1989-01-01

Method for producing isotopically enriched material by vibration-vibration excitation of gaseous molecules wherein a middle mass isotope of an isotopic mixture including lighter and heavier mass isotopes preferentially populates a higher vibrational mode and chemically reacts to provide a product in which it is enriched. The method can be used for vibration-vibration enrichment of .sup.17 O in a CO reactant mixture.

Method for Improving Mg Doping During Group-III Nitride MOCVD

DOEpatents

Creighton, J. Randall; Wang, George T.

2008-11-11

A method for improving Mg doping of Group III-N materials grown by MOCVD preventing condensation in the gas phase or on reactor surfaces of adducts of magnesocene and ammonia by suitably heating reactor surfaces between the location of mixing of the magnesocene and ammonia reactants and the Group III-nitride surface whereon growth is to occur.

Combination of Cation Exchange and Quantized Ostwald Ripening for Controlling Size Distribution of Lead Chalcogenide Quantum Dots

DOE PAGES

Zhang, Changwang; Xia, Yong; Zhang, Zhiming; ...

2017-03-22

A new strategy for narrowing the size distribution of colloidal quantum dots (QDs) was developed by combining cation exchange and quantized Ostwald ripening. Medium-sized reactant CdS(e) QDs were subjected to cation exchange to form the target PbS(e) QDs, and then small reactant CdS(e) QDs were added which were converted to small PbS(e) dots via cation exchange. The small-sized ensemble of PbS(e) QDs dissolved completely rapidly and released a large amount of monomers, promoting the growth and size-focusing of the medium-sized ensemble of PbS(e) QDs. The addition of small reactant QDs can be repeated to continuously reduce the size distribution. Themore » new method was applied to synthesize PbSe and PbS QDs with extremely narrow size distributions and as a bonus they have hybrid surface passivation. In conclusion, the size distribution of prepared PbSe and PbS QDs are as low as 3.6% and 4.3%, respectively, leading to hexagonal close packing in monolayer and highly ordered three-dimensional superlattice.« less

Combination of Cation Exchange and Quantized Ostwald Ripening for Controlling Size Distribution of Lead Chalcogenide Quantum Dots

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

Zhang, Changwang; Xia, Yong; Zhang, Zhiming

A new strategy for narrowing the size distribution of colloidal quantum dots (QDs) was developed by combining cation exchange and quantized Ostwald ripening. Medium-sized reactant CdS(e) QDs were subjected to cation exchange to form the target PbS(e) QDs, and then small reactant CdS(e) QDs were added which were converted to small PbS(e) dots via cation exchange. The small-sized ensemble of PbS(e) QDs dissolved completely rapidly and released a large amount of monomers, promoting the growth and size-focusing of the medium-sized ensemble of PbS(e) QDs. The addition of small reactant QDs can be repeated to continuously reduce the size distribution. Themore » new method was applied to synthesize PbSe and PbS QDs with extremely narrow size distributions and as a bonus they have hybrid surface passivation. In conclusion, the size distribution of prepared PbSe and PbS QDs are as low as 3.6% and 4.3%, respectively, leading to hexagonal close packing in monolayer and highly ordered three-dimensional superlattice.« less

Effect of surface curvature on diffusion-limited reactions on a curved surface

NASA Astrophysics Data System (ADS)

Eun, Changsun

2017-11-01

To investigate how the curvature of a reactive surface can affect reaction kinetics, we use a simple model in which a diffusion-limited bimolecular reaction occurs on a curved surface that is hollowed inward, flat, or extended outward while keeping the reactive area on the surface constant. By numerically solving the diffusion equation for this model using the finite element method, we find that the rate constant is a non-linear function of the surface curvature and that there is an optimal curvature providing the maximum value of the rate constant, which indicates that a spherical reactant whose entire surface is reactive (a uniformly reactive sphere) is not the most reactive species for a given reactive surface area. We discuss how this result arises from the interplay between two opposing effects: the exposedness of the reactive area to its partner reactants, which causes the rate constant to increase as the curvature increases, and the competition occurring on the reactive surface, which decreases the rate constant. This study helps us to understand the role of curvature in surface reactions and allows us to rationally design reactants that provide a high reaction rate.

Development of ultrasonically levitated drops as microreactors for study of enzyme kinetics and potential as a universal portable analysis system

NASA Astrophysics Data System (ADS)

Scheeline, A.; Pierre, Z.; Field, C. R.; Ginsberg, M. D.

2009-05-01

Development of microfluidics has focused on carrying out chemical synthesis and analysis in ever-smaller volumes of solution. In most cases, flow systems are made of either quartz, glass, or an easily moldable polymer such as polydimethylsiloxane (Whitesides 2006). As the system shrinks, the ratio of surface area to volume increases. For studies of either free radical chemistry or protein chemistry, this is undesirable. Proteins stick to surfaces, biofilms grow on surfaces, and radicals annihilate on walls (Lewis et al. 2006). Thus, under those circumstances where small amounts of reactants must be employed, typical microfluidic systems are incompatible with the chemistry one wishes to study. We have developed an alternative approach. We use ultrasonically levitated microliter drops as well mixed microreactors. Depending on whether capillaries (to form the drop) and electrochemical sensors are in contact with the drop or whether there are no contacting solids, the ratio of solid surface area to volume is low or zero. The only interface seen by reactants is a liquid/air interface (or, more generally, liquid/gas, as any gas may be used to support the drop). While drop levitation has been reported since at least the 1940's, we are the second group to carry out enzyme reactions in levitated drops, (Weis; Nardozzi 2005) and have fabricated the lowest power levitator in the literature (Field; Scheeline 2007). The low consumption aspects of ordinary microfluidics combine with a contact-free determination cell (the levitated drop) that ensures against cross-contamination, minimizes the likelihood of biofilm formation, and is robust to changes in temperature and humidity (Lide 1992). We report kinetics measurements in levitated drops and explain how outgrowths of these accomplishments will lead to portable chemistry/biology laboratories well suited to detection of a wide range of chemical and biological agents in the asymmetric battlefield environment.

DON'T BE TRICKED BY YOUR INTEGRATED RATE PLOT!

EPA Science Inventory

Reaction order can be determined from kinetic data in a variety of ways. Two methods commonly employed are comparison of initial rates (while varying reactant concentration) and plotting integrated rate expressions. Both of these are introduced in general and physical chemistry t...

‘Greener’ Chemical Syntheses Using Mechanochemical Mixing or Microwave and Ultrasound Irradiation

EPA Science Inventory

Various emerging ‘greener’ strategic pathways researched primarily in the author’s own laboratory are summarized. They include solvent-free mechanochemical methods and microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of less-expensive and recyclabl...

Single cell performance studies on the FE/CR Redox Energy Storage System using mixed reactant solutions at elevated temperature

NASA Technical Reports Server (NTRS)

Gahn, R. F.; Hagedorn, N. H.; Ling, J. S.

1983-01-01

Experimental studies in a 14.5 sq cm single cell system using mixed reactant solutions at 65 C are described. Systems were tested under isothermal conditions, i.e., reactants and the cell were at the same temperature. Charging and discharging performance were evaluated by measuring watt-hour and coulombic efficiencies, voltage-current relationships, hydrogen evolution and membrane resistivity. Watt-hour efficiencies ranged from 86 percent at 43 ma/sq cm to 75 percent at 129 ma/sq cm with corresponding coulombic efficiencies of 92 percent and 97 percent, respectively. Hydrogen evolution was less than 1 percent of the charge coulumbic capacity during charge-discharge cycling. Bismuth amd bismuth-lead catalyzed chromium electrodes maintained reversible performance and low hydrogen evolution under normal and adverse cycling conditions. Reblending of the anode and cathode solutions was successfully demonstrated to compensate for osmotic volume changes. Improved performance was obtained with mixed reactant systems in comparison to the unmixed reactant systems. Previously announced in STAR as N83-25042

Single cell performance studies on the Fe/Cr Redox Energy Storage System using mixed reactant solutions at elevated temperature

NASA Technical Reports Server (NTRS)

Gahn, R. F.; Hagedorn, N. H.; Ling, J. S.

1983-01-01

Experimental studies in a 14.5 sq cm single cell system using mixed reactant solutions at 65 C are described. Systems were tested under isothermal conditions i.e., reactants and the cell were at the same temperature. Charging and discharging performance were evaluted by measuring watt-hour and coulombic efficiencies, voltage-current relationships, hydrogen evolution and membrane resistivity. Watt-hour efficiencies ranged from 86% at 43 ma/sq cm to 75% at 129 ma/sq cm with corresponding coulombic efficiencies of 92% and 97%, respectively. Hydrogen evolution was less than 1% of the charge coulombic capacity during charge-discharge cycling. Bismuth and bismuth-lead catalyzed chromium electrodes maintained reversible performance and low hydrogen evolution under normal and adverse cycling conditions. Reblending of the anode and cathode solutions was successfully demonstrated to compensate for osmotic volume changes. Improved performance was obtained with mixed reactant systems in comparison to the unmixed reactant systems.

Generative complexity of Gray-Scott model

NASA Astrophysics Data System (ADS)

Adamatzky, Andrew

2018-03-01

In the Gray-Scott reaction-diffusion system one reactant is constantly fed in the system, another reactant is reproduced by consuming the supplied reactant and also converted to an inert product. The rate of feeding one reactant in the system and the rate of removing another reactant from the system determine configurations of concentration profiles: stripes, spots, waves. We calculate the generative complexity-a morphological complexity of concentration profiles grown from a point-wise perturbation of the medium-of the Gray-Scott system for a range of the feeding and removal rates. The morphological complexity is evaluated using Shannon entropy, Simpson diversity, approximation of Lempel-Ziv complexity, and expressivity (Shannon entropy divided by space-filling). We analyse behaviour of the systems with highest values of the generative morphological complexity and show that the Gray-Scott systems expressing highest levels of the complexity are composed of the wave-fragments (similar to wave-fragments in sub-excitable media) and travelling localisations (similar to quasi-dissipative solitons and gliders in Conway's Game of Life).

Mixed feed evaporator

DOEpatents

Vakil, Himanshu B.; Kosky, Philip G.

1982-01-01

In the preparation of the gaseous reactant feed to undergo a chemical reaction requiring the presence of steam, the efficiency of overall power utilization is improved by premixing the gaseous reactant feed with water and then heating to evaporate the water in the presence of the gaseous reactant feed, the heating fluid utilized being at a temperature below the boiling point of water at the pressure in the volume where the evaporation occurs.

Al{sub 2}O{sub 3} - TiO{sub 2}-A simple sol-gel strategy to the synthesis of low temperature sintered alumina-aluminium titanate composites through a core-shell approach

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

Jayasankar, M.; Ananthakumar, S.; Mukundan, P.

A simple sol-gel based core-shell approach for the synthesis of alumina-aluminium titanate composite is reported. Alumina is the core and titania is the shell. The coating of titania has been performed in aqueous medium on alumina particle by means of heterocoagulation of titanyl chloride. Further heat treatment results in low temperature formation of aluminium titanate as well as low temperature sintering of alumina-aluminium titanate composites. The lowering of the reaction temperature can be attributed to the maximisation of the contact surface between the reactants due to the core-shell approach involving nanoparticles. The mechanism of formation of aluminium titanate and themore » observations on densification features in the present process are compared with that of mixture of oxides under identical conditions. The sintered alumina-aluminium titanate composite has an average grain size of 2 {mu}m. - Graphical abstract: The article presents a simple sol-gel process through core-shell approach to the synthesis of low temperature sintered alumina-aluminium titanate. The lowering of the reaction temperature can be attributed to the maximisation of the contact surface between the reactant due to the core-shell approach. This material showed the better microstructure control compared to the standard solid-state mixing route.« less

A Novel Computational Method to Reduce Leaky Reaction in DNA Strand Displacement.

PubMed

Li, Xin; Wang, Xun; Song, Tao; Lu, Wei; Chen, Zhihua; Shi, Xiaolong

2015-01-01

DNA strand displacement technique is widely used in DNA programming, DNA biosensors, and gene analysis. In DNA strand displacement, leaky reactions can cause DNA signals decay and detecting DNA signals fails. The mostly used method to avoid leakage is cleaning up after upstream leaky reactions, and it remains a challenge to develop reliable DNA strand displacement technique with low leakage. In this work, we address the challenge by experimentally evaluating the basic factors, including reaction time, ratio of reactants, and ion concentration to the leakage in DNA strand displacement. Specifically, fluorescent probes and a hairpin structure reporting DNA strand are designed to detect the output of DNA strand displacement, and thus can evaluate the leakage of DNA strand displacement reactions with different reaction time, ratios of reactants, and ion concentrations. From the obtained data, mathematical models for evaluating leakage are achieved by curve derivation. As a result, it is obtained that long time incubation, high concentration of fuel strand, and inappropriate amount of ion concentration can weaken leaky reactions. This contributes to a method to set proper reaction conditions to reduce leakage in DNA strand displacement.

Method for performing site-specific affinity fractionation for use in DNA sequencing

DOEpatents

Mirzabekov, Andrei Darievich; Lysov, Yuri Petrovich; Dubley, Svetlana A.

1999-01-01

A method for fractionating and sequencing DNA via affinity interaction is provided comprising contacting cleaved DNA to a first array of oligonucleotide molecules to facilitate hybridization between said cleaved DNA and the molecules; extracting the hybridized DNA from the molecules; contacting said extracted hybridized DNA with a second array of oligonucleotide molecules, wherein the oligonucleotide molecules in the second array have specified base sequences that are complementary to said extracted hybridized DNA; and attaching labeled DNA to the second array of oligonucleotide molecules, wherein the labeled re-hybridized DNA have sequences that are complementary to the oligomers. The invention further provides a method for performing multi-step conversions of the chemical structure of compounds comprising supplying an array of polyacrylamide vessels separated by hydrophobic surfaces; immobilizing a plurality of reactants, such as enzymes, in the vessels so that each vessel contains one reactant; contacting the compounds to each of the vessels in a predetermined sequence and for a sufficient time to convert the compounds to a desired state; and isolating the converted compounds from said array.

Miniaturized reaction vessel system, method for performing site-specific biochemical reactions and affinity fractionation for use in DNA sequencing

DOEpatents

Mirzabekov, Andrei Darievich; Lysov, Yuri Petrovich; Dubley, Svetlana A.

2000-01-01

A method for fractionating and sequencing DNA via affinity interaction is provided comprising contacting cleaved DNA to a first array of oligonucleotide molecules to facilitate hybridization between said cleaved DNA and the molecules; extracting the hybridized DNA from the molecules; contacting said extracted hybridized DNA with a second array of oligonucleotide molecules, wherein the oligonucleotide molecules in the second array have specified base sequences that are complementary to said extracted hybridized DNA; and attaching labeled DNA to the second array of oligonucleotide molecules, wherein the labeled re-hybridized DNA have sequences that are complementary to the oligomers. The invention further provides a method for performing multi-step conversions of the chemical structure of compounds comprising supplying an array of polyacrylamide vessels separated by hydrophobic surfaces; immobilizing a plurality of reactants, such as enzymes, in the vessels so that each vessel contains one reactant; contacting the compounds to each of the vessels in a predetermined sequence and for a sufficient time to convert the compounds to a desired state; and isolating the converted compounds from said array.

Method for performing site-specific affinity fractionation for use in DNA sequencing

DOEpatents

Mirzabekov, A.D.; Lysov, Y.P.; Dubley, S.A.

1999-05-18

A method for fractionating and sequencing DNA via affinity interaction is provided comprising contacting cleaved DNA to a first array of oligonucleotide molecules to facilitate hybridization between the cleaved DNA and the molecules; extracting the hybridized DNA from the molecules; contacting the extracted hybridized DNA with a second array of oligonucleotide molecules, wherein the oligonucleotide molecules in the second array have specified base sequences that are complementary to the extracted hybridized DNA; and attaching labeled DNA to the second array of oligonucleotide molecules, wherein the labeled re-hybridized DNA have sequences that are complementary to the oligomers. The invention further provides a method for performing multi-step conversions of the chemical structure of compounds comprising supplying an array of polyacrylamide vessels separated by hydrophobic surfaces; immobilizing a plurality of reactants, such as enzymes, in the vessels so that each vessel contains one reactant; contacting the compounds to each of the vessels in a predetermined sequence and for a sufficient time to convert the compounds to a desired state; and isolating the converted compounds from the array. 14 figs.

Characterization of Nano-Hydroxyapatite Synthesized from Sea Shells Through Wet Chemical Method

NASA Astrophysics Data System (ADS)

Santhosh, S.; Prabu, S. Balasivanandha

2012-10-01

Nano-hydroxyapatite (HA) was synthesized by a wet chemical reaction using powdered sea shells (CaO) as starting material which was converted to calcium hydroxide (Ca(OH)2) and subsequently reacted with phosphoric acid (H3PO4). Initially raw sea shells (CaCO3) were thermally converted to amorphous calcium oxide by heat treatment. Two sets of experiments were done; in the first experiment, HA powder was dried in an electric furnace and in the second experiment, the reactants were irradiated in a domestic microwave oven followed by microwave drying. In each set of experiments, the concentrations of the reactants were decreased gradually. HA was synthesized by slow addition of phosphoric acid (H3PO4) in to calcium hydroxide (Ca(OH)2) maintaining the pH of the solution at 10 to avoid the formation of calcium deficient apatites. In both the experiments, Ca:P ratio of 1.67 was maintained for the reagents. The synthesized samples showed X-ray diffraction (XRD) patterns corresponding to hydroxyapatite. The wet chemical process with furnace drying resulted in HA particles of size 7-34 nm, whereas microwave irradiated process yielded HA particles of size 34-102 nm as evidenced from XRD analyses. The above experimental work done by wet chemical synthesis to produce HA powder from sea shells is a simple processing method at room temperature. Microwave irradiation leads to uniform crystallite sizes as evident from this study, at differing concentrations of the reactants and is a comparatively easy method to synthesize HA. The high resolution scanning electron microscopy (HRSEM)/transmission electron microscopic (TEM) analyses revealed the characteristic rod-shaped nanoparticles of HA for the present study.

Simplified half-life methods for the analysis of kinetic data

NASA Technical Reports Server (NTRS)

Eberhart, J. G.; Levin, E.

1988-01-01

The analysis of reaction rate data has as its goal the determination of the order rate constant which characterize the data. Chemical reactions with one reactant and present simplified methods for accomplishing this goal are considered. The approaches presented involve the use of half lives or other fractional lives. These methods are particularly useful for the more elementary discussions of kinetics found in general and physical chemistry courses.

Quantum chemistry study of dielectric materials deposition

NASA Astrophysics Data System (ADS)

Widjaja, Yuniarto

The drive to continually decrease the device dimensions of integrated circuits in the microelectronics industry requires that deposited films approach subnanometer thicknesses. Hence, a fundamental understanding of the physics and chemistry of film deposition is important to obtain better control of the properties of the deposited film. We use ab initio quantum chemistry calculations to explore chemical reactions at the atomic level. Important thermodynamic and kinetic parameters are then obtained, which can then be used as inputs in constructing first-principles based reactor models. Studies of new systems for which data are not available can be conducted as well. In this dissertation, we use quantum chemistry simulations to study the deposition of gate dielectrics for metal-oxide-semiconductor (MOS) devices. The focus of this study is on heterogeneous reactions between gaseous precursors and solid surfaces. Adsorbate-surface interactions introduce additional degrees of complexity compared to the corresponding gas-phase or solid-state reactions. The applicability and accuracy of cluster approximations to represent solid surfaces are first investigated. The majority of our results are obtained using B3LYP density functional theory (DFT). The structures of reactants, products, and transition states are obtained, followed by calculations of thermochemical and kinetic properties. Whenever experimental data are available, qualitative and/or quantitative comparisons are drawn. Atomistic mechanisms and the energetics of several reactions leading to the deposition of SiO2, Si3N4, and potential new high-kappa materials such as ZrO2, HfO2, and Al 2O3 have been explored in this dissertation. Competing reaction pathways are explored for each of the deposition reactions studied. For example, the potential energy surface (PES) for ZrO2 ALD shows that the reactions proceed through a trapping-mediated mechanism, which results in a competition between desorption and decomposition of the gaseous reactants, i.e. ZrCl4 and H2O, on the ZrO2 surface. This competition results in relatively low saturation coverage, which consequently leads to a slow growth rate and possibly affects the thickness uniformity and conformality. The insights gained are then used to systematically improve deposition reactions. For instance, from the ZrO2 ALD PES, we are able to suggest the use of high temperature and pressure to obtain higher surface coverage.

METHOD OF PREPARING PuF$sub 4$

DOEpatents

Heath, R.E.; Florin, A.E.

1957-12-01

A method is presented for the preparation of plutonium tetrafluoride from plutonium trifluoride. This is accomplished by contacting the trifluoride with hydrogen fluoride in the presence of oxygen. The preferred temperature for the reaction is in the neighborhood of 600 deg C and the preferred reactant mixture consists of HF mixed with from 5 to 20 volume% of O/sub 2/.

Computational methods for diffusion-influenced biochemical reactions.

PubMed

Dobrzynski, Maciej; Rodríguez, Jordi Vidal; Kaandorp, Jaap A; Blom, Joke G

2007-08-01

We compare stochastic computational methods accounting for space and discrete nature of reactants in biochemical systems. Implementations based on Brownian dynamics (BD) and the reaction-diffusion master equation are applied to a simplified gene expression model and to a signal transduction pathway in Escherichia coli. In the regime where the number of molecules is small and reactions are diffusion-limited predicted fluctuations in the product number vary between the methods, while the average is the same. Computational approaches at the level of the reaction-diffusion master equation compute the same fluctuations as the reference result obtained from the particle-based method if the size of the sub-volumes is comparable to the diameter of reactants. Using numerical simulations of reversible binding of a pair of molecules we argue that the disagreement in predicted fluctuations is due to different modeling of inter-arrival times between reaction events. Simulations for a more complex biological study show that the different approaches lead to different results due to modeling issues. Finally, we present the physical assumptions behind the mesoscopic models for the reaction-diffusion systems. Input files for the simulations and the source code of GMP can be found under the following address: http://www.cwi.nl/projects/sic/bioinformatics2007/

Chelating agent-free, vapor-assisted crystallization method to synthesize hierarchical microporous/mesoporous MIL-125 (Ti).

PubMed

McNamara, Nicholas D; Hicks, Jason C

2015-03-11

Titanium-based microporous heterogeneous catalysts are widely studied but are often limited by the accessibility of reactants to active sites. Metal-organic frameworks (MOFs), such as MIL-125 (Ti), exhibit enhanced surface areas due to their high intrinsic microporosity, but the pore diameters of most microporous MOFs are often too small to allow for the diffusion of larger reactants (>7 Å) relevant to petroleum and biomass upgrading. In this work, hierarchical microporous MIL-125 exhibiting significantly enhanced interparticle mesoporosity was synthesized using a chelating-free, vapor-assisted crystallization method. The resulting hierarchical MOF was examined as an active catalyst for the oxidation of dibenzothiophene (DBT) with tert-butyl hydroperoxide and outperformed the solely microporous analogue. This was attributed to greater access of the substrate to surface active sites, as the pores in the microporous analogues were of inadequate size to accommodate DBT. Moreover, thiophene adsorption studies suggested the mesoporous MOF contained larger amounts of unsaturated metal sites that could enhance the observed catalytic activity.

Zinc-chlorine battery plant system and method

DOEpatents

Whittlesey, Curtis C.; Mashikian, Matthew S.

1981-01-01

A zinc-chlorine battery plant system and method of redirecting the electrical current around a failed battery module. The battery plant includes a power conditioning unit, a plurality of battery modules connected electrically in series to form battery strings, a plurality of battery strings electrically connected in parallel to the power conditioning unit, and a bypass switch for each battery module in the battery plant. The bypass switch includes a normally open main contact across the power terminals of the battery module, and a set of normally closed auxiliary contacts for controlling the supply of reactants electrochemically transformed in the cells of the battery module. Upon the determination of a failure condition, the bypass switch for the failed battery module is energized to close the main contact and open the auxiliary contacts. Within a short time, the electrical current through the battery module will substantially decrease due to the cutoff of the supply of reactants, and the electrical current flow through the battery string will be redirected through the main contact of the bypass switch.

Compartmented electrode structure

DOEpatents

Vissers, Donald R.; Shimotake, Hiroshi; Gay, Eddie C.; Martino, Fredric J.

1977-06-14

Electrodes for secondary electrochemical cells are provided with compartments for containing particles of the electrode reactant. The compartments are defined by partitions that are generally impenetrable to the particles of reactant and, in some instances, to the liquid electrolyte used in the cell. During cycling of the cell, reactant material initially loaded into a particular compartment is prevented from migrating and concentrating within the lower portion of the electrode or those portions of the electrode that exhibit reduced electrical resistance.

Nozzle erosion characterization and minimization for high-pressure rocket motor applications

NASA Astrophysics Data System (ADS)

Evans, Brian

Understanding of the processes that cause nozzle throat erosion and developing methods for mitigation of erosion rate can allow higher operating pressures for advanced rocket motors. However, erosion of the nozzle throat region, which is a strong function of operating pressure, must be controlled to realize the performance gains of higher operating pressures. The objective of this work was the study the nozzle erosion rates at a broad range of pressures from 7 to 34.5 MPa (1,000 to 5,000 psia) using two different rocket motors. The first is an instrumented solidpropellant motor (ISPM), which uses two baseline solid propellants; one is a non-metallized propellant called Propellant S and the other is a metallized propellant called Propellant M. The second test rig is a non-metallized solid-propellant rocket motor simulator (RMS). The RMS is a gas rocket with the ability to vary the combustion-product species composition by systematically varying the flow rates of gaseous reactants. Several reactant mixtures were utilized in the study to determine the relative importance of different oxidizing species (such as H2O, OH, and CO2). Both test rigs are equipped with a windowed nozzle section for real-time X-ray radiography diagnostics of the instantaneous throat variations for deducing the instantaneous erosion rates. The nozzle test section for both motors can also incorporate a nozzle boundary-layer control system (NBLCS) as a means of nozzle erosion mitigation. The effectiveness of the NBLCS at preventing nozzle throat erosion was demonstrated for both the RMS and the ISPM motors at chamber pressures up to 34 MPa (4930 psia). All tests conducted with the NBLCS showed signs of coning of the propellant surface, leading to increased mass burning rate and resultant chamber pressure. Two correlations were developed for the nozzle erosion rates from solid propellant testing, one for metallized propellant and one for non-metallized propellants. The non-metallized propellant correlation also incorporates the RMS data, accounting for swirling flow of the products in the RMS combustor. These correlations are useful for rocket nozzle designs. The correlation for non-metallized propellant and RMS firings was developed in terms of the effective oxidizer mass fraction and effective Reynolds number. The results calculated from this correlation were compared with measured erosion rate data within +/-15% or 0.05 mm/s (2 mils/s). For metallized propellant, the nozzle erosion rate was found to be relatively independent of the concentration of oxidizing species due to the diffusion-controlled process and the partial surface coverage by the liquid Al/Al2O3 layer. The nozzle erosion rate was also found to be lower than those of non-metallized propellant cases. Agreement between predicted and measured erosion rates was found to be within +/-20% or 0.04 mm/s (2 mils/s).

Detonation Velocity Calculations of Explosives with Slowly-Burning Constituents

NASA Astrophysics Data System (ADS)

Howard, W. Michael; Souers, P. Clark; Fried, Laurence E.

1997-07-01

The thermochemical code Equilbrium CHEETAH has been modified to allow partial reaction of constituents and partial flow of heat. Solid or liquid reactants are described by Einstein oscillators, whose temperatures can be changed to allow heat transfer. Hydroxy-terminated-poly-budadiene, mixed with RDX or HMX, does not react, as shown by the effect on the calculated detonation velocity. Aluminum and ammonium perchlorate in composites also do not react. Only partial heat flow also takes place in the unreacted materials. These results show that the usual assumption of total burn in a thermochemical code is probably incorrect, at least in the sonic reaction zone that drives the detonation velocity. A kinetic code would be the logical extension of this work.

Label-assisted mass spectrometry for the acceleration of reaction discovery and optimization

NASA Astrophysics Data System (ADS)

Cabrera-Pardo, Jaime R.; Chai, David I.; Liu, Song; Mrksich, Milan; Kozmin, Sergey A.

2013-05-01

The identification of new reactions expands our knowledge of chemical reactivity and enables new synthetic applications. Accelerating the pace of this discovery process remains challenging. We describe a highly effective and simple platform for screening a large number of potential chemical reactions in order to discover and optimize previously unknown catalytic transformations, thereby revealing new chemical reactivity. Our strategy is based on labelling one of the reactants with a polyaromatic chemical tag, which selectively undergoes a photoionization/desorption process upon laser irradiation, without the assistance of an external matrix, and enables rapid mass spectrometric detection of any products originating from such labelled reactants in complex reaction mixtures without any chromatographic separation. This method was successfully used for high-throughput discovery and subsequent optimization of two previously unknown benzannulation reactions.

Pulsed discharge ionization source for miniature ion mobility spectrometers

DOEpatents

Xu, Jun; Ramsey, J. Michael; Whitten, William B.

2004-11-23

A method and apparatus is disclosed for flowing a sample gas and a reactant gas (38, 43) past a corona discharge electrode (26) situated at a first location in an ion drift chamber (24), applying a pulsed voltage waveform comprising a varying pulse component and a dc bias component to the corona discharge electrode (26) to cause a corona which in turn produces ions from the sample gas and the reactant gas, applying a dc bias to the ion drift chamber (24) to cause the ions to drift to a second location (25) in the ion drift chamber (24), detecting the ions at the second location (25) in the drift chamber (24), and timing the period for the ions to drift from the corona discharge electrode to the selected location in the drift chamber.

Thermal synthesis apparatus

DOEpatents

Fincke, James R [Idaho Falls, ID; Detering, Brent A [Idaho Falls, ID

2009-08-18

An apparatus for thermal conversion of one or more reactants to desired end products includes an insulated reactor chamber having a high temperature heater such as a plasma torch at its inlet end and, optionally, a restrictive convergent-divergent nozzle at its outlet end. In a thermal conversion method, reactants are injected upstream from the reactor chamber and thoroughly mixed with the plasma stream before entering the reactor chamber. The reactor chamber has a reaction zone that is maintained at a substantially uniform temperature. The resulting heated gaseous stream is then rapidly cooled by passage through the nozzle, which "freezes" the desired end product(s) in the heated equilibrium reaction stage, or is discharged through an outlet pipe without the convergent-divergent nozzle. The desired end products are then separated from the gaseous stream.

Recycling of hazardous solid waste material using high-temperature solar process heat. 2. Reactor design and experimentation.

PubMed

Schaffner, Beatrice; Meier, Anton; Wuillemin, Daniel; Hoffelner, Wolfgang; Steinfeld, Aldo

2003-01-01

A novel high-temperature solar chemical reactor is proposed for the thermal recycling of hazardous solid waste material using concentrated solar power. It features two cavities in series, with the inner one functioning as the solar absorber and the outer one functioning as the reaction chamber. The solar reactor can handle thermochemical processes at temperatures above 1,300 K involving multiphases and controlled atmospheres. It further allows for batch or continuous mode of operation and for easy adjustment of the residence time of the reactants to match the kinetics of the reaction. A 10-kW solar reactor prototype was designed and tested for the carbothermic reduction of electric arc furnace dusts (EAFD). The reactor was subjected to mean solar flux intensities of 2,000 kW m(-2) and operated in both batch and continuous mode within the temperature range of 1,120-1,400 K. Extraction of over 90% of the toxic compounds originally contained in the EAFD was achieved while the condensable products of the off-gas contained mainly Zn, Pb, and Cl. The use of concentrated solar energy as the source of process heat offers the possibility of converting hazardous solid waste material into valuable commodities for processes in closed and sustainable material cycles.

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

Wong, J.; Larson, E.M.; Holt, J.B.

Real-time synchrotron diffraction has been used to monitor the phase transformations of highly exothermic, fast self-propagating solid combustion reactions on a subsecond time scale down to 100 milliseconds and in some instances to 10 milliseconds. Three systems were investigated: Ti + C {yields} TiC; Ti + C + xNi {yields} TiC + Ni-Ti alloy; and Al + Ni {yields} AlNi. In all three reactions, the first step was the melting of the metal reactants. Formation of TiC in the first two reactions was completed within 400 milliseconds of the melting of the Ti metal, indicating that the formation of TiCmore » took place during the passage of the combustion wave front. In the Al + Ni reaction, however, passage of the wave front was followed by the appearance and disappearance of at least one intermediate in the afterburn region. The final AlNi was formed some 5 seconds later and exhibited a delayed appearance of the (210) reflection, which tends to support a phase transformation from a disordered AlNi phase at high temperature to an ordered CsCl structure some 20 seconds later. This new experimental approach can be used to study the chemical dynamics of high-temperature solid-state phenomena and to provide the needed database to test various models for solid combustion. 28 refs., 4 figs.« less

Interaction of turbulent premixed flames with combustion products: Role of stoichiometry

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

Coriton, Bruno Rene Leon; Frank, Jonathan H.; Gomez, Alessandro

Stabilization methods of turbulent flames often involve mixing of reactants with hot products of combustion. The stabilizing effect of combustion product enthalpy has been long recognized, but the role played by the chemical composition of the product gases is typically overlooked. We employ a counterflow system to pinpoint the effects of the combustion product stoichiometry on the structure of turbulent premixed flames under conditions of both stable burning and local extinction. To that end, a turbulent jet of lean-to-rich, CH 4/O 2/N 2-premixed reactants at a turbulent Reynolds number of 1050 was opposed to a stream of hot products ofmore » combustion that were generated in a preburner. While the combustion product stream temperature was kept constant, its stoichiometry was varied independently from that of the reactant stream, leading to reactant-to-product stratification of relevance to practical combustion systems. The detailed structure of the turbulent flame front was analyzed in two series of experiments using laser-induced fluorescence (LIF): joint CH 2O LIF and OH LIF measurements and joint CO LIF and OH LIF measurements. Results revealed that a decrease in local CH 2O+OH and CO+OH reaction rates coincide with the depletion of OH radicals in the vicinity of the combustion product stream. These critical combustion reaction rates were more readily quenched in the presence of products of combustion from a stoichiometric flame, whereas they were favored by lean combustion products. As a result, stoichiometric combustion products contributed to a greater occurrence of local extinction. Furthermore, they limited the capacity of premixed reactants to ignite and of the turbulent premixed flames to stabilize. In contrast, lean and rich combustion products facilitated flame ignition and stability and reduced the rate of local extinction. The influence of the combustion product stream on the turbulent flame front was limited to a zone of approximately two millimeters from the gas mixing layer interface (GMLI) of the product stream. As a result, flame fronts that were separated from the GMLI by larger distances were unaffected by the product stream stoichiometry.« less

Interaction of turbulent premixed flames with combustion products: Role of stoichiometry

DOE PAGES

Coriton, Bruno Rene Leon; Frank, Jonathan H.; Gomez, Alessandro

2016-05-30

Stabilization methods of turbulent flames often involve mixing of reactants with hot products of combustion. The stabilizing effect of combustion product enthalpy has been long recognized, but the role played by the chemical composition of the product gases is typically overlooked. We employ a counterflow system to pinpoint the effects of the combustion product stoichiometry on the structure of turbulent premixed flames under conditions of both stable burning and local extinction. To that end, a turbulent jet of lean-to-rich, CH 4/O 2/N 2-premixed reactants at a turbulent Reynolds number of 1050 was opposed to a stream of hot products ofmore » combustion that were generated in a preburner. While the combustion product stream temperature was kept constant, its stoichiometry was varied independently from that of the reactant stream, leading to reactant-to-product stratification of relevance to practical combustion systems. The detailed structure of the turbulent flame front was analyzed in two series of experiments using laser-induced fluorescence (LIF): joint CH 2O LIF and OH LIF measurements and joint CO LIF and OH LIF measurements. Results revealed that a decrease in local CH 2O+OH and CO+OH reaction rates coincide with the depletion of OH radicals in the vicinity of the combustion product stream. These critical combustion reaction rates were more readily quenched in the presence of products of combustion from a stoichiometric flame, whereas they were favored by lean combustion products. As a result, stoichiometric combustion products contributed to a greater occurrence of local extinction. Furthermore, they limited the capacity of premixed reactants to ignite and of the turbulent premixed flames to stabilize. In contrast, lean and rich combustion products facilitated flame ignition and stability and reduced the rate of local extinction. The influence of the combustion product stream on the turbulent flame front was limited to a zone of approximately two millimeters from the gas mixing layer interface (GMLI) of the product stream. As a result, flame fronts that were separated from the GMLI by larger distances were unaffected by the product stream stoichiometry.« less

Reaction of benzene with atomic carbon: pathways to fulvenallene and the fulvenallenyl radical in extraterrestrial atmospheres and the interstellar medium.

PubMed

da Silva, Gabriel

2014-06-05

The reaction of benzene with ground-state atomic carbon, C((3)P), has been investigated using the G3X-K composite quantum chemical method. A suite of novel energetically favorable pathways that lead to previously unconsidered products are identified. Reaction is initiated by barrierless C atom cycloaddition to benzene on the triplet surface, producing a vibrationally excited [C7H6]* adduct that can dissociate to the cycloheptatrienyl radical (+ H) via a relatively loose transition state 4.4 kcal mol(-1) below the reactant energies. This study also identifies that this reaction adduct can isomerize to generate five-membered ring intermediates that can further dissociate to the global C7H5 minima, the fulvenallenyl radical (+ H), or to c-C5H4 and acetylene, with limiting barriers around 20 and 10 kcal mol(-1) below the reactants, respectively. If intersystem crossing to the singlet surface occurs, isomerization pathways that are lower-yet in energy are available leading to the C7H6 minima fulvenallene, with all barriers over 40 kcal mol(-1) below the reactants. From here further barrierless fragmentation to fulvenallenyl + H can proceed at ca. 25 kcal mol(-1) below the reactants. In the reducing atmospheres of planets like Jupiter and satellites like Titan, where benzene and C((3)P) are both expected, it is proposed that fulvenallene and the fulvenallenyl radical would be the dominant products of the C6H6 + C((3)P) reaction. Fulvenallenyl may also be a significant reaction product under collision-free conditions representative of the interstellar medium, although further work is required here to confirm the identity of the C7H5 radical product.

Product interactions and feedback in diffusion-controlled reactions

NASA Astrophysics Data System (ADS)

Roa, Rafael; Siegl, Toni; Kim, Won Kyu; Dzubiella, Joachim

2018-02-01

Steric or attractive interactions among reactants or between reactants and inert crowders can substantially influence the total rate of a diffusion-influenced reaction in the liquid phase. However, the role of the product species, which has typically different physical properties than the reactant species, has been disregarded so far. Here we study the effects of reactant-product and product-product interactions as well as asymmetric diffusion properties on the rate of diffusion-controlled reactions in the classical Smoluchowski-setup for chemical transformations at a perfect catalytic sphere. For this, we solve the diffusion equation with appropriate boundary conditions coupled by a mean-field approach on the second virial level to account for the particle interactions. We find that all particle spatial distributions and the total rate can change significantly, depending on the diffusion and interaction properties of the accumulated products. Complex competing and self-regulating (homeostatic) or self-amplifying effects are observed for the system, leading to both decrease and increase in the rates, as the presence of interacting products feeds back to the reactant flux and thus the rate with which the products are generated.

Improved Analytical Performance of Negative 63Ni Ion Mobility Spectrometry for On-line Measurement of Propofol Using Dichloromethane as Dopant

NASA Astrophysics Data System (ADS)

Zhou, Qinghua; Hua, Lei; Wang, Changsong; Li, Enyou; Li, Haiyang

2015-01-01

On-line monitoring of propofol in exhaled air is a potential way to evaluate the anaesthesia depth for patients during surgery. In this study, a negative 63Ni ionization high resolution ion mobility spectrometer with Bradbury-Nielsen-Gate-Grid structure was built to measure propofol with reactant ions Cl-(H2O) n using dichloromethane as dopant. Instead of forming three propofol ions (M - H)-, M · O2 -, and (M2 - H)- with reactant ions O2 -(H2O) n , only product ion M · Cl- was produced when introducing dichloromethane gas. The peak-to-peak resolution ( R p-p) between reactant ions Cl-(H2O) n and product ion M · Cl- was 17.4, which was 1.6 times larger than that between O2 -(H2O) n and product ion. Furthermore, the linear response range using reactant ions Cl-(H2O) n was 3.5 times wider than that obtained with reactant ions O2 -(H2O) n .

FindPrimaryPairs: An efficient algorithm for predicting element-transferring reactant/product pairs in metabolic networks.

PubMed

Steffensen, Jon Lund; Dufault-Thompson, Keith; Zhang, Ying

2018-01-01

The metabolism of individual organisms and biological communities can be viewed as a network of metabolites connected to each other through chemical reactions. In metabolic networks, chemical reactions transform reactants into products, thereby transferring elements between these metabolites. Knowledge of how elements are transferred through reactant/product pairs allows for the identification of primary compound connections through a metabolic network. However, such information is not readily available and is often challenging to obtain for large reaction databases or genome-scale metabolic models. In this study, a new algorithm was developed for automatically predicting the element-transferring reactant/product pairs using the limited information available in the standard representation of metabolic networks. The algorithm demonstrated high efficiency in analyzing large datasets and provided accurate predictions when benchmarked with manually curated data. Applying the algorithm to the visualization of metabolic networks highlighted pathways of primary reactant/product connections and provided an organized view of element-transferring biochemical transformations. The algorithm was implemented as a new function in the open source software package PSAMM in the release v0.30 (https://zhanglab.github.io/psamm/).

The effect of synthetic method and annealing temperature on metal site preference in Al(1-x)Ga(x)FeO3.

PubMed

Walker, James D S; Grosvenor, Andrew P

2013-08-05

Magnetoelectric materials couple both magnetic and electronic properties, making them attractive for use in multifunctional devices. The magnetoelectric AFeO3 compounds (Pna2(1); A = Al, Ga) have received attention as the properties of the system depend on composition as well as the synthetic method used. Al(1-x)Ga(x)FeO3. (0 ≤ x ≤ 1) was synthesized by the sol-gel and coprecipitation methods and studied by X-ray absorption near-edge spectroscopy (XANES). Al L(2,3-), Ga K-, and Fe K-edge XANES spectra were collected to examine how the average metal coordination number (CN) changes with the synthetic method. Al and Fe were found to prefer octahedral sites, while Ga prefers the tetrahedral site. It was found that composition played a larger role in determining site occupancies than synthetic method. Samples made by the sol-gel or ceramic methods (reported previously; Walker, J. D. S.; Grosvenor, A. P. J. Solid State Chem. 2013, 197, 147-153) showed smaller spectral changes than samples made via the coprecipitation method. This is attributed to greater ion mobility in samples synthesized via coprecipitation as the reactants do not have a long-range polymeric or oxide network during synthesis like samples synthesized via the sol-gel or ceramic method. Increasing annealing temperature increases the average coordination number of Al, and to a lesser extent Ga, while the average coordination number of Fe decreases. This study indicates that greater disorder is observed when the Al(1-x)Ga(x)FeO3. compounds have high Al content, and when annealed at higher temperatures.

Electrogenerated chemiluminescence of tris(2,2' bipyridine)ruthenium(II) using common biological buffers as co-reactant, pH buffer and supporting electrolyte.

PubMed

Kebede, Noah; Francis, Paul S; Barbante, Gregory J; Hogan, Conor F

2015-11-07

A series of aliphatic tertiary amines (HEPES, POPSO, EPPS and BIS-TRIS) commonly used to buffer the pH in biological experiments, were examined as alternative, non-toxic co-reactants for the electrogenerated chemiluminescence (ECL) of tris(2,2'-bipyridine)ruthenium(ii) ([Ru(bpy)3](2+)). These were found to be very attractive as "multi-tasking" reagents, serving not only as co-reactants, but also fulfiling the roles of pH buffer and supporting electrolyte within an aqueous environment; thus significantly simplifying the overall ECL analysis. Sub-nanomolar detection limits were obtained for [Ru(bpy)3](2+) in the presence of BIS-TRIS, making this species an valuable option for co-reactant ECL-based bioanalytical applications.

Alkali metal carbon dioxide electrochemical system for energy storage and/or conversion of carbon dioxide to oxygen

NASA Technical Reports Server (NTRS)

Hagedorn, Norman H. (Inventor)

1993-01-01

An alkali metal, such as lithium, is the anodic reactant; carbon dioxide or a mixture of carbon dioxide and carbon monoxide is the cathodic reactant; and carbonate of the alkali metal is the electrolyte in an electrochemical cell for the storage and delivery of electrical energy. Additionally, alkali metal-carbon dioxide battery systems include a plurality of such electrochemical cells. Gold is a preferred catalyst for reducing the carbon dioxide at the cathode. The fuel cell of the invention produces electrochemical energy through the use of an anodic reactant which is extremely energetic and light, and a cathodic reactant which can be extracted from its environment and therefore exacts no transportation penalty. The invention is, therefore, especially useful in extraterrestrial environments.

Transient Catalytic Combustor Model With Detailed Gas and Surface Chemistry

NASA Technical Reports Server (NTRS)

Struk, Peter M.; Dietrich, Daniel L.; Mellish, Benjamin P.; Miller, Fletcher J.; Tien, James S.

2005-01-01

In this work, we numerically investigate the transient combustion of a premixed gas mixture in a narrow, perfectly-insulated, catalytic channel which can represent an interior channel of a catalytic monolith. The model assumes a quasi-steady gas-phase and a transient, thermally thin solid phase. The gas phase is one-dimensional, but it does account for heat and mass transfer in a direction perpendicular to the flow via appropriate heat and mass transfer coefficients. The model neglects axial conduction in both the gas and in the solid. The model includes both detailed gas-phase reactions and catalytic surface reactions. The reactants modeled so far include lean mixtures of dry CO and CO/H2 mixtures, with pure oxygen as the oxidizer. The results include transient computations of light-off and system response to inlet condition variations. In some cases, the model predicts two different steady-state solutions depending on whether the channel is initially hot or cold. Additionally, the model suggests that the catalytic ignition of CO/O2 mixtures is extremely sensitive to small variations of inlet equivalence ratios and parts per million levels of H2.

Eco-friendly synthesis for MCM-41 nanoporous materials using the non-reacted reagents in mother liquor.

PubMed

Ng, Eng-Poh; Goh, Jia-Yi; Ling, Tau Chuan; Mukti, Rino R

2013-03-04

Nanoporous materials such as Mobil composite material number 41 (MCM-41) are attractive for applications such as catalysis, adsorption, supports, and carriers. Green synthesis of MCM-41 is particularly appealing because the chemical reagents are useful and valuable. We report on the eco-friendly synthesis of MCM-41 nanoporous materials via multi-cycle approach by re-using the non-reacted reagents in supernatant as mother liquor after separating the solid product. This approach was achieved via minimal requirement of chemical compensation where additional fresh reactants were added into the mother liquor followed by pH adjustment after each cycle of synthesis. The solid product of each successive batch was collected and characterized while the non-reacted reagents in supernatant can be recovered and re-used to produce subsequent cycle of MCM-41. The multi-cycle synthesis is demonstrated up to three times in this research. This approach suggests a low cost and eco-friendly synthesis of nanoporous material since less waste is discarded after the product has been collected, and in addition, product yield can be maintained at the high level.

Eco-friendly synthesis for MCM-41 nanoporous materials using the non-reacted reagents in mother liquor

PubMed Central

2013-01-01

Nanoporous materials such as Mobil composite material number 41 (MCM-41) are attractive for applications such as catalysis, adsorption, supports, and carriers. Green synthesis of MCM-41 is particularly appealing because the chemical reagents are useful and valuable. We report on the eco-friendly synthesis of MCM-41 nanoporous materials via multi-cycle approach by re-using the non-reacted reagents in supernatant as mother liquor after separating the solid product. This approach was achieved via minimal requirement of chemical compensation where additional fresh reactants were added into the mother liquor followed by pH adjustment after each cycle of synthesis. The solid product of each successive batch was collected and characterized while the non-reacted reagents in supernatant can be recovered and re-used to produce subsequent cycle of MCM-41. The multi-cycle synthesis is demonstrated up to three times in this research. This approach suggests a low cost and eco-friendly synthesis of nanoporous material since less waste is discarded after the product has been collected, and in addition, product yield can be maintained at the high level. PMID:23497184

Micromechanics investigation of expansive reactions in chemoelastic concrete.

PubMed

Lemarchand, Eric; Dormieux, Luc; Ulm, Franz-Josef

2005-11-15

Expansive reactions damage porous materials through the formation of reaction products of a volume in excess of the available space left by the reactants and the natural porosity of the material. This leads to pressurizing the pore space accessible to the reaction products, which differs when the chemical reaction is through-solution or topochemical or both in nature. This paper investigates expansive reactions from a micromechanical point of view, which allows bridging the scale from the local chemo-mechanical mechanisms to the macroscopically observable stress-free expansion. In particular, the study of the effect of morphology of the pore space, in which the chemical expansion occurs locally, on the macroscopically observable expansion is the main focus of this paper. The first part revisits the through-solution and the topochemical reaction mechanism within the framework of micro-macro-homogenization theories, and the effect of the microscopic geometry of pores and microcracks in the solid matrix on the macroscopic chemical expansion is examined. The second part deals with the transition from a topochemical to a through-solution-like mechanism that occurs in a solid matrix with inclusions (cracks, pores) of different morphology.

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

Alnajjar, Mikhail S.; Quigley, David; Kuntamukkula, Murty

Due to the inherent nature of pyrophoric substances to ignite spontaneously upon exposure to air, special precautions must be taken to ensure their safe handling and use. Pyrophoric gases (such as diborane, dichloroborane, phosphine, etc.) are typically the easiest class of pyrophoric substances to handle since the gas can be plumbed directly to the application and used remotely. Pyrophoric solids and liquids, however, require the user to physically manipulate them when transferring them from one container to another. Failure to follow proper safety precautions could result in serious injury or unintended consequences to laboratory personnel.12 Because of this danger, pyrophoricsmore » should be handled only by experienced personnel. Users with limited experience must be trained on how to handle pyrophoric reagents and consult with a knowledgeable staff member prior to performing the experimental task. The purpose of this article is three fold: 1) to provide guidelines and general safety precautions to avoid accidents, 2) describe proper techniques on how to successfully handle, store, and dispose of pyrophoric liquids and solids, and 3) illustrate best practices for working with this class of reactants in a laboratory environment.« less

Eco-friendly synthesis for MCM-41 nanoporous materials using the non-reacted reagents in mother liquor

NASA Astrophysics Data System (ADS)

Ng, Eng-Poh; Goh, Jia-Yi; Ling, Tau Chuan; Mukti, Rino R.

2013-03-01

Nanoporous materials such as Mobil composite material number 41 (MCM-41) are attractive for applications such as catalysis, adsorption, supports, and carriers. Green synthesis of MCM-41 is particularly appealing because the chemical reagents are useful and valuable. We report on the eco-friendly synthesis of MCM-41 nanoporous materials via multi-cycle approach by re-using the non-reacted reagents in supernatant as mother liquor after separating the solid product. This approach was achieved via minimal requirement of chemical compensation where additional fresh reactants were added into the mother liquor followed by pH adjustment after each cycle of synthesis. The solid product of each successive batch was collected and characterized while the non-reacted reagents in supernatant can be recovered and re-used to produce subsequent cycle of MCM-41. The multi-cycle synthesis is demonstrated up to three times in this research. This approach suggests a low cost and eco-friendly synthesis of nanoporous material since less waste is discarded after the product has been collected, and in addition, product yield can be maintained at the high level.

Acetic acid effects on enhancement of growth rate and reduction of amorphous carbon deposition on CNT arrays along a growth window in a floating catalyst reactor

NASA Astrophysics Data System (ADS)

Maghrebi, Morteza; Khodadadi, Abbas Ali; Mortazavi, Yadollah; Sane, Ali; Rahimi, Mohsen; Shirazi, Yaser; Tsakadze, Zviad; Mhaisalkar, Subodh

2009-11-01

The mm-long carbon nanotube (CNT) arrays were grown in a floating catalyst reactor, using xylene-ferrocene and a small amount of acetic acid as the feed. The CNT arrays deposited on a quartz substrate at several positions along the reactor were extensively characterized using Raman spectroscopy, scanning electron microscopy, X-ray diffraction, high-resolution transmission electron microscopy, and optical microscopy. Various characterization methods consistently reveal that the acetic acid additive to the feed alleviates deposition of amorphous carbon layer, which gradually thickens CNTs along the reactor. The acetic acid also resulted in a higher growth rate along the so-called growth window, where CNT arrays are deposited on the quartz substrate. High-performance liquid chromatography of extracted byproducts (PAHs) confirmed the presence of some polycyclic aromatic hydrocarbons. The solid weight of PAHs decreased upon addition of ferrocene as the catalyst precursor, as well as of acetic acid to xylene feed. The results suggest that primary light products of xylene pyrolysis can be competitive reactants for both catalytic and subsequent pyrolytic reactions. They may also be more efficient feeds for CNT growth than xylene itself.

Silica-promoted Diels-Alder reactions in carbon dioxide from gaseous to supercritical conditions

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

Weinstein, R.D.; Renslo, A.R.; Danheiser, R.L.

1999-04-15

Amorphous fumed silica (SiO{sub 2}) was shown to increase yields and selectivities of several Diels-Alder reactions in gaseous and supercritical CO{sub 2}. Pressure effects on the Diels-Alder reaction were explored using methyl vinyl ketone and penta-1,3-diene at 80 C. The selectivity of the reaction was not affected by pressure/density. As pressure was increased, the yield decreased. At the reaction temperature, adsorption isotherms at various pressures were obtained for the reactants and the Diels-Alder adduct. As expected when pressure is increased, the ratio of the amount of reactants adsorbed to the amount of reactants in the fluid phase decreases, thus causingmore » the yield to decrease. The Langmuir adsorption model fit the adsorption data. The Langmuir equilibrium partitioning constants all decreased with increasing pressure. The effect of temperature on adsorption was experimentally determined and traditional heats of adsorption were calculated. However, since supercritical CO{sub 2} is a highly compressible fluid, it is logical to examine the effect of temperature at constant density. In this case, entropies of adsorption were obtained. The thermodynamic properties that influence the real enthalpy and entropy of adsorption were derived. Methods of doping the silica and improving yields and selectivities were also explored.« less

Enhancing chemical reactions

DOEpatents

Morrey, John R.

1978-01-01

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

State relations for a two-phase mixture of reacting explosives and applications

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

Kubota, Shiro; Saburi, Tei; Ogata, Yuji

2007-10-15

To assess the assumptions behind the two phase mixture rule for reacting explosives, the shock-to-detonation transition process was calculated for high explosives using a finite difference method. An ignition and growth model and the Jones-Wilkins-Lee (JWL) equations of state were employed. The simple mixture rule assumes that the reacting explosive is a simple mixture of the reactant and product components. Four different assumptions, such as that of thermal equilibrium and isotropy, were adopted to calculate the pressure. The main purpose of this paper is to present the answer to the question of why the numerical results of shock-initiation are insensitivemore » to the assumptions adopted. The equations of state for reactants and products were assessed by considering plots of the specific internal energy E and specific volume V. If the slopes of the constant-pressure lines for both components in the E-V plane are almost the same, it is demonstrated that the numerical results are insensitive to the assumptions adopted. We have found that the relation for the specific volumes of the two components can be approximately expressed by a single curve of the specific volume of the reactant vs that of the products. We discuss this relationship in terms of the results of the numerical simulation. (author)« less

Compact hydrogenator

NASA Technical Reports Server (NTRS)

Simmonds, P. G. (Inventor)

1974-01-01

The development and characteristics of a hydrogenating apparatus are described. The device consists of a reaction chamber which is selectively permeable to atomic hydrogen and catalytically active to a hydrogenating reaction. In one device, hydrogen is pumped out of the reaction chamber while the reactant remains inside to remove molecular hydrogen so that more atomic hydrogen can pass through the walls. In another device, the reactant is pumped through the reaction chamber, and the hydrogen is removed from the material leaving the chamber. The reactant is then cycled through the chamber.

Tailor making high performance graphite fiber reinforced PMR polyimides

NASA Technical Reports Server (NTRS)

Serafini, T. T.; Vannucci, R. D.

1974-01-01

Studies performed to demonstrate the feasibility of using the polymerization of monomer reactants (PMR) approach to tailor make processable polyimide matrix resins are described. Monomeric reactant solutions containing the dimethyl ester of 3,3',4,4' -benzophenonetetracarboxylic acid, 4, 4' -methylenedianiline and the monomethyl ester of 5-norbornene-2, 3-dicarboxylic acid were used to impregnate Hercules HTS graphite fiber. Six different monomeric reactant stoichiometries were studied. The processing characteristics and elevated temperature mechanical properties of the PMR polyimide/HTS graphite fiber composites are described.

Fuel-Cell Structure Prevents Membrane Drying

NASA Technical Reports Server (NTRS)

Mcelroy, J.

1986-01-01

Embossed plates direct flows of reactants and coolant. Membrane-type fuel-cell battery has improved reactant flow and heat removal. Compact, lightweight battery produces high current and power without drying of membranes.

Oxygen-resistant hydrogenases and methods for designing and making same

DOEpatents

King, Paul [Golden, CO; Ghirardi, Maria L [Lakewood, CO; Seibert, Michael [Lakewood, CO

2009-03-10

The invention provides oxygen- resistant iron-hydrogenases ([Fe]-hydrogenases) for use in the production of H2. Methods used in the design and engineering of the oxygen-resistant [Fe]-hydrogenases are disclosed, as are the methods of transforming and culturing appropriate host cells with the oxygen-resistant [Fe]-hydrogenases. Finally, the invention provides methods for utilizing the transformed, oxygen insensitive, host cells in the bulk production of H.sub.2 in a light catalyzed reaction having water as the reactant.

Oxygen-resistant hydrogenases and methods for designing and making same

DOEpatents

King, Paul; Ghirardi, Maria Lucia; Seibert, Michael

2014-03-04

The invention provides oxygen-resistant iron-hydrogenases ([Fe]-hydrogenases) for use in the production of H.sub.2. Methods used in the design and engineering of the oxygen-resistant [Fe]-hydrogenases are disclosed, as are the methods of transforming and culturing appropriate host cells with the oxygen-resistant [Fe]-hydrogenases. Finally, the invention provides methods for utilizing the transformed, oxygen insensitive, host cells in the bulk production of H.sub.2 in a light catalyzed reaction having water as the reactant.

Characterization of the Kinetics of NF3-Fluorination of NpO2

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

Casella, Andrew M.; Scheele, Randall D.; McNamara, Bruce K.

2015-12-23

The exploitation of selected actinide and fission product fluoride volatilities has long been considered as a potentially attractive compact method for recycling used nuclear fuels to avoid generating the large volumes of radioactive waste arising from aqueous reprocessing [1-7]. The most developed process uses the aggressive and hazardous fluorinating agents hydrogen fluoride (HF) and/or molecular fluorine (F2) at high temperatures to volatilize the greatest fraction of the used nuclear fuel into a single gas stream. The volatilized fluorides are subsequently separated using a series of fractionation and condensation columns to recover the valuable fuel constituents and fission products. In pursuitmore » of a safer and less complicated approach, we investigated an alternative fluoride volatility-based process using the less hazardous fluorinating agent nitrogen trifluoride (NF3) and leveraging its less aggressive nature to selectively evolve fission product and actinide fluorides from the solid phase based on their reaction temperatures into a single recycle stream [8-15]. In this approach, successive isothermal treatments using NF3 will first evolve the more thermally susceptible used nuclear fuel constituents leaving the other constituents in the residual solids until subsequent isothermal temperature treatments cause these others to volatilize. During investigation of this process, individual neat used fuel components were treated with isothermal NF3 in an attempt to characterize the kinetics of each fluorination reaction to provide input into the design of a new volatile fluoride separations approach. In these directed investigations, complex behavior was observed between NF3 and certain solid reactants such as the actinide oxides of uranium, plutonium, and neptunium. Given the similar thermal reaction susceptibilities of neptunium oxide (NpO2) and uranium dioxide (UO2) and the importance of Np and U, we initially focused our efforts on determining the reaction kinetic parameters for NpO2. Characterizing the NF3 fluorination of NpO2 using established models for gas-solid reactions [16] proved unsuccessful so we developed a series of successive fundamental reaction mechanisms to characterize the observed successive fluorination reactions leading to production of the volatile neptunium hexafluoride (NpF6).« less

CW deuterium fluoride chemical laser with reactant combination C2H4/NF3

NASA Astrophysics Data System (ADS)

Jiang, Zhongfu; Hua, Weihong

1998-05-01

The characters of combustion driven cw deuterium fluoride (DF) chemical laser with C2H4/NF3 reactant were numerically investigated. The numerical simulation was carried out using compressibility scaling method--a finite difference technique for the numerical integration of the steady and unsteady Navier-stokes equations for reactive flow. The small signal gain and the flow field were calculated. The numerical results shown that active zone length of the cw DF chemical laser with C2H4/NF3 is very long, which is about 6 cm, and the average cavity pressure is about 7 torr as the combustion pressure is about 1.5 atm. These results shown that the DF chemical laser with C2H4/NF3 is suitable for high cavity pressure performance.

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

Jansen, Andrew N.; Vaughey, John T.; Chen, Zonghai

The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturatedmore » moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte is selected to have a higher redox potential than the redox reactant of the negative electrolyte.« less

A rapid, convenient, solventless green approach for the synthesis of oximes using grindstone chemistry.

PubMed

Saikia, Lakhinath; Baruah, Jejiron Maheswari; Thakur, Ashim Jyoti

2011-10-04

Synthesis of oximes is an important reaction in organic chemistry, because these versatile oximes are used for protection, purification, and characterization of carbonyl compounds. Nitriles, amides via Beckmann rearrangement, nitro compounds, nitrones, amines, and azaheterocycles can be synthesised from oximes. They also find applications for selective α-activation. In inorganic chemistry, oximes act as a versatile ligand.Several procedures for the preparation of oximes exist, but, most of them have not addressed the green chemistry issue. They are associated with generation of pollutants, requirement of high reaction temperature, low yields, lack of a generalized procedure, etc. Hence, there is a demand for developing an efficient, convenient, and non-polluting or less polluting alternative method for the preparation of oximes. In this context, bismuth compounds are very useful as they are cheap in general, commercially available, air stable crystalline solids, safe, and non-toxic, hence easy to handle. Carbonyl compounds (aliphatic, heterocyclic, and aromatic) were converted into the corresponding oximes in excellent yields by simply grinding the reactants at room temperature without using any solvent in the presence of Bi2O3. Most importantly, this method minimizes waste disposal problems, provides a simple yet efficient example of unconventional methodology and requires short time. We have developed a novel, quick, environmentally safe, and clean synthesis of aldoximes and ketoximes under solvent-free grinding condition.

Rapid and direct synthesis of complex perovskite oxides through a highly energetic planetary milling

PubMed Central

Lee, Gyoung-Ja; Park, Eun-Kwang; Yang, Sun-A; Park, Jin-Ju; Bu, Sang-Don; Lee, Min-Ku

2017-01-01

The search for a new and facile synthetic route that is simple, economical and environmentally safe is one of the most challenging issues related to the synthesis of functional complex oxides. Herein, we report the expeditious synthesis of single-phase perovskite oxides by a high-rate mechanochemical reaction, which is generally difficult through conventional milling methods. With the help of a highly energetic planetary ball mill, lead-free piezoelectric perovskite oxides of (Bi, Na)TiO3, (K, Na)NbO3 and their modified complex compositions were directly synthesized with low contamination. The reaction time necessary to fully convert the micron-sized reactant powder mixture into a single-phase perovskite structure was markedly short at only 30–40 min regardless of the chemical composition. The cumulative kinetic energy required to overtake the activation period necessary for predominant formation of perovskite products was ca. 387 kJ/g for (Bi, Na)TiO3 and ca. 580 kJ/g for (K, Na)NbO3. The mechanochemically derived powders, when sintered, showed piezoelectric performance capabilities comparable to those of powders obtained by conventional solid-state reaction processes. The observed mechanochemical synthetic route may lead to the realization of a rapid, one-step preparation method by which to create other promising functional oxides without time-consuming homogenization and high-temperature calcination powder procedures. PMID:28387324

A Novel Computational Method to Reduce Leaky Reaction in DNA Strand Displacement

PubMed Central

Li, Xin; Wang, Xun; Song, Tao; Lu, Wei; Chen, Zhihua; Shi, Xiaolong

2015-01-01

DNA strand displacement technique is widely used in DNA programming, DNA biosensors, and gene analysis. In DNA strand displacement, leaky reactions can cause DNA signals decay and detecting DNA signals fails. The mostly used method to avoid leakage is cleaning up after upstream leaky reactions, and it remains a challenge to develop reliable DNA strand displacement technique with low leakage. In this work, we address the challenge by experimentally evaluating the basic factors, including reaction time, ratio of reactants, and ion concentration to the leakage in DNA strand displacement. Specifically, fluorescent probes and a hairpin structure reporting DNA strand are designed to detect the output of DNA strand displacement, and thus can evaluate the leakage of DNA strand displacement reactions with different reaction time, ratios of reactants, and ion concentrations. From the obtained data, mathematical models for evaluating leakage are achieved by curve derivation. As a result, it is obtained that long time incubation, high concentration of fuel strand, and inappropriate amount of ion concentration can weaken leaky reactions. This contributes to a method to set proper reaction conditions to reduce leakage in DNA strand displacement. PMID:26491602

Gas-Phase Reaction Pathways and Rate Coefficients for the Dichlorosilane-Hydrogen and Trichlorosilane-Hydrogen Systems

NASA Technical Reports Server (NTRS)

Dateo, Christopher E.; Walch, Stephen P.

2002-01-01

As part of NASA Ames Research Center's Integrated Process Team on Device/Process Modeling and Nanotechnology our goal is to create/contribute to a gas-phase chemical database for use in modeling microelectronics devices. In particular, we use ab initio methods to determine chemical reaction pathways and to evaluate reaction rate coefficients. Our initial studies concern reactions involved in the dichlorosilane-hydrogen (SiCl2H2--H2) and trichlorosilane-hydrogen (SiCl2H-H2) systems. Reactant, saddle point (transition state), and product geometries and their vibrational harmonic frequencies are determined using the complete-active-space self-consistent-field (CASSCF) electronic structure method with the correlation consistent polarized valence double-zeta basis set (cc-pVDZ). Reaction pathways are constructed by following the imaginary frequency mode of the saddle point to both the reactant and product. Accurate energetics are determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations (CCSD(T)) extrapolated to the complete basis set limit. Using the data from the electronic structure calculations, reaction rate coefficients are obtained using conventional and variational transition state and RRKM theories.

Method for dry etching of transition metals

DOEpatents

Ashby, C.I.H.; Baca, A.G.; Esherick, P.; Parmeter, J.E.; Rieger, D.J.; Shul, R.J.

1998-09-29

A method for dry etching of transition metals is disclosed. The method for dry etching of a transition metal (or a transition metal alloy such as a silicide) on a substrate comprises providing at least one nitrogen- or phosphorus-containing {pi}-acceptor ligand in proximity to the transition metal, and etching the transition metal to form a volatile transition metal/{pi}-acceptor ligand complex. The dry etching may be performed in a plasma etching system such as a reactive ion etching (RIE) system, a downstream plasma etching system (i.e. a plasma afterglow), a chemically-assisted ion beam etching (CAIBE) system or the like. The dry etching may also be performed by generating the {pi}-acceptor ligands directly from a ligand source gas (e.g. nitrosyl ligands generated from nitric oxide), or from contact with energized particles such as photons, electrons, ions, atoms, or molecules. In some preferred embodiments of the present invention, an intermediary reactant species such as carbonyl or a halide ligand is used for an initial chemical reaction with the transition metal, with the intermediary reactant species being replaced at least in part by the {pi}-acceptor ligand for forming the volatile transition metal/{pi}-acceptor ligand complex.

Method for dry etching of transition metals

DOEpatents

Ashby, Carol I. H.; Baca, Albert G.; Esherick, Peter; Parmeter, John E.; Rieger, Dennis J.; Shul, Randy J.

1998-01-01

A method for dry etching of transition metals. The method for dry etching of a transition metal (or a transition metal alloy such as a silicide) on a substrate comprises providing at least one nitrogen- or phosphorous-containing .pi.-acceptor ligand in proximity to the transition metal, and etching the transition metal to form a volatile transition metal/.pi.-acceptor ligand complex. The dry etching may be performed in a plasma etching system such as a reactive ion etching (RIE) system, a downstream plasma etching system (i.e. a plasma afterglow), a chemically-assisted ion beam etching (CAIBE) system or the like. The dry etching may also be performed by generating the .pi.-acceptor ligands directly from a ligand source gas (e.g. nitrosyl ligands generated from nitric oxide), or from contact with energized particles such as photons, electrons, ions, atoms, or molecules. In some preferred embodiments of the present invention, an intermediary reactant species such as carbonyl or a halide ligand is used for an initial chemical reaction with the transition metal, with the intermediary reactant species being replaced at least in part by the .pi.-acceptor ligand for forming the volatile transition metal/.pi.-acceptor ligand complex.

Bacterial and Thermochemical Sulfate Reduction in Diagenetic Settings - Old and New Insights

NASA Astrophysics Data System (ADS)

Machel, H.

2006-12-01

The association of dissolved sulfate and hydrocarbons is thermodynamically unstable in virtually all diagenetic environments. Hence, redox-reactions occur, whereby sulfate is reduced by hydrocarbons either bacterially (bacterial sulfate reduction = BSR) or inorganically (thermochemical sulfate reduction = TSR). Based on empirical evidence, BSR and TSR occur in two mutually exclusive thermal regimes, i.e., low-T and high-T diagenetic environments, respectively. BSR is common in diagenetic settings at T = 0 - 80 ° C. Above this T range, almost all sulfate reducers cease to metabolize. Those few types of hyperthermophiles that can form H2S at higher T appear to be very rare and do not normally occur and/or metabolize in geologic settings that are otherwise conducive to BSR. TSR appears to be common in geologic settings at T = 100 - 140 ° C, but in some settings T up to 180 ° C appears to be necessary. TSR does not have a sharply defined, generally valid minimum T because the onset and rate of TSR are governed by several factors that vary from place to place, i.e., the composition of the available organic reactants, kinetic inhibitors and/or catalysts, anhydrite dissolution rates, wettability, as well as migration and diffusion rates of the major reactants. A well- defined, specific minimum T for TSR can be expected only where the reservoir conditions are fairly homogeneous on the scale of a field or a play. BSR is geologically instantaneous in most geologic settings. Rates of TSR are much lower, but still geologically significant. TSR may form sour gas reservoirs and/or MVT deposits in several tens of thousands to a few million years at T = 100 - 140 ° C. BSR and TSR may be exothermic or endothermic, depending mainly on the presence or absence of specific organic reactants. The main organic reactants for BSR are organic acids and other products of aerobic or fermentative biodegradation, and those for TSR are branched and n-alkanes, followed by cyclic and mono-aromatic species, in the gasoline range. Sulfate is derived almost invariably from the dissolution of gypsum and/or anhydrite, which may be primary or secondary deposits at or near the redox-reaction site(s). The products of BSR and TSR are similar, but their relative amounts vary widely and are determined by a number of locally variable factors, including availability of reactants, formation water chemistry, and wettability. The primary inorganic reaction products in both thermal regimes are H2S (HS-) and HCO3- (CO2). The presence of alkali earth metals often results in the formation of carbonates, particularly calcite and dolomite. Iron sulfides, galena, and sphalerite form as by-products of H2S generation, if the respective transition or base metals are present or transported to a BSR/TSR reaction site. Elemental sulfur may accumulate as a volumetrically significant net reaction product, usually when the system runs out of reactive hydrocarbons. Solid bitumen may form as a by-product of both BSR and TSR.

Identification of Enzyme Genes Using Chemical Structure Alignments of Substrate-Product Pairs.

PubMed

Moriya, Yuki; Yamada, Takuji; Okuda, Shujiro; Nakagawa, Zenichi; Kotera, Masaaki; Tokimatsu, Toshiaki; Kanehisa, Minoru; Goto, Susumu

2016-03-28

Although there are several databases that contain data on many metabolites and reactions in biochemical pathways, there is still a big gap in the numbers between experimentally identified enzymes and metabolites. It is supposed that many catalytic enzyme genes are still unknown. Although there are previous studies that estimate the number of candidate enzyme genes, these studies required some additional information aside from the structures of metabolites such as gene expression and order in the genome. In this study, we developed a novel method to identify a candidate enzyme gene of a reaction using the chemical structures of the substrate-product pair (reactant pair). The proposed method is based on a search for similar reactant pairs in a reference database and offers ortholog groups that possibly mediate the given reaction. We applied the proposed method to two experimentally validated reactions. As a result, we confirmed that the histidine transaminase was correctly identified. Although our method could not directly identify the asparagine oxo-acid transaminase, we successfully found the paralog gene most similar to the correct enzyme gene. We also applied our method to infer candidate enzyme genes in the mesaconate pathway. The advantage of our method lies in the prediction of possible genes for orphan enzyme reactions where any associated gene sequences are not determined yet. We believe that this approach will facilitate experimental identification of genes for orphan enzymes.

Mass transfer and carbon isotope evolution in natural water systems

USGS Publications Warehouse

Wigley, T.M.L.; Plummer, Niel; Pearson, F.J.

1978-01-01

This paper presents a theoretical treatment of the evolution of the carbon isotopes C13 and C14 in natural waters and in precipitates which derive from such waters. The effects of an arbitrary number of sources (such as dissolution of carbonate minerals and oxidation of organic material) and sinks (such as mineral precipitation, CO2 degassing and production of methane), and of equilibrium fractionation between solid, gas and aqueous phases are considered. The results are expressed as equations relating changes in isotopic composition to changes in conventional carbonate chemistry. One implication of the equations is that the isotopic composition of an aqueous phase may approach a limiting value whenever there are simultaneous inputs and outputs of carbonate. In order to unambiguously interpret isotopic data from carbonate precipitates and identify reactants and products in reacting natural waters, it is essential that isotopic changes are determined chiefly by reactant and product stoichiometry, independent of reaction path. We demonstrate that this is so by means of quantitative examples. The evolution equations are applied to: 1. (1) carbon-14 dating of groundwaters; 2. (2) interpretation of the isotopic composition of carbonate precipitates, carbonate cements and diagenetically altered carbonates; and 3. (3) the identification of chemical reaction stoichiometry. These applications are illustrated by examples which show the variation of ??C13 in solutions and in precipitates formed under a variety of conditions involving incongruent dissolution, CO2 degassing, methane production and mineral precipitation. ?? 1978.

Ion transport membrane reactor systems and methods for producing synthesis gas

DOEpatents

Repasky, John Michael

2015-05-12

Embodiments of the present invention provide cost-effective systems and methods for producing a synthesis gas product using a steam reformer system and an ion transport membrane (ITM) reactor having multiple stages, without requiring inter-stage reactant injections. Embodiments of the present invention also provide techniques for compensating for membrane performance degradation and other changes in system operating conditions that negatively affect synthesis gas production.

Fuel cell system with separating structure bonded to electrolyte

DOEpatents

Bourgeois, Richard Scott; Gudlavalleti, Sauri; Quek, Shu Ching; Hasz, Wayne Charles; Powers, James Daniel

2010-09-28

A fuel cell assembly comprises a separating structure configured for separating a first reactant and a second reactant wherein the separating structure has an opening therein. The fuel cell assembly further comprises a fuel cell comprising a first electrode, a second electrode, and an electrolyte interposed between the first and second electrodes, and a passage configured to introduce the second reactant to the second electrode. The electrolyte is bonded to the separating structure with the first electrode being situated within the opening, and the second electrode being situated within the passage.

Sequential Excitation Preparation of Molecular Energy Levels with Special Structural and Chemical Properties.

DTIC Science & Technology

1986-01-06

D.E. Reisner, and P.H. Vaccaro, pp. 393-404 in Lasers as Reactants and Probes in Chemistry, (eds. W.M. Jackson and A.B. Harvey) Howard University Press...as Reactants and Probes in Chemistry, Howard University (May 1982). 4. J.L. Kinsey, "An Outsider’s View of the Spectroscopy of Polyatomic Systems...Kinsey, C. Kittrell, D.E. Reisner, and P.H. Vaccaro, pp. 393-404 in Lasers as Reactants and Probes in Chemistry (eds. W.M. Jackson and A.B. Harvey), Howard

Methane Post-Processing for Oxygen Loop Closure

NASA Technical Reports Server (NTRS)

Greenwood, Zachary W.; Abney, Morgan B.; Miller, Lee

2016-01-01

State-of-the-art United States Atmospheric Revitalization carbon dioxide (CO2) reduction is based on the Sabatier reaction process, which recovers approximately 50% of the oxygen (O2) from crew metabolic CO2. Oxygen recovery from carbon dioxide is constrained by the limited availability of reactant hydrogen. Post-processing of methane to recover hydrogen with the Umpqua Research Company Plasma Pyrolysis Assembly (PPA) has the potential to further close the Atmospheric Revitalization oxygen loop. The PPA decomposes methane into hydrogen and hydrocarbons, predominantly acetylene, and a small amount of solid carbon. The hydrogen must then be purified before it can be recycled for additional oxygen recovery. Long duration testing and evaluation of a four crew-member sized PPA and a discussion of hydrogen recycling system architectures are presented.

Charge transfer complex between 2,3-diaminopyridine with chloranilic acid. Synthesis, characterization and DFT, TD-DFT computational studies

NASA Astrophysics Data System (ADS)

Al-Ahmary, Khairia M.; Habeeb, Moustafa M.; Al-Obidan, Areej H.

2018-05-01

New charge transfer complex (CTC) between the electron donor 2,3-diaminopyridine (DAP) with the electron acceptor chloranilic (CLA) acid has been synthesized and characterized experimentally and theoretically using a variety of physicochemical techniques. The experimental work included the use of elemental analysis, UV-vis, IR and 1H NMR studies to characterize the complex. Electronic spectra have been carried out in different hydrogen bonded solvents, methanol (MeOH), acetonitrile (AN) and 1:1 mixture from AN-MeOH. The molecular composition of the complex was identified to be 1:1 from Jobs and molar ratio methods. The stability constant was determined using minimum-maximum absorbances method where it recorded high values confirming the high stability of the formed complex. The solid complex was prepared and characterized by elemental analysis that confirmed its formation in 1:1 stoichiometric ratio. Both IR and NMR studies asserted the existence of proton and charge transfers in the formed complex. For supporting the experimental results, DFT computations were carried out using B3LYP/6-31G(d,p) method to compute the optimized structures of the reactants and complex, their geometrical parameters, reactivity parameters, molecular electrostatic potential map and frontier molecular orbitals. The analysis of DFT results strongly confirmed the high stability of the formed complex based on existing charge transfer beside proton transfer hydrogen bonding concordant with experimental results. The origin of electronic spectra was analyzed using TD-DFT method where the observed λmax are strongly consisted with the computed ones. TD-DFT showed the contributed states for various electronic transitions.

Biochemical thermodynamics: applications of Mathematica.

PubMed

Alberty, Robert A

2006-01-01

The most efficient way to store thermodynamic data on enzyme-catalyzed reactions is to use matrices of species properties. Since equilibrium in enzyme-catalyzed reactions is reached at specified pH values, the thermodynamics of the reactions is discussed in terms of transformed thermodynamic properties. These transformed thermodynamic properties are complicated functions of temperature, pH, and ionic strength that can be calculated from the matrices of species values. The most important of these transformed thermodynamic properties is the standard transformed Gibbs energy of formation of a reactant (sum of species). It is the most important because when this function of temperature, pH, and ionic strength is known, all the other standard transformed properties can be calculated by taking partial derivatives. The species database in this package contains data matrices for 199 reactants. For 94 of these reactants, standard enthalpies of formation of species are known, and so standard transformed Gibbs energies, standard transformed enthalpies, standard transformed entropies, and average numbers of hydrogen atoms can be calculated as functions of temperature, pH, and ionic strength. For reactions between these 94 reactants, the changes in these properties can be calculated over a range of temperatures, pHs, and ionic strengths, and so can apparent equilibrium constants. For the other 105 reactants, only standard transformed Gibbs energies of formation and average numbers of hydrogen atoms at 298.15 K can be calculated. The loading of this package provides functions of pH and ionic strength at 298.15 K for standard transformed Gibbs energies of formation and average numbers of hydrogen atoms for 199 reactants. It also provides functions of temperature, pH, and ionic strength for the standard transformed Gibbs energies of formation, standard transformed enthalpies of formation, standard transformed entropies of formation, and average numbers of hydrogen atoms for 94 reactants. Thus loading this package makes available 774 mathematical functions for these properties. These functions can be added and subtracted to obtain changes in these properties in biochemical reactions and apparent equilibrium constants.

Process and apparatus for obtaining silicon from fluosilicic acid

DOEpatents

Sancier, Kenneth M.

1985-07-16

Process for producing low cost, high purity solar grade Si wherein a reduction reaction, preferably the reduction of SiF.sub.4, by an alkali metal (liquid Na preferred) is carried out essentialy continuously by injecting of reactants in substantially stoichiometric proportions into a reaction chamber having a controlled temperature thereby to form a mist or dispersion of reactants. The reactants being supplied at such a rate and temperature that the reaction takes place far enough away from the entry region to avoid plugging of reactants at the entry region, the reaction is completed and whereby essentially all reaction product solidifies and forms a free flowing powder before reaction product hits a reaction chamber wall. Thus, the reaction product does not adhere to the reaction chamber wall or pick up impurities therefrom. Separation of reaction products is easily carried out by either a leach or melt separation process.

NASA redox storage system development project

NASA Technical Reports Server (NTRS)

1983-01-01

The operating temperature was raised from 25 C to 65 C, which enhanced the kinetics of the chromium electrode charging reactions. The design of the auxiliary electrochemical cell, which is used to keep both reactants at the same state of charge, was modified, leading to better and more stable performance. Preliminary testing has shown that the four tank mode of operation improves energy efficiency as much as 5 percentage points over the conventional two tank mode. Another variation in operating mode, the use of mixed reactants, potentially offers several very attractive advantages. Preliminary reactant cost studies lend further weight to the feasibility of the mixed reactant concept. Electrode studies show that reproducibility of performance is very dependent on the pyrolysis temperature at which the carbon/graphite felt substrate is formed. Membrane development work continued to concentrate on cost reduction and the enhancement of resistivity and selectivity.

Fuel cell with interdigitated porous flow-field

DOEpatents

Wilson, Mahlon S.

1997-01-01

A polymer electrolyte membrane (PEM) fuel cell is formed with an improved system for distributing gaseous reactants to the membrane surface. A PEM fuel cell has an ionic transport membrane with opposed catalytic surfaces formed thereon and separates gaseous reactants that undergo reactions at the catalytic surfaces of the membrane. The fuel cell may also include a thin gas diffusion layer having first and second sides with a first side contacting at least one of the catalytic surfaces. A macroporous flow-field with interdigitated inlet and outlet reactant channels contacts the second side of the thin gas diffusion layer for distributing one of the gaseous reactants over the thin gas diffusion layer for transport to an adjacent one of the catalytic surfaces of the membrane. The porous flow field may be formed from a hydrophilic material and provides uniform support across the backside of the electrode assembly to facilitate the use of thin backing layers.

NASA Redox Project status summary

NASA Technical Reports Server (NTRS)

Hagedorn, N. H.

1983-01-01

This report is a summary of the results of the Redox Project effort during Cy 1982. It was presented at the Fifth U.S. Department of Energy Battery and Electrochemical Contractors Conference, Arlington, Va., Dec. 7-9, 1982. The major development during 1982 was the shift from Redox system operation at 25 C with unmixed reactants to operation at 65 C with mixed reactants. This change has made possible a two- or three-fold increase in operating current density, to about 65 mA/sq cm, and an increase in reactant utilization from 40% to about 90%. Both of these improvements will lead to significant system cost reductions. Contract studies have indicated that Redox reactant costs also will be moderate. A new catalyst for the chromuim electrode offers all the advantages of the conventional gold-lead catalyst while being easier to apply and more forgiving in use.

Fuel cell with interdigitated porous flow-field

DOEpatents

Wilson, M.S.

1997-06-24

A polymer electrolyte membrane (PEM) fuel cell is formed with an improved system for distributing gaseous reactants to the membrane surface. A PEM fuel cell has an ionic transport membrane with opposed catalytic surfaces formed thereon and separates gaseous reactants that undergo reactions at the catalytic surfaces of the membrane. The fuel cell may also include a thin gas diffusion layer having first and second sides with a first side contacting at least one of the catalytic surfaces. A macroporous flow-field with interdigitated inlet and outlet reactant channels contacts the second side of the thin gas diffusion layer for distributing one of the gaseous reactants over the thin gas diffusion layer for transport to an adjacent one of the catalytic surfaces of the membrane. The porous flow field may be formed from a hydrophilic material and provides uniform support across the backside of the electrode assembly to facilitate the use of thin backing layers. 9 figs.

Method for preparing actinide nitrides

DOEpatents

Bryan, G.H.; Cleveland, J.M.; Heiple, C.R.

1975-12-01

Actinide nitrides, and particularly plutonium and uranium nitrides, are prepared by reacting an ammonia solution of an actinide compound with an ammonia solution of a reactant or reductant metal, to form finely divided actinide nitride precipitate which may then be appropriately separated from the solution. The actinide nitride precipitate is particularly suitable for forming nuclear fuels.

Oxidation and Reduction Reactions in Organic Chemistry

ERIC Educational Resources Information Center

Shibley, Ivan A., Jr.; Amaral, Katie E.; Aurentz, David J.; McCaully, Ronald J.

2010-01-01

A variety of approaches to the concept of oxidation and reduction appear in organic textbooks. The method proposed here is different than most published approaches. The oxidation state is calculated by totaling the number of heterogeneous atoms, [pi]-bonds, and rings. A comparison of the oxidation states of reactant and product determine what type…

Catalyst, method of making, and reactions using the catalyst

DOEpatents

Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Gao, Yufei [Kennewick, WA

2009-03-03

The present invention includes a catalyst having a layered structure with, (1) a porous support, (2) a buffer layer, (3) an interfacial layer, and optionally (4) a catalyst layer. The invention also provides a process in which a reactant is converted to a product by passing through a reaction chamber containing the catalyst.

Catalyst, method of making, and reactions using the catalyst

DOEpatents

Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Gao, Yufei [Kennewick, WA

2002-08-27

The present invention includes a catalyst having a layered structure with, (1) a porous support, (2) a buffer layer, (3) an interfacial layer, and optionally (4) a catalyst layer. The invention also provides a process in which a reactant is converted to a product by passing through a reaction chamber containing the catalyst.

Catalyst, Method Of Making, And Reactions Using The Catalyst

DOEpatents

Tonkovich, Anna Lee Y.; Wang, Yong; Gao, Yufei

2004-07-13

The present invention includes a catalyst having a layered structure with, (1) a porous support, (2) a buffer layer, (3) an interfacial layer, and optionally (4) a catalyst layer. The invention also provides a process in which a reactant is converted to a product by passing through a reaction chamber containing the catalyst.

Improved flow cytometer measurement of binding assays

NASA Astrophysics Data System (ADS)

Saunders, G. C.

1984-05-01

A method of measuring binding assays is carried out with different size particles wherein the binding assay sample is run through a flow cytometer without separating the sample from the marking agent. The amount of a binding reactant present in a sample is determined by providing particles with a coating of binder and also known quantity of smaller particles with a coating of binder reactant. The smaller particles also contain a fluorescent chemical. The particles are combined with the sample and the binding reaction is allowed to occur for a set length of time followed by combining the smaller particles with the mixture of the particles and the sample produced and allowing the binding reactions to proceed to equilibrium. The fluorescence and light scatter of the combined mixture is then measured as the combined mixture passes through a flow cytometer equipped with a laser to bring about fluorescence, and the number of fluorescent events are compared. A similar method is also provided for determining the amount of antigen present in the sample by providing spheres with an antibody coating and some smaller spheres with an antigen coating.

Thermo-stoichiometric behavior of aluminum-nickel nanoheater particles fabricated by galvanic replacement reaction

NASA Astrophysics Data System (ADS)

Buckley, Jacqueline L.

2010-03-01

Al-Ni reactive nano-structures are gaining interest for various applications in aerospace, nano-manufacturing, and biomedical fields. However, nano-material behavior can vary from macro-scale. There has been no systematic study of Al-Ni exothermic reaction and intermetallic formation for nano-scale reactants. Therefore, this study aims to investigate deviations from the established Al-Ni phase diagram, with the premise that the intermetallic formation temperatures are expected to be lower for nano-reactants due to higher surface energy. Additionally, it is important to gain better understanding and control of the galvanic replacement reaction (GRR) fabrication method, which, in terms of producing Al-Ni bi-metallic nanoparticles, is a completely novel scheme. With an adapted phase diagram, intermetallic product and heat output of nanoparticles from any given stage of GRR process can be predicted. Al-Ni nanoparticles having ignitable Al-Ni ratios were fabricated via GRR method. Effects of composition and temperature on intermetallic formation were studied by in-situ XRD analysis. Effects of environment and heating rate on the Al-Ni exothermic reaction were also investigated.

Liquid Phase Plasma Synthesis of Iron Oxide Nanoparticles on Nitrogen-Doped Activated Carbon Resulting in Nanocomposite for Supercapacitor Applications.

PubMed

Lee, Heon; Lee, Won-June; Park, Young-Kwon; Ki, Seo Jin; Kim, Byung-Joo; Jung, Sang-Chul

2018-03-25

Iron oxide nanoparticles supported on nitrogen-doped activated carbon powder were synthesized using an innovative plasma-in-liquid method, called the liquid phase plasma (LPP) method. Nitrogen-doped carbon (NC) was prepared by a primary LPP reaction using an ammonium chloride reactant solution, and an iron oxide/NC composite (IONCC) was prepared by a secondary LPP reaction using an iron chloride reactant solution. The nitrogen component at 3.77 at. % formed uniformly over the activated carbon (AC) surface after a 1 h LPP reaction. Iron oxide nanoparticles, 40~100 nm in size, were impregnated homogeneously over the NC surface after the LPP reaction, and were identified as Fe₃O₄ by X-ray photoelectron spectroscopy and X-ray diffraction. NC and IONCCs exhibited pseudo-capacitive characteristics, and their specific capacitance and cycling stability were superior to those of bare AC. The nitrogen content on the NC surface increased the compatibility and charge transfer rate, and the composites containing iron oxide exhibited a lower equivalent series resistance.

Optical calorimetry in microfluidic droplets.

PubMed

Chamoun, Jacob; Pattekar, Ashish; Afshinmanesh, Farzaneh; Martini, Joerg; Recht, Michael I

2018-05-29

A novel microfluidic calorimeter that measures the enthalpy change of reactions occurring in 100 μm diameter aqueous droplets in fluoropolymer oil has been developed. The aqueous reactants flow into a microfluidic droplet generation chip in separate fluidic channels, limiting contact between the streams until immediately before they form the droplet. The diffusion-driven mixing of reactants is predominantly restricted to within the droplet. The temperature change in droplets due to the heat of reaction is measured optically by recording the reflectance spectra of encapsulated thermochromic liquid crystals (TLC) that are added to one of the reactant streams. As the droplets travel through the channel, the spectral characteristics of the TLC represent the internal temperature, allowing optical measurement with a precision of ≈6 mK. The microfluidic chip and all fluids are temperature controlled, and the reaction heat within droplets raises their temperature until thermal diffusion dissipates the heat into the surrounding oil and chip walls. Position resolved optical temperature measurement of the droplets allows calculation of the heat of reaction by analyzing the droplet temperature profile over time. Channel dimensions, droplet generation rate, droplet size, reactant stream flows and oil flow rate are carefully balanced to provide rapid diffusional mixing of reactants compared to thermal diffusion, while avoiding thermal "quenching" due to contact between the droplets and the chip walls. Compared to conventional microcalorimetry, which has been used in this work to provide reference measurements, this new continuous flow droplet calorimeter has the potential to perform titrations ≈1000-fold faster while using ≈400-fold less reactants per titration.

Development of a High Reliability Compact Air Independent PEMFC Power System

NASA Technical Reports Server (NTRS)

Vasquez, Arturo; Wynne, Bob

2013-01-01

Autonomous Underwater Vehicles (AUV's) have received increasing attention in recent years as military and commercial users look for means to maintain a mobile and persistent presence in the undersea world. Compact, neutrally buoyant power systems are needed for both small and large vehicles. Historically, batteries have been employed in these applications, but the energy density and therefore mission duration are limited with current battery technologies. Vehicles with stored energy requirements greater than approximately 10 kWh have an alternate means to get long duration power. High efficiency Proton Exchange Membrane (PEM) fuel cell systems utilizing pure hydrogen and oxygen reactants show the potential for an order of magnitude energy density improvement over batteries as long as the subsystems are compact. One key aspect to achieving a compact and energy dense system is the design of the fuel cell balance of plant (BOP). Recent fuel cell work, initially focused on NASA applications requiring high reliability, has developed systems that can meet target power and energy densities. Passive flow through systems using ejector driven reactant (EDR) circulation have been developed to provide high reactant flow and water management within the stack, with minimal parasitic losses compared to blowers. The ejectors and recirculation loops, along with valves and other BOP instrumentation, have been incorporated within the stack end plate. In addition, components for water management and reactant conditioning have been incorporated within the stack to further minimize the BOP. These BOP systems are thermally and functionally integrated into the stack hardware and fit into the small volumes required for AUV and future NASA applications to maximize the volume available for reactants. These integrated systems provide a compact solution for the fuel cell BOP and maximize the efficiency and reliability of the system. Designs have been developed for multiple applications ranging from less than 1 kWe to 70 kWe. These systems occupy a very small portion of the overall energy system, allowing most of the system volume to be used for reactants. The fuel cell systems have been optimized to use reactants efficiently with high stack efficiency and low parasitic losses. The resulting compact, highly efficient fuel cell system provides exceptional reactant utilization and energy density. Key design variables and supporting test data are presented. Future development activities are described.

Theory and simulation of the time-dependent rate coefficients of diffusion-influenced reactions.

PubMed Central

Zhou, H X; Szabo, A

1996-01-01

A general formalism is developed for calculating the time-dependent rate coefficient k(t) of an irreversible diffusion-influenced reaction. This formalism allows one to treat most factors that affect k(t), including rotational Brownian motion and conformational gating of reactant molecules and orientation constraint for product formation. At long times k(t) is shown to have the asymptotic expansion k(infinity)[1 + k(infinity) (pie Dt)-1/2 /4 pie D + ...], where D is the relative translational diffusion constant. An approximate analytical method for calculating k(t) is presented. This is based on the approximation that the probability density of the reactant pair in the reactive region keeps the equilibrium distribution but with a decreasing amplitude. The rate coefficient then is determined by the Green function in the absence of chemical reaction. Within the framework of this approximation, two general relations are obtained. The first relation allows the rate coefficient for an arbitrary amplitude of the reactivity to be found if the rate coefficient for one amplitude of the reactivity is known. The second relation allows the rate coefficient in the presence of conformational gating to be found from that in the absence of conformational gating. The ratio k(t)/k(0) is shown to be the survival probability of the reactant pair at time t starting from an initial distribution that is localized in the reactive region. This relation forms the basis of the calculation of k(t) through Brownian dynamics simulations. Two simulation procedures involving the propagation of nonreactive trajectories initiated only from the reactive region are described and illustrated on a model system. Both analytical and simulation results demonstrate the accuracy of the equilibrium-distribution approximation method. PMID:8913584

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

PubMed Central

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

2014-01-01

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

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

PubMed

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

2014-01-01

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

Simultaneous measurement at multiple depths of in situ rates of denitrification in the bed of a groundwater-fed river

NASA Astrophysics Data System (ADS)

Lansdown, Katrina; Trimmer, Mark; Heppell, Kate

2010-05-01

Typically characterised by steep chemical gradients and variable redox conditions, the hyporheic zone is considered a 'hotpot' or site of enhanced biogeochemical activity in the aquatic environment. As such the importance of the hyporheic zone for the attenuation of nutrients such as nitrate in a fluvial network has long been recognised. Controls on nitrogen transformations, however, especially at depths greater than 10cm below the sediment-water interface, remain comparatively less understood. Most work aimed at quantifying denitrification in the hyporheic zone has involved laboratory incubation of recovered sediments which is likely to affect the estimate of the true in situ rate. Results of such studies are usually cited as 'potential' rates of denitrification and have undoubtedly improved the understanding of nitrogen cycling in the aquatic environment. There is, however, a need for in situ measurement to improve our knowledge of nitrogen cycling in the river bed. Here, rates of denitrification in the hyporheic zone have been measured at multiple depths, simultaneously using 'push-pull' methodology (e.g. Snodgrass and Kitanidis 1998). The 'push-pull' technique involves injection of a solution containing reactant(s) (e.g. nitrate) and a conservative tracer (e.g. chloride) into the sediment and extraction of pore water samples over time. Recovered samples are screened for the removal of reactant(s) and/or the accumulation of products(s). Temporal changes in the conservative tracer are used to correct the concentration of the reactant(s) and product(s) for dispersion and advection. The disadvantage of the 'traditional' 'push-pull' methodology is that rates of nitrate removal are measured rather than rates of denitrification. In this research, comparison of measured and 'corrected' nitrate concentrations allowed the rate of nitrate removal (or production) to be quantified. In order to determine in situ rates of denitrification we used 15N-enriched nitrate as the reactant in the 'push-pull' experiments and measured the accumulation of 29N2 and 30N2 over time. Rates of denitrification were then calculated using the isotope pairing technique (as per Nielsen 1992; Sanders and Trimmer 2006). Measurements have been made at up to 40cm depth in the river bed using a miniprobe system developed from the design of Sanders and Trimmer (2006) in order to validate the experimental approach. Previous work conducted at the study site (R. Leith, Cumbria, UK) suggested than ambient conditions would not be ideal for in situ measurement of denitrification rates using 'push-pull' methodology. Slow rates of denitrification were measured during laboratory incubations of the sandy sediment (M. Trimmer, unpublished data), and the velocity of flow in the hyporheic zone would limit the duration of the in situ measurement (Käser et al. 2009). Despite difficulties posed by the site, we have measured in situ rates of denitrification at multiple depths in the hyporheic zone simultaneously. We also report measurement of in situ rates of denitrification below the zone of surface water - ground water mixing. In future we will use the experimental technique described in this paper to quantify (i) variation in N transformation rates with depth; and (ii) spatial variation in rates of nitrate consumption/production within the river bed. Käser, DH, Binley, A, Heathwaite, AL and Krause, S (2009) Spatio-temporal variations of hyporheic flow in a riffle-pool sequence. Hydrological Processes 23: 2138 - 2149. Nielsen, LP (1992) Denitrification in sediment determined from nitrogen isotope pairing. FEMS Microbiology Ecology 86: 357 - 362. Sanders, IA and Trimmer, M (2006) In situ application of the 15NO3- isotope pairing technique to measure denitrification in sediments at the surface water-groundwater interface. Limnology and oceanography: Methods 4: 142 - 152. Snodgrass, MF and Kitanidis, PK (1998) A method to infer in situ reaction rates from push-pull experiments. Ground Water 36(4): 645 - 650.

Method and apparatus for continuously referenced analysis of reactive components in solution

DOEpatents

Bostick, W.D.; Denton, M.S.; Dinsmore, S.R.

1979-07-31

A continuously referenced apparatus for measuring the concentration of a reactive chemical species in solution comprises in combination conduit means for introducing a sample solution, means for introducing one or more reactants into a sample solution, and a stream separator disposed within the conduit means for separating the sample solution into a first sample stream and a second sample stream. A reactor is disposed in fluid communication with the first sample stream. A reaction takes place between the reactants introduced and the reactive chemical species of interest, causing the consumption or production of an indicator species in the first sample stream. Measurement means such as a photometric system are disposed in communication with the first and second sample streams, and the outputs of the measurement means are compared to provide a blanked measurement of the concentration of indicator species. The apparatus is particularly suitable for measurement of isoenzymes in body tissues or fluids.

Rapid hybridization of nucleic acids using isotachophoresis

PubMed Central

Bercovici, Moran; Han, Crystal M.; Liao, Joseph C.; Santiago, Juan G.

2012-01-01

We use isotachophoresis (ITP) to control and increase the rate of nucleic acid hybridization reactions in free solution. We present a new physical model, validation experiments, and demonstrations of this assay. We studied the coupled physicochemical processes of preconcentration, mixing, and chemical reaction kinetics under ITP. Our experimentally validated model enables a closed form solution for ITP-aided reaction kinetics, and reveals a new characteristic time scale which correctly predicts order 10,000-fold speed-up of chemical reaction rate for order 100 pM reactants, and greater enhancement at lower concentrations. At 500 pM concentration, we measured a reaction time which is 14,000-fold lower than that predicted for standard second-order hybridization. The model and method are generally applicable to acceleration of reactions involving nucleic acids, and may be applicable to a wide range of reactions involving ionic reactants. PMID:22733732

Predicting Upscaled Behavior of Aqueous Reactants in Heterogeneous Porous Media

NASA Astrophysics Data System (ADS)

Wright, E. E.; Hansen, S. K.; Bolster, D.; Richter, D. H.; Vesselinov, V. V.

2017-12-01

When modeling reactive transport, reaction rates are often overestimated due to the improper assumption of perfect mixing at the support scale of the transport model. In reality, fronts tend to form between participants in thermodynamically favorable reactions, leading to segregation of reactants into islands or fingers. When such a configuration arises, reactions are limited to the interface between the reactive solutes. Closure methods for estimating control-volume-effective reaction rates in terms of quantities defined at the control volume scale do not presently exist, but their development is crucial for effective field-scale modeling. We attack this problem through a combination of analytical and numerical means. Specifically, we numerically study reactive transport through an ensemble of realizations of two-dimensional heterogeneous porous media. We then employ regression analysis to calibrate an analytically-derived relationship between reaction rate and various dimensionless quantities representing conductivity-field heterogeneity and the respective strengths of diffusion, reaction and advection.

Simulation of SiO2 etching in an inductively coupled CF4 plasma

NASA Astrophysics Data System (ADS)

Xu, Qing; Li, Yu-Xing; Li, Xiao-Ning; Wang, Jia-Bin; Yang, Fan; Yang, Yi; Ren, Tian-Ling

2017-02-01

Plasma etching technology is an indispensable processing method in the manufacturing process of semiconductor devices. Because of the high fluorine/carbon ratio of CF4, the CF4 gas is often used for etching SiO2. A commercial software ESI-CFD is used to simulate the process of plasma etching with an inductively coupled plasma model. For the simulation part, CFD-ACE is used to simulate the chamber, and CFD-TOPO is used to simulate the surface of the sample. The effects of chamber pressure, bias voltage and ICP power on the reactant particles were investigated, and the etching profiles of SiO2 were obtained. Simulation can be used to predict the effects of reaction conditions on the density, energy and angular distributions of reactant particles, which can play a good role in guiding the etching process.

Communication: State-to-state dynamics of the Cl + H2O → HCl + OH reaction: Energy flow into reaction coordinate and transition-state control of product energy disposal.

PubMed

Zhao, Bin; Sun, Zhigang; Guo, Hua

2015-06-28

Quantum state-to-state dynamics of a prototypical four-atom reaction, namely, Cl + H2O → HCl + OH, is investigated for the first time in full dimensionality using a transition-state wave packet method. The state-to-state reactivity and its dependence on the reactant internal excitations are analyzed and found to share many similarities both energetically and dynamically with the H + H2O → H2 + OH reaction. The strong enhancement of reactivity by the H2O stretching vibrational excitations in both reactions is attributed to the favorable energy flow into the reaction coordinate near the transition state. On the other hand, the insensitivity of the product state distributions with regard to reactant internal excitation stems apparently from the transition-state control of product energy disposal.

The equilibrium of the reaction catalysed by citrate oxaloacetate-lyase

PubMed Central

Tate, S. S.; Datta, S. P.

1965-01-01

1. A method of preparation and purification of citrate oxaloacetate-lyase (EC 4.1.3.6) from Aerobacter aerogenes is described. 2. The equilibrium of this reaction has been determined at pH 8·4 and 25°. It has been shown that K, i.e. [citrate3−]/[oxaloacetateketo2−][acetate −], is 3·08±0·72, but that Kapp., i.e. [total citrate]/[total oxaloacetate][total acetate], is markedly affected by the initial concentrations of the reactants and magnesium. 3. The free-energy change during the cleavage of citrate has been calculated and compared with data from other sources. 4. The free energy of hydrolysis of acetyl-CoA has been evaluated from the present data. 5. A detailed knowledge of the interactions of the reactants with metal ions has been shown to be important in the calculation of the equilibrium constant and related thermodynamic functions. PMID:14348207

Theoretical study of the photo-isomerisation reactions of 1,2-dihydro-1,2-phosphaborine and 1,2-dihydro-1,2-alumazaine

NASA Astrophysics Data System (ADS)

Su, Ming-Der

2015-07-01

The mechanisms of the photochemical isomerisation reactions are investigated theoretically using the model systems, 1,2-dihydro-1,2-phosphaborine (5) and 1,2-dihydro-1,2-alumazaine (6), using the CAS(6,6)/6-311G(d,p) and MP2-CAS-(6,6)/6-311++G(3df,3pd)//CAS(6,6)/6-311G(d,p) methods. For each model reactant, three reaction pathways, which lead to three kinds of photo-isomers, are examined. The structures of the conical intersections, which play a key role in such photo-rearrangements, are determined. The thermal (or dark) reactions of the reactant species are also examined, using the same level of theory, to provide a qualitative explanation of the reaction pathways. These model investigations demonstrate that the preferred reaction route for these two aromatic heterocyclics is as follows: reactant → Franck-Condon region → conical intersection → photoproduct. The theoretical evidences anticipate that after irradiation of 5, the photoproduct yield of the Dewar BP-isomer, 8, should be larger than that of the Dewar BP-isomer, 7, whereas no Dewar BP-isomer 9 can be observed. Moreover, the present theoretical data predict after irradiation of 6, all three Dewar AlN-isomers (10, 11, and 12) and the starting molecule, 6, are produced.

Tested Demonstrations.

ERIC Educational Resources Information Center

Gilbert, George L., Ed.

1983-01-01

Free radical chlorination of methane is used in organic chemistry to introduce free radical/chain reactions. In spite of its common occurrence, demonstrations of the reaction are uncommon. Therefore, such a demonstration is provided, including background information, preparation of reactants/reaction vessel, introduction of reactants, irradiation,…

Processable high temperature resistant polymer matrix materials

NASA Technical Reports Server (NTRS)

Serafini, T. T.

1975-01-01

A review is presented of studies conducted with addition-cured polyimides, giving particular attention to an improved method involving in situ polymerization of monomer reactants (PMR) on the surface of the reinforcing fibers. The studies show that the PMR approach provides a powerful method for fabricating high performance polymer matrix composites. Significant advantages of the PMR approach are related to the superior high temperature properties of the obtained material, lower cost, greater safety, and processing versatility.

Method for the synthesis of chlorosilanes

DOEpatents

Wheeler, D.R.; Pollagi, T.P.

1999-08-17

A novel method is described for the synthesis of chlorinated or partially chlorinated organosilanes and organopolysilanes. The chlorination is effected by contacting an organosilanes or organopolysilanes with anhydrous CuCl{sub 2} in a nonpolar alkane solvent, preferably pentane or hexadecane, without the use of a catalyst. Copper metal, which is easily filtered, is a reaction product. The filtrate containing the chlorinated organosilane or organopolysilane can be used directly as a reactant to produce, for example, aminoorganosilanes.

Method for the synthesis of chlorosilanes

DOEpatents

Wheeler, David R.; Pollagi, Timothy P.

1999-01-01

A novel method for the synthesis of chlorinated or partially chlorinated organosilanes and organopolysilanes. The chlorination is effected by contacting an organosilanes or organopolysilanes with anhydrous CuCl.sub.2 in a nonpolar alkane solvent, preferably pentane or hexadecane, without the use of a catalyst. Copper metal, which is easily filtered, is a reaction product. The filtrate containing the chlorinated organosilane or organopolysilane can be used directly as a reactant to produce, for example, aminoorganosilanes.

The effects of combined therapy of rheumatoid arthritis on the acute phase reactants.

PubMed

Rexhepi, Sylejman; Rexhepi, Mjellma; Sahatçiu-Meka, Vjollca; Pllana, Ejup; Dragusha, Gani; Gashi, Masar; Rexhepi, Blerta

2009-01-01

The paper presents the results of studies of acute phase reactants in the 60 treated patients with rheumatoid arthritis. Patients were divided into two groups, depending on the applied treatment: group I (n = 30) was treated with methotrexate, sulfasalazine and hydroxychloroquine, and group II (n = 30) with methotrexate. The results of our study shows that there is a statistically significant reduction in the value of acute phase reactants and clinical parameters after treatment in both investigated groups of patients, and also a significant statistical difference between the first and second group of treated patients.

The Impact of the Flow Field Heterogeneity and of the Injection Rate on the Effective Reaction Rates in Carbonates: a Study at the Pore Scale

NASA Astrophysics Data System (ADS)

Nunes, J. P. P.; Bijeljic, B.; Blunt, M. J.

2015-12-01

Carbonate rocks are notoriously difficult to characterize. Their abrupt facies variations give rise to drastic changes in the petrophysical properties of the reservoir. Such heterogeneity, when further associated with variations in rock mineralogy due to diagenetic processes, result in a challenging scenario to model from the pore to the field scale. Micro-CT imaging is one of the most promising technologies to characterize porous rocks. The understanding at the pore scale of reactive and non-reactive transport is being pushed forward by recent developments in both imaging capability - 3D images with resolution of a few microns - and in modeling techniques - flow simulations in giga-cell models. We will present a particle-based method capable of predicting the evolution of petrophysical properties of carbonate cores subjected to CO2 injection at reservoir conditions (i.e. high pressures and temperatures). Reactive flow is simulated directly on the voxels of high resolution micro-CT images of rocks. Reactants are tracked using a semi-analytical streamline tracing algorithm and rock-fluid interaction is controlled by the diffusive flux of particles from the pores to the grains. We study the impact of the flow field heterogeneity and of the injection rate on the sample-averaged (i.e. effective) reaction rate of calcite dissolution in three rocks of increasing complexity: a beadpack, an oolitic limestone and a bioclastic limestone. We show how decreases in the overall dissolution rate depend on both the complexity of the pore space and also on the flow rate. This occurs even in chemically homogenous rocks. Our results suggest that the large differences observed between laboratory and field scale rates could, in part, be explained by the inhomogeneity in the flow field at the pore scale and the consequent transport-limited flux of reactants at the solid surface. Our results give valuable insight into the processes governing carbonate dissolution and provide a starting point to the refinement of upscaling techniques for reactive flows. Potential impacts for reservoir development and monitoring will also be discussed.

Reactant conversion in homogeneous turbulence: Mathematical modeling, computational validations and practical applications

NASA Technical Reports Server (NTRS)

Madnia, C. K.; Frankel, S. H.; Givi, P.

1992-01-01

Closed form analytical expressions are obtained for predicting the limited rate of reactant conversion in a binary reaction of the type F + rO yields (1 + r) Product in unpremixed homogeneous turbulence. These relations are obtained by means of a single point Probability Density Function (PDF) method based on the Amplitude Mapping Closure. It is demonstrated that with this model, the maximum rate of the reactants' decay can be conveniently expressed in terms of definite integrals of the Parabolic Cylinder Functions. For the cases with complete initial segregation, it is shown that the results agree very closely with those predicted by employing a Beta density of the first kind for an appropriately defined Shvab-Zeldovich scalar variable. With this assumption, the final results can also be expressed in terms of closed form analytical expressions which are based on the Incomplete Beta Functions. With both models, the dependence of the results on the stoichiometric coefficient and the equivalence ratio can be expressed in an explicit manner. For a stoichiometric mixture, the analytical results simplify significantly. In the mapping closure, these results are expressed in terms of simple trigonometric functions. For the Beta density model, they are in the form of Gamma Functions. In all the cases considered, the results are shown to agree well with data generated by Direct Numerical Simulations (DNS). Due to the simplicity of these expressions and because of nice mathematical features of the Parabolic Cylinder and the Incomplete Beta Functions, these models are recommended for estimating the limiting rate of reactant conversion in homogeneous reacting flows. These results also provide useful insights in assessing the extent of validity of turbulence closures in the modeling of unpremixed reacting flows. Some discussions are provided on the extension of the model for treating more complicated reacting systems including realistic kinetics schemes and multi-scalar mixing with finite rate chemical reactions in more complex configurations.

Method for facilitating catalyzed oxidation reactions, device for facilitating catalyzed oxidation reactions

DOEpatents

Beuhler, Robert J [East Moriches, NY; White, Michael G [Blue Point, NY; Hrbek, Jan [Rocky Point, NY

2006-08-15

A catalytic process for the oxidation of organic. Oxygen is loaded into a metal foil by heating the foil while in contact with an oxygen-containing fluid. After cooling the oxygen-activated foil to room temperature, oxygen diffuses through the foil and oxidizes reactants exposed to the other side of the foil.

Investigating the Mechanism of Heteroaromatic Decarboxylation Using Solvent Kinetic Isotope Effects and Eyring Transition-State Theory

ERIC Educational Resources Information Center

Mundle, Scott O. C.; Opinska, Liliana Guevara; Kluger, Ronald; Dicks, Andrew P.

2011-01-01

An upper-level mechanistic organic experiment is outlined where undergraduates measure kinetic rate constants for decarboxylation of pyrrole-2-carboxylic acid by the initial-rates method. UV spectroscopy is used to monitor reactant disappearance in both hydrochloric acid and deuterium chloride at different temperatures. Individual data are pooled…

Crossed Molecular Beam Studies and Dynamics of Decomposition of Chemically Activated Radicals

DOE R&D Accomplishments Database

Lee, Y. T.

1973-09-01

The power of the crossed molecular beams method in the investigation of the dynamics of chemical reactions lies mainly in the direct observation of the consequences of single collisions of well controlled reactant molecules. The primary experimental observations which provide information on reaction dynamics are the measurements of angular and velocity distributions of reaction products.

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

Suuberg, E.M.; Lilly, W.D.; Aarna, I.

This project is concerned with the mechanism of reduction of both NO and N{sub 2}O by carbons. It was recognized some years ago that NO formed during fluidized bed coal combustion can be heterogeneously reduced in-situ by the carbonaceous solid intermediates of combustion. This has been recently supplemented by the knowledge that heterogeneous reaction with carbon can also play an important role in reducing emissions of N{sub 2}, but that the NO-carbon reactions might also contribute to formation of N{sub 2}. The precise role of carbon in N{sub 2} reduction and formation has yet to be established. Interest in themore » N{sub 2} and N{sub 2}O-char reactions has been significant in connection with both combustor modeling, as well as in design of post-combustion NO{sub x} control strategies. In our studies, a DuPont thermogravimetric analyzer (TGA) is used for the char reactivity studies. The temperature and mass are recorded as function of time, using a Macintosh computer and software for simultaneous apparatus control and data acquisition. Specific surface areas of char samples were determined by the N{sub 2} BET method at 77 K. A standard flow-type adsorption device (Quantasorb) was used for the measurements. Prior to surface area analysis, all samples were outgassed in a flow of nitrogen at 573 K for 3 hours. The carbonaceous solids used were resin char, graphite, coconut char and a Wyodak coal char. As was noted in the last report, carbons derived from different original materials show quite similar behaviors, in terms of the trends, but there are significant differences in actual reaction rates. It was shown that the spread of the reaction rate data from different studies, when expressed on a mass of carbon reactant- or surface area-basis, was almost the same.« less

Synthesis of high-quality diesel with furfural and 2-methylfuran from hemicellulose.

PubMed

Li, Guangyi; Li, Ning; Wang, Zhiqiang; Li, Changzhi; Wang, Aiqin; Wang, Xiaodong; Cong, Yu; Zhang, Tao

2012-10-01

Hydroxyalkylation-alkylation (HAA) coupled with hydrodeoxygenation is a promising route for the synthesis of renewable high-quality diesel or jet fuel. In this work, a series of solid-acid catalysts were firstly used for HAA between lignocellulose-derived furan and carbonyl compounds. Among the investigated catalysts, Nafion-212 resin demonstrated the highest activity and stability. Owing to the high activity of the reactants and the advantage in industrial integration, the HAA of 2-methylfuran (2-MF) and furfural can be considered as a prospective route in future applications. Catalyst loading, reaction temperature, and time had evident effects on the HAA of 2-MF and furfural over Nafion-212 resin. Finally, the HAA product of 2-MF and furfural was hydrogenated over a Pd/C catalyst and hydrodeoxygenated over Pt-loaded solid-acid catalysts. Pt/zirconium phosphate (Pt/ZrP) was found to be the best catalyst for hydrodeoxygenation. Over the 4 % Pt/ZrP catalyst, a 94 % carbon yield of diesel and 75 % carbon yield of C15 hydrocarbons (with 6-butylundecane as the major component) was achieved. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Correlation of Intermolecular Acyl Transfer Reactivity with Noncovalent Lattice Interactions in Molecular Crystals: Toward Prediction of Reactivity of Organic Molecules in the Solid State.

PubMed

Krishnaswamy, Shobhana; Shashidhar, Mysore S

2018-04-06

Intermolecular acyl transfer reactivity in several molecular crystals was studied, and the outcome of the reactivity was analyzed in the light of structural information obtained from the crystals of the reactants. Minor changes in the molecular structure resulted in significant variations in the noncovalent interactions and packing of molecules in the crystal lattice, which drastically affected the facility of the intermolecular acyl transfer reactivity in these crystals. Analysis of the reactivity vs crystal structure data revealed dependence of the reactivity on electrophile···nucleophile interactions and C-H···π interactions between the reacting molecules. The presence of these noncovalent interactions augmented the acyl transfer reactivity, while their absence hindered the reactivity of the molecules in the crystal. The validity of these correlations allows the prediction of intermolecular acyl transfer reactivity in crystals and co-crystals of unknown reactivity. This crystal structure-reactivity correlation parallels the molecular structure-reactivity correlation in solution-state reactions, widely accepted as organic functional group transformations, and sets the stage for the development of a similar approach for reactions in the solid state.

Properties of nanostructured undoped ZrO{sub 2} thin film electrolytes by plasma enhanced atomic layer deposition for thin film solid oxide fuel cells

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

Cho, Gu Young; Noh, Seungtak; Lee, Yoon Ho

2016-01-15

Nanostructured ZrO{sub 2} thin films were prepared by thermal atomic layer deposition (ALD) and by plasma-enhanced atomic layer deposition (PEALD). The effects of the deposition conditions of temperature, reactant, plasma power, and duration upon the physical and chemical properties of ZrO{sub 2} films were investigated. The ZrO{sub 2} films by PEALD were polycrystalline and had low contamination, rough surfaces, and relatively large grains. Increasing the plasma power and duration led to a clear polycrystalline structure with relatively large grains due to the additional energy imparted by the plasma. After characterization, the films were incorporated as electrolytes in thin film solidmore » oxide fuel cells, and the performance was measured at 500 °C. Despite similar structure and cathode morphology of the cells studied, the thin film solid oxide fuel cell with the ZrO{sub 2} thin film electrolyte by the thermal ALD at 250 °C exhibited the highest power density (38 mW/cm{sup 2}) because of the lowest average grain size at cathode/electrolyte interface.« less

Still's Disease in a Pediatric Patient after Liver Transplantation.

PubMed

Meza, Juan-Carlos; Muñoz-Buitrón, Evelyn; Bonilla-Abadía, Fabio; Cañas, Carlos Alberto; Tobón, Gabriel J

2013-01-01

Still's disease (SD) is a multisystemic inflammatory disease characterized by persistent arthritis and in many cases with fever of unknown origin. Diagnosis of SD is challenging because of nonspecific characteristics and especially in the case of a patient with solid organ transplantation and immunosuppressive therapy where multiple causes of fever are possible. There is no diagnostic test for SD, even though some useful diagnostic criteria or laboratory findings, such as serum ferritin levels, have been proposed, and useful imaging studies for the diagnosis or followup of SD have not been developed. We report the case of a 9-year-old child who presented with high grade fever associated with joint pain after a history of liver transplantation and immunosuppressive therapy. Laboratory tests showed increased acute phase reactants, elevated ferritin, and leukocytosis. An 18 F-fluorodeoxyglucose positron emission tomography (18F-FDG PET) was performed identifying abnormal hypermetabolic areas localized in spleen, transplanted liver, and bone marrow secondary to inflammatory process. All infectious, autoimmune, and malignant causes were ruled out. A diagnosis of SD was performed and a steroid-based regimen was initiated with adequate response and no evidence of recurrence. To our knowledge this is the first case of SD following a solid organ transplant.

Wet in situ transesterification of microalgae using ethyl acetate as a co-solvent and reactant.

PubMed

Park, Jeongseok; Kim, Bora; Chang, Yong Keun; Lee, Jae W

2017-04-01

This study addresses wet in situ transesterification of microalgae for the production of biodiesel by introducing ethyl acetate as both reactant and co-solvent. Ethyl acetate and acid catalyst are mixed with wet microalgae in one pot and the mixture is heated for simultaneous lipid extraction and transesterification. As a single reactant and co-solvent, ethyl acetate can provide higher FAEE yield and more saccharification of carbohydrates than the case of binary ethanol and chloroform as a reactant and a co-solvent. The optimal yield was 97.8wt% at 114°C and 4.06M catalyst with 6.67mlEtOAC/g dried algae based on experimental results and response surface methodology (RSM). This wet in situ transesterification of microalgae using ethyl acetate doesn't require an additional co-solvent and it also promises more economic benefit as combining extraction and transesterification in a single process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nanoribbon field-effect transistors as direct and label-free sensors of enzyme-substrate interactions

NASA Astrophysics Data System (ADS)

Mu, Luye; Droujinine, Ilia; Rajan, Nitin; Sawtelle, Sonya; Reed, Mark

2015-03-01

The ability to measure enzyme-substrate interactions is essential in areas such as diagnostics, treatment, and biochemical screens. Many enzymatic reactions alter the pH of its environment, suggesting of a simple and direct method for detection. We show the ability of Al2O3-coated Si nanoribbon field-effect transistor biosensors to sensitively measure various aspects of enzyme-substrate interactions through measuring the pH. Urea in phosphate buffered saline (PBS) and penicillinase in PBS and urine were measured to limits of <200 μM and 0.02 units/mL, respectively. We also show the ability to extract accurate kinetics from the interaction of acetylcholine and its esterase. Prior work on FET sensors has been limited by the use of surface functionalization, which not only alters enzyme-substrate affinity, but also makes enzyme activity quantification difficult. Our method involves direct detection of reactions in solution without requiring alteration to the reactants, allowing us to obtain repeatable results and sensitive limits of detection. This method is a simple, inexpensive, and effective platform for detection of enzymatic reactions, and can be readily generalized to many unrelated classes of reactants. This work was supported in part by U.S. Army Research Office and Air Force Research Laboratory.

Incorporating Virtual Reactions into a Logic-based Ligand-based Virtual Screening Method to Discover New Leads

PubMed Central

Reynolds, Christopher R; Muggleton, Stephen H; Sternberg, Michael J E

2015-01-01

The use of virtual screening has become increasingly central to the drug development pipeline, with ligand-based virtual screening used to screen databases of compounds to predict their bioactivity against a target. These databases can only represent a small fraction of chemical space, and this paper describes a method of exploring synthetic space by applying virtual reactions to promising compounds within a database, and generating focussed libraries of predicted derivatives. A ligand-based virtual screening tool Investigational Novel Drug Discovery by Example (INDDEx) is used as the basis for a system of virtual reactions. The use of virtual reactions is estimated to open up a potential space of 1.21×1012 potential molecules. A de novo design algorithm known as Partial Logical-Rule Reactant Selection (PLoRRS) is introduced and incorporated into the INDDEx methodology. PLoRRS uses logical rules from the INDDEx model to select reactants for the de novo generation of potentially active products. The PLoRRS method is found to increase significantly the likelihood of retrieving molecules similar to known actives with a p-value of 0.016. Case studies demonstrate that the virtual reactions produce molecules highly similar to known actives, including known blockbuster drugs. PMID:26583052

NiCo as catalyst for magnetically induced dry reforming of methane

NASA Astrophysics Data System (ADS)

Varsano, F.; Bellusci, M.; Provino, A.; Petrecca, M.

2018-03-01

In this paper we report the activation of the dry reforming reaction by induction heating of a NiCo alloy. The catalyst plays a double role, serving both as a promoter for the reforming reaction and producing the heat induced by dissipation of the electromagnetic energy. The elevated temperatures imposed by the reforming reaction suggest the choice of an alloy with a Curie temperature >800°C. In this respect Ni:Co ratio 60:40 was chosen. Alloy active sites for CH4and CO2activation are created by a mechanochemical treatment of the alloy that increases solid-state defects. The catalyst has been successfully tested in a continuous-flow reactor working under atmospheric pressure. Methane conversion and hydrogen production yields have been measured as a function of the applied magnetic field, reactant flow rate and time on stream.

Dip-pen nanopatterning of photosensitive conducting polymer using a monomer ink

NASA Astrophysics Data System (ADS)

Su, Ming; Aslam, Mohammed; Fu, Lei; Wu, Nianqiang; Dravid, Vinayak P.

2004-05-01

Controlled patterning of conducting polymers at a micro- or nanoscale is the first step towards the fabrication of miniaturized functional devices. Here, we introduce an approach for the nanopatterning of conducting polymers using an improved monomer "ink" in dip-pen nanolithography (DPN). The nominal monomer "ink" is converted, in situ, to its conducting solid-state polymeric form after patterned. Proof-of-concept experiments have been performed with acid-promoted polymerization of pyrrole in a less reactive environment (tetrahydrofuran). The ratios of reactants are optimized to give an appropriate rate to match the operation of DPN. A similar synthesis process for the same polymer in its bulk form shows a high conductance and crystalline structure. The miniaturized conducting polymer sensors with light detection ability are fabricated by DPN using the improved ink formula, and exhibit excellent response, recovery, and sensitivity parameters.

Sodium-sulfur battery flight experiment definition study

NASA Technical Reports Server (NTRS)

Chang, Rebecca; Minck, Robert

1990-01-01

Sodium-sulfur batteries are considered to be one of the most likely battery systems for space applications. Compared with the Ni-H2 or Ni-Co battery systems, Na-S batteries offer a mass reduction by a factor of 2 to 4, representing significant launch cost savings or increased payload mass capabilities. The Na-S battery operates at between 300 and 400 C, using liquid sodium and sulfur/polysulfide electrodes and solid ceramic electrolyte; the transport of the electrode materials to the surface of the electrolyte is through wicking/capillary forces. This paper describes five tests identified for the Na-S battery flight experiment definition study, which include the cell characterization test, the reactant distribution test, the current/temperature distribution test, the freeze/thaw test, and the multicell LEO test. A schematic diagram of Na-S cell is included.

Supply of reactants for Redox bulk energy storage systems

NASA Technical Reports Server (NTRS)

Gahn, R. F.

1978-01-01

World resources, reserves, production, and costs of reactant materials, iron, chromium, titanium and bromine for proposed redox cell bulk energy storage systems are reviewed. Supplying required materials for multimegawatt hour systems appears to be feasible even at current production levels. Iron and chromium ores are the most abundant and lowest cost of four reactants. Chromium is not a domestic reserve, but redox system installations would represent a small fraction of U.S. imports. Vast quantities of bromine are available, but present production is low and therefore cost is high. Titanium is currently available at reasonable cost, with ample reserves available for the next fifty years.

PMR polyimide composites for aerospace applications. [Polymerization of Monomer Reactants

NASA Technical Reports Server (NTRS)

Serafini, T. T.

1984-01-01

A novel class of addition-type polyimides has been developed in response to the need for high temperature polymers with improved processability. The new plastic materials are known as PMR (for in situ polymerization of monomer reactants) polyimides. The highly processable PMR polyimides have made it possible to realize much of the potential of high temperature resistant polymers. Monomer reactant combinations for several PMR polyimides have been identified. The present investigation is concerned with a review of the current status of PMR polyimides. Attention is given to details of PMR polyimide chemistry, the processing of composites and their properties, and aerospace applications of PMR-15 polyimide composites.

Heat recirculating cooler for fluid stream pollutant removal

DOEpatents

Richards, George A.; Berry, David A.

2008-10-28

A process by which heat is removed from a reactant fluid to reach the operating temperature of a known pollutant removal method and said heat is recirculated to raise the temperature of the product fluid. The process can be utilized whenever an intermediate step reaction requires a lower reaction temperature than the prior and next steps. The benefits of a heat-recirculating cooler include the ability to use known pollutant removal methods and increased thermal efficiency of the system.

UV absorption control of thin film growth

DOEpatents

Biefeld, Robert M.; Hebner, Gregory A.; Killeen, Kevin P.; Zuhoski, Steven P.

1991-01-01

A system for monitoring and controlling the rate of growth of thin films in an atmosphere of reactant gases measures the UV absorbance of the atmosphere and calculates the partial pressure of the gases. The flow of reactant gases is controlled in response to the partial pressure.

Operando chemistry of catalyst surfaces during catalysis.

PubMed

Dou, Jian; Sun, Zaicheng; Opalade, Adedamola A; Wang, Nan; Fu, Wensheng; Tao, Franklin Feng

2017-04-03

Chemistry of a catalyst surface during catalysis is crucial for a fundamental understanding of mechanism of a catalytic reaction performed on the catalyst in the gas or liquid phase. Due to the pressure- or molecular density-dependent entropy contribution of gas or liquid phase of the reactants and the potential formation of a catalyst surface during catalysis different from that observed in an ex situ condition, the characterization of the surface of a catalyst under reaction conditions and during catalysis can be significant and even necessary for understanding the catalytic mechanism at a molecular level. Electron-based analytical techniques are challenging for studying catalyst nanoparticles in the gas or liquid phase although they are necessary techniques to employ. Instrumentation and further development of these electron-based techniques have now made in situ/operando studies of catalysts possible. New insights into the chemistry and structure of catalyst nanoparticles have been uncovered over the last decades. Herein, the origin of the differences between ex situ and in situ/operando studies of catalysts, and the technical challenges faced as well as the corresponding instrumentation and innovations utilized for characterizing catalysts under reaction conditions and during catalysis, are discussed. The restructuring of catalyst surfaces driven by the pressure of reactant(s) around a catalyst, restructuring in reactant(s) driven by reaction temperature and restructuring during catalysis are also reviewed herein. The remaining challenges and possible solutions are briefly discussed.

Mechanism of Phenol Alkylation in Zeolite H-BEA Using In Situ Solid-State NMR Spectroscopy

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

Zhao, Zhenchao; Shi, Hui; Wan, Chuan

Alkylation of phenolic compounds in the liquid phase is of fundamental and practical importance to the conversion of biomass-derived feedstocks into fuels and chemicals. In this work, the reaction mechanism for phenol alkylation with cyclohexanol and cyclohexene has been investigated on a commercial HBEA zeolite by in situ 13C MAS NMR, using decalin as the solvent. From the variable temperature 13C MAS NMR measurements of phenol and cyclohexanol adsorption on HBEA from decalin solutions, it is shown that the two molecules have similar adsorption strength in the HBEA pore. Phenol alkylation with cyclohexanol, however, becomes significantly measurable only after cyclohexanolmore » is largely converted to cyclohexene via dehydration. This is in contrast to the initially rapid alkylation of phenol when using cyclohexene as the co-reactant. 13C isotope scrambling results demonstrate that the electrophile, presumably cyclohexyl carbenium ion, is directly formed in a protonation step when cyclohexene is the co-reactant, but requires re-adsorption of the alcohol dehydration product, cyclohexene, when cyclohexanol dimer is the dominant surface species (e.g., at 0.5 M cyclohexanol concentration) that is unable to generate carbenium ion. At the initial reaction stage of phenol-cyclohexanol alkylation on HBEA, the presence of the cyclohexanol dimer species hinders the adsorption of cyclohexene at the Brønsted acid site and the subsequent activation of the more potent electrophile (carbenium ion). Isotope scrambling data also show that intramolecular rearrangement of cyclohexyl phenyl ether, the O-alkylation product, does not significantly contribute to the formation of C-alkylation products.« less

Electric Current Activated Combustion Synthesis and Chemical Ovens Under Terrestrial and Reduced Gravity Conditions

NASA Technical Reports Server (NTRS)

Unuvar, C.; Fredrick, D.; Anselmi-Tamburini, U.; Manerbino, A.; Guigne, J. Y.; Munir, Z. A.; Shaw, B. D.

2004-01-01

Combustion synthesis (CS) generally involves mixing reactants together (e.g., metal powders) and igniting the mixture. Typically, a reaction wave will pass through the sample. In field activated combustion synthesis (FACS), the addition of an electric field has a marked effect on the dynamics of wave propagation and on the nature, composition, and homogeneity of the product as well as capillary flow, mass-transport in porous media, and Marangoni flows, which are influenced by gravity. The objective is to understand the role of an electric field in CS reactions under conditions where gravity-related effects are suppressed or altered. The systems being studied are Ti+Al and Ti+3Al. Two different ignition orientations have been used to observe effects of gravity when one of the reactants becomes molten. This consequentially influences the position and concentration of the electric current, which in turn influences the entire process. Experiments have also been performed in microgravity conditions. This process has been named Microgravity Field Activated Combustion Synthesis (MFACS). Effects of gravity have been demonstrated, where the reaction wave temperature and velocity demonstrate considerable differences besides the changes of combustion mechanisms with the different high currents applied. Also the threshold for the formation of a stable reaction wave is increased under zero gravity conditions. Electric current was also utilized with a chemical oven technique, where inserts of aluminum with minute amounts of tungsten and tantalum were used to allow observation of effects of settling of the higher density solid particles in liquid aluminum at the present temperature profile and wave velocity of the reaction.

Trapping in water - an important prerequisite for complex reactivity in astrophysical ices: the case of acetone (CH3)2C = O and ammonia NH3

NASA Astrophysics Data System (ADS)

Fresneau, Aurélien; Danger, Grégoire; Rimola, Albert; Theule, Patrice; Duvernay, Fabrice; Chiavassa, Thierry

2014-10-01

Water is the most abundant compound in interstellar and cometary ices. Laboratory experiments on ice analogues have shown that water has a great influence on the chemical activity of these ices. In this study, we investigated the reactivity of acetone-ammonia ices, showing that water is an essential component in chemical reactions with high activation energies. In a water-free binary ice, acetone and ammonia do not react due to high activation energy, as the reactants desorb before reacting (at 120 and 140 K, respectively). By contrast, our study shows that under experimental conditions of ˜150 K, this reaction does occur in the presence of water. Here, water traps reactants in the solid phase above their desorption temperatures, allowing them to gather thermal energy as the reaction proceeds. Using infrared spectroscopy and mass spectrometry associated with isotopic labelling, as well as quantum chemical calculations, 2-aminopropan-2-ol (2HN-C(CH3)2-OH) was identified as the acetone-ammonia reaction product. The formation of this product may represent the first step towards formation of 2-aminoisobutyric acid (AIB) in the Strecker synthesis. The activation energy for the formation of 2-aminopropan-2-ol was measured to be 42 ± 3 kJ mol-1, while its desorption energy equalled 61.3 ± 0.1 kJ mol-1. Our work demonstrates that astrophysical water, rather than being a non-thermally reactive species, is crucial for the evolution of complex chemistry occurring in the Universe.

Negative electrode catalyst for the iron chromium redox energy storage system

NASA Technical Reports Server (NTRS)

Gahn, R. F.; Hagedorn, N. H. (Inventor)

1985-01-01

A redox cell which operates at elevated temperatures and which utilizes the same two metal couples in each of the two reactant fluids is disclosed. Each fluid includes a bismuth salt and may also include a lead salt. A low cost, cation permselective membrane separates the reactant fluids.

A Simple DWBA (’Franck-Condon’) Treatment of H-Atom Transfers between Two Heavy Particles.

DTIC Science & Technology

1984-07-02

integral over the reactants’ and products’ wavefunctions and the interaction potential. )Permanent address: DIpartarnento de Quirnica Fisica y Quimica... Cuantica , USniversidad Autonomna de Madrid, Cantoblanco. Madrid-34, Spain. blContribution No. 7020. -2- The reactants’ and products’ wavelunctions

Manufacture of silicon carbide using solar energy

DOEpatents

Glatzmaier, Gregory C.

1992-01-01

A method is described for producing silicon carbide particles using solar energy. The method is efficient and avoids the need for use of electrical energy to heat the reactants. Finely divided silica and carbon are admixed and placed in a solar-heated reaction chamber for a time sufficient to cause a reaction between the ingredients to form silicon carbide of very small particle size. No grinding of silicon carbide is required to obtain small particles. The method may be carried out as a batch process or as a continuous process.

Combined energy production and waste management in manned spacecraft utilizing on-demand hydrogen production and fuel cells

NASA Astrophysics Data System (ADS)

Elitzur, Shani; Rosenband, Valery; Gany, Alon

2016-11-01

Energy supply and waste management are among the most significant challenges in human spacecraft. Great efforts are invested in managing solid waste, recycling grey water and urine, cleaning the atmosphere, removing CO2, generating and saving energy, and making further use of components and products. This paper describes and investigates a concept for managing waste water and urine to simultaneously produce electric and heat energies as well as fresh water. It utilizes an original technique for aluminum activation to react spontaneously with water at room temperature to produce hydrogen on-site and on-demand. This reaction has further been proven to be effective also when using waste water and urine. Applying the hydrogen produced in a fuel cell, one obtains electric energy as well as fresh (drinking) water. The method was compared to the traditional energy production technology of the Space Shuttle, which is based on storing the fuel cell reactants, hydrogen and oxygen, in cryogenic tanks. It is shown that the alternative concept presented here may provide improved safety, compactness (reduction of more than one half of the volume of the hydrogen storage system), and management of waste liquids for energy generation and drinking water production. Nevertheless, it adds mass compared to the cryogenic hydrogen technology. It is concluded that the proposed method may be used as an emergency and backup power system as well as an additional hydrogen source for extended missions in human spacecraft.

Origin of carbon in aromatic and olefin products derived from HZSM-5 catalyzed co-pyrolysis of cellulose and plastics via isotopic labeling

USDA-ARS?s Scientific Manuscript database

Catalytic pyrolysis over HZSM-5 is an effective method for the conversion of biomass to aromatic hydrocarbons, albeit with low yield and short catalyst lifetimes. Addition of co-reactants rich in carbon and hydrogen can enhance yield and possibly increase catalyst lifetimes by reducing coke formati...

Thermoelectrochemical system and method

DOEpatents

Ludwig, F.A.; Townsend, C.W.; Eliash, B.M.

1995-11-28

A thermal electrochemical system is described in which an electrical current is generated between a cathode immersed in a concentrated aqueous solution of phosphoric acid and an anode immersed in a molten salt solution of ammonium phosphate and monohydric ammonium phosphate. Reactants consumed at the electrodes during the electrochemical reaction are thermochemically regenerated and recycled to the electrodes to provide continuous operation of the system. 5 figs.

Fast quench reactor and method

DOEpatents

Detering, Brent A.; Donaldson, Alan D.; Fincke, James R.; Kong, Peter C.

2002-01-01

A fast quench reaction includes a reactor chamber having a high temperature heating means such as a plasma torch at its inlet and a restrictive convergent-divergent nozzle at its outlet end. Reactants are injected into the reactor chamber. The resulting heated gaseous stream is then rapidly cooled by passage through the nozzle. This "freezes" the desired end product(s) in the heated equilibrium reaction stage.

Pulsed jet combustion generator for premixed charge engines

DOEpatents

Oppenheim, A. K.; Stewart, H. E.; Hom, K.

1990-01-01

A method and device for generating pulsed jets which will form plumes comprising eddie structures, which will entrain a fuel/air mixture from the head space of an internal combustion engine, and mixing this fuel/air mixture with a pre-ignited fuel/air mixture of the plumes thereby causing combustion of the reactants to occur within the interior of the eddie structures.

Fast quench reactor and method

DOEpatents

Detering, Brent A.; Donaldson, Alan D.; Fincke, James R.; Kong, Peter C.

1998-01-01

A fast quench reaction includes a reactor chamber having a high temperature heating means such as a plasma torch at its inlet and a restrictive convergent-divergent nozzle at its outlet end. Reactants are injected into the reactor chamber. The resulting heated gaseous stream is then rapidly cooled by passage through the nozzle. This "freezes" the desired end product(s) in the heated equilibrium reaction stage.

Fast quench reactor and method

DOEpatents

Detering, Brent A.; Donaldson, Alan D.; Fincke, James R.; Kong, Peter C.

2002-09-24

A fast quench reaction includes a reactor chamber having a high temperature heating means such as a plasma torch at its inlet and a restrictive convergent-divergent nozzle at its outlet end. Reactants are injected into the reactor chamber. The resulting heated gaseous stream is then rapidly cooled by passage through the nozzle. This "freezes" the desired end product(s) in the heated equilibrium reaction stage.

Mix Model Comparison of Low Feed-Through Implosions

NASA Astrophysics Data System (ADS)

Pino, Jesse; MacLaren, S.; Greenough, J.; Casey, D.; Dewald, E.; Dittrich, T.; Khan, S.; Ma, T.; Sacks, R.; Salmonson, J.; Smalyuk, V.; Tipton, R.; Kyrala, G.

2016-10-01

The CD Mix campaign previously demonstrated the use of nuclear diagnostics to study the mix of separated reactants in plastic capsule implosions at the NIF. Recently, the separated reactants technique has been applied to the Two Shock (TS) implosion platform, which is designed to minimize this feed-through and isolate local mix at the gas-ablator interface and produce core yields in good agreement with 1D clean simulations. The effects of both inner surface roughness and convergence ratio have been probed. The TT, DT, and DD neutron signals respectively give information about core gas performance, gas-shell atomic mix, and heating of the shell. In this talk, we describe efforts to model these implosions using high-resolution 2D ARES simulations. Various methods of interfacial mix will be considered, including the Reynolds-Averaged Navier Stokes (RANS) KL method as well as and a multicomponent enhanced diffusivity model with species, thermal, and pressure gradient terms. We also give predictions of a upcoming campaign to investigate Mid-Z mixing by adding a Ge dopant to the CD layer. LLNL-ABS-697251 This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Low-Temperature Catalytic Process To Produce Hydrocarbons From Sugars

DOEpatents

Cortright, Randy D.; Dumesic, James A.

2005-11-15

Disclosed is a method of producing hydrogen from oxygenated hydrocarbon reactants, such as methanol, glycerol, sugars (e.g. glucose and xylose), or sugar alcohols (e.g. sorbitol). The method takes place in the condensed liquid phase. The method includes the steps of reacting water and a water-soluble oxygenated hydrocarbon in the presence of a metal-containing catalyst. The catalyst contains a metal selected from the group consisting of Group VIIIB transitional metals, alloys thereof, and mixtures thereof. The disclosed method can be run at lower temperatures than those used in the conventional steam reforming of alkanes.

NASA redox storage system development project, calendar year 1982

NASA Technical Reports Server (NTRS)

1983-01-01

Development was continued for iron-chromium battery operation at 65 C. Membranes that were adequate at 25 C were shown to be unacceptable at 65 C with regard to selectivity. This led to the elevated-temperature, mixed-reactant mode of operation, in which each reactant solution, when discharged, contains both ferrous and chromic chlorides. This operating mode allows the use of very low-resistivity membranes, resulting in high energy efficiencies at current densities. It also allows the use of very simple techniques to correct for solvent or reactant transfer through cell membranes. Screening of candidate catalysts for the chromium electrode led to the development of a bismuth-lead candidate having several attractive characteristics.

Magic angle spinning nuclear magnetic resonance apparatus and process for high-resolution in situ investigations

DOEpatents

Hu, Jian Zhi; Sears, Jr., Jesse A.; Hoyt, David W.; Mehta, Hardeep S.; Peden, Charles H. F.

2015-11-24

A continuous-flow (CF) magic angle sample spinning (CF-MAS) NMR rotor and probe are described for investigating reaction dynamics, stable intermediates/transition states, and mechanisms of catalytic reactions in situ. The rotor includes a sample chamber of a flow-through design with a large sample volume that delivers a flow of reactants through a catalyst bed contained within the sample cell allowing in-situ investigations of reactants and products. Flow through the sample chamber improves diffusion of reactants and products through the catalyst. The large volume of the sample chamber enhances sensitivity permitting in situ .sup.13C CF-MAS studies at natural abundance.

Hot-filament chemical vapor deposition chamber and process with multiple gas inlets

DOEpatents

Deng, Xunming; Povolny, Henry S.

2004-06-29

A thin film deposition method uses a vacuum confinement cup that employs a dense hot filament and multiple gas inlets. At least one reactant gas is introduced into the confinement cup both near and spaced apart from the heated filament. An electrode inside the confinement cup is used to generate plasma for film deposition. The method is used to deposit advanced thin films (such as silicon based thin films) at a high quality and at a high deposition rate.

Aqueous phase removal of nitrogen from nitrogen compounds

DOEpatents

Fassbender, Alex G.

1993-01-01

A method is disclosed for denitrification of compounds containing nitrogen present in aqueous waste streams. The method comprises the steps of (1) identifying the types of nitrogen compounds present in a waste stream, (2) determining the concentrations of nitrogen compounds, (3) balancing oxidized and reduced form of nitrogen by adding a reactant, and (4) heating the mixture to a predetermined reaction temperature from about 300.degree. C. to about 600.degree. C., thereby resulting in less harmful nitrogen and oxygen gas, hydroxides, alcohols, and hydrocarbons.

Method of controllong the deposition of hydrogenated amorphous silicon and apparatus therefor

DOEpatents

Hanak, Joseph J.

1985-06-25

An improved method and apparatus for the controlled deposition of a layer of hydrogenated amorphous silicon on a substrate. Means is provided for the illumination of the coated surface of the substrate and measurement of the resulting photovoltage at the outermost layer of the coating. Means is further provided for admixing amounts of p type and n type dopants to the reactant gas in response to the measured photovoltage to achieve a desired level and type of doping of the deposited layer.

Method of producing ternary lead molybdenum sulfides

DOEpatents

Foner, Simon; McNiff, Jr., Edward J.; Alexander, Edwin J.

1977-02-01

The method of preparing Pb.sub.x Mo.sub.y S.sub.z where x = 0.8-1.1, y = 4.5-5.6, and z = 5.4-7.2 comprising the steps of mixing commercial reagent grade powders of the reactants, heating in a sealed, evacuated reaction vessel to a temperature of 950.degree.-1150.degree. C, maintaining the temperature until the compound is formed, and then cooling the compound at a controlled rate not in excess of 4.degree. C per minute.

Organic chemistry on solid surfaces

NASA Astrophysics Data System (ADS)

Ma, Zhen; Zaera, Francisco

2006-07-01

Chemistry on solid surfaces is central to many areas of practical interest such as heterogeneous catalysis, tribology, electrochemistry, and materials processing. With the development of many surface-sensitive analytical techniques in the past decades, great advances have been possible in our understanding of such surface chemistry at the molecular level. Earlier studies with model systems, single crystals in particular, have provided rich information about the adsorption and reaction kinetics of simple inorganic molecules. More recently, the same approach has been expanded to the study of the surface chemistry of relatively complex organic molecules, in large measure in connection with the selective synthesis of fine chemicals and pharmaceuticals. In this report, the chemical reactions of organic molecules and fragments on solid surfaces, mainly on single crystals of metals but also on crystals of metal oxides, carbides, nitrides, phosphides, sulfides and semiconductors as well as on more complex models such as bimetallics, alloys, and supported particles, are reviewed. A scheme borrowed from the organometallic and organic chemistry literature is followed in which key examples of representative reactions are cited first, and general reactivity trends in terms of both the reactants and the nature of the surface are then identified to highlight important mechanistic details. An attempt has been made to emphasize recent advances, but key earlier examples are cited as needed. Finally, correlations between surface and organometallic and organic chemistry, the relevance of surface reactions to applied catalysis and materials functionalization, and some promising future directions in this area are briefly discussed.

Elementary reaction modeling of reversible CO/CO2 electrochemical conversion on patterned nickel electrodes

NASA Astrophysics Data System (ADS)

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

2018-03-01

CO/CO2 are the major gas reactant/product in the fuel electrode of reversible solid oxide cells (RSOC). This study proposes a two-charge-transfer-step mechanism to describe the reaction and transfer processes of CO-CO2 electrochemical conversion on a patterned Ni electrode of RSOC. An elementary reaction model is developed to couple two charge transfer reactions, C(Ni)+O2-(YSZ) ↔ CO(Ni)+(YSZ) +2e- and CO(Ni)+O2-(YSZ) ↔ CO2(Ni)+(YSZ)+2e-, with adsorption/desorption, surface chemical reactions and surface diffusion. This model well validates in both solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) modes by the experimental data from a patterned Ni electrode with 10 μm stripe width at different pCO (0-0.25 atm), pCO2 (0-0.35 atm) and operating temperature (600-700 °C). This model indicates SOEC mode is dominated by charge transfer step C(Ni)+O2-(YSZ)↔CO(Ni)+(YSZ) +2e-, while SOFC mode by CO(Ni)+ O2-(YSZ)↔CO2(Ni)+(YSZ)+2e- on the patterned Ni electrode. The sensitivity analysis shows charge transfer step is the major rate-determining step for RSOC, besides, surface diffusion of CO and CO2 as well as CO2 adsorption also plays a significant role in the electrochemical reaction of SOEC while surface diffusion of CO and CO2 desorption could be co-limiting in SOFC.

High-temperature electrolysis of CO2-enriched mixtures by using fuel-electrode supported La0.6Sr0.4CoO3/YSZ/Ni-YSZ solid oxide cells

NASA Astrophysics Data System (ADS)

Kim, Si-Won; Bae, Yonggyun; Yoon, Kyung Joong; Lee, Jong-Ho; Lee, Jong-Heun; Hong, Jongsup

2018-02-01

To mitigate CO2 emissions, its reduction by high-temperature electrolysis using solid oxide cells is extensively investigated, for which excessive steam supply is assumed. However, such condition may degrade its feasibility due to massive energy required for generating hot steam, implying the needs for lowering steam demand. In this study, high-temperature electrolysis of CO2-enriched mixtures by using fuel-electrode supported La0.6Sr0.4CoO3/YSZ/Ni-YSZ solid oxide cells is considered to satisfy such needs. The effect of internal and external steam supply on its electrochemical performance and gas productivity is elucidated. It is shown that the steam produced in-situ inside the fuel-electrode by a reverse water gas shift reaction may decrease significantly the electrochemical resistance of dry CO2-fed operations, attributed to self-sustaining positive thermo-electrochemical reaction loop. This mechanism is conspicuous at low current density, whereas it is no longer effective at high current density in which total reactant concentrations for electrolysis is critical. To overcome such limitations, a small amount of external steam supply to the CO2-enriched feed stream may be needed, but this lowers the CO2 conversion and CO/H2 selectivity. Based on these results, it is discussed that there can be minimum steam supply sufficient for guaranteeing both low electrochemical resistance and high gas productivity.

Teachers' Misconceptions about the Effects of Addition of More Reactants or Products on Chemical Equilibrium

ERIC Educational Resources Information Center

Cheung, Derek; Ma, Hong-jia; Yang, Jie

2009-01-01

The importance of research on misconceptions about chemical equilibrium is well recognized by educators, but in the past, researchers' interest has centered on student misconceptions and has neglected teacher misconceptions. Focusing on the effects of adding more reactants or products on chemical equilibrium, this article discusses the various…

The Roles of Acids and Bases in Enzyme Catalysis

ERIC Educational Resources Information Center

Weiss, Hilton M.

2007-01-01

Many organic reactions are catalyzed by strong acids or bases that protonate or deprotonate neutral reactants leading to reactive cations or anions that proceed to products. In enzyme reactions, only weak acids and bases are available to hydrogen bond to reactants and to transfer protons in response to developing charges. Understanding this…

Chronocoulometry: A Convenient, Rapid and Reliable Technique for Detection and Determination of Adsorbed Reactants.

ERIC Educational Resources Information Center

Anson, Fred C.; Osteryoung, Robert A.

1983-01-01

Measurement of the time dependence of the flow of charge constitutes the procedure known as chronocoulometry. Although the technique is useful in a variety of electrochemical measurements, the discussion focuses on the evaluation of reactant adsorption, the application for which the technique was originally devised. (JN)

CATALYST-FREE REACTIONS UNDER SOLVENT-FEE CONDITIONS: MICROWAVE-ASSISTED SYNTHESIS OF HETEROCYCLIC HYDRAZONES BELOW THE MELTING POINT OF NEAT REACTANTS: JOURNAL ARTICLE

EPA Science Inventory

NRMRL-CIN-1437 Jeselnik, M., Varma*, R.S., Polanc, S., and Kocevar, M. Catalyst-free Reactions under Solvent-fee Conditions: Microwave-assisted Synthesis of Heterocyclic Hydrazones below the Melting Point of Neat Reactants. Published in: Chemical Communications 18:1716-1717 (200...

Spatially Localized Chemical Patterns around an A + B → Oscillator Front.

PubMed

Budroni, M A; Lemaigre, L; Escala, D M; Muñuzuri, A P; De Wit, A

2016-02-18

When two gels, each loaded with a different set of reactants A and B of an oscillatory reaction, are brought into contact, reaction-diffusion patterns such as waves or Turing patterns can develop in the reactive contact zone. The initial condition which separates the reactants at the beginning leads to a localization in space of the different dynamical regimes accessible to the chemical oscillator. We study here both numerically and experimentally the composite traveling structures resulting from the interaction between chemical fronts and localized waves in the case in which the reactants of such an A + B → oscillator system are those of the canonical Belousov-Zhabotinsky (BZ) oscillating reaction. A transition between different dynamics is obtained by varying the initial concentration of the organic substrate of the BZ reactants, which is one of the parameters controlling the local excitability. We show that the dynamical regime (excitable or oscillatory) characterizing the BZ oscillator in the initial contact area is the key feature which determines the spatiotemporal evolution of the system. The experimental results are in qualitative agreement with the theoretical predictions.

The Advantages of Non-Flow-Through Fuel Cell Power Systems for Aerospace Applications

NASA Technical Reports Server (NTRS)

Hoberecht, Mark; Burke, Kenneth; Jakupca, Ian

2011-01-01

NASA has been developing proton-exchange-membrane (PEM) fuel cell power systems for the past decade, as an upgraded technology to the alkaline fuel cells which presently provide power for the Shuttle Orbiter. All fuel cell power systems consist of one or more fuel cell stacks in combination with appropriate balance-of-plant hardware. Traditional PEM fuel cells are characterized as flow-through, in which recirculating reactant streams remove product water from the fuel cell stack. NASA recently embarked on the development of non-flow-through fuel cell systems, in which reactants are dead-ended into the fuel cell stack and product water is removed by internal wicks. This simplifies the fuel cell power system by eliminating the need for pumps to provide reactant circulation, and mechanical water separators to remove the product water from the recirculating reactant streams. By eliminating these mechanical components, the resulting fuel cell power system has lower mass, volume, and parasitic power requirements, along with higher reliability and longer life. These improved non-flow-through fuel cell power systems therefore offer significant advantages for many aerospace applications.

Crossover behavior of the thermal conductance and Kramers’ transition rate theory

DOE PAGES

Velizhanin, Kirill A.; Sahu, Subin; Chien, Chih -Chun; ...

2015-12-04

Kramers’ theory frames chemical reaction rates in solution as reactants overcoming a barrier in the presence of friction and noise. For weak coupling to the solution, the reaction rate is limited by the rate at which the solution can restore equilibrium after a subset of reactants have surmounted the barrier to become products. For strong coupling, there are always sufficiently energetic reactants. However, the solution returns many of the intermediate states back to the reactants before the product fully forms. Here, we demonstrate that the thermal conductance displays an analogous physical response to the friction and noise that drive themore » heat current through a material or structure. A crossover behavior emerges where the thermal reservoirs dominate the conductance at the extremes and only in the intermediate region are the intrinsic properties of the lattice manifest. Finally, not only does this shed new light on Kramers’ classic turnover problem, this result is significant for the design of devices for thermal management and other applications, as well as the proper simulation of transport at the nanoscale.« less

Is Freedom Contagious? A Self-Regulatory Model of Reactance and Sensitivity to Deviant Peers.

PubMed

Leander, N Pontus; vanDellen, Michelle R; Rachl-Willberger, Judith; Shah, James Y; Fitzsimons, Gavan J; Chartrand, Tanya L

2016-12-01

Psychological reactance is typically assumed to motivate resistance to controlling peer influences and societal prohibitions. However, some peer influences encourage behaviors prohibited by society. We consider whether reactant individuals are sensitive to such opportunities to enhance their autonomy. We specifically propose a self-regulatory perspective on reactance, wherein freedom/autonomy is the superordinate goal, and thus highly reactant individuals will be sensitive to peer influences that could enhance their behavioral freedoms. In two studies, we find that reactant individuals can be cooperative in response to autonomy-supportive peer influences. Participants read a scenario in which a peer's intentions to engage in substance use were manipulated to imply freedom of choice or not. Results indicated that highly reactant participants were sensitive to deviant peers whose own behavior towards alcohol (Study 1, N = 160) or marijuana (Study 2, N = 124) appeared to be motivated by autonomy and thus afforded free choice. Altogether, the results support a self-regulatory model of reactance, wherein deviant peer influence can be a means to pursue autonomy.

Chirality in adsorption on solid surfaces.

PubMed

Zaera, Francisco

2017-12-07

In the present review we survey the main advances made in recent years on the understanding of chemical chirality at solid surfaces. Chirality is an important topic, made particularly relevant by the homochiral nature of the biochemistry of life on Earth, and many chiral chemical reactions involve solid surfaces. Here we start our discussion with a description of surface chirality and of the different ways that chirality can be bestowed on solid surfaces. We then expand on the studies carried out to date to understand the adsorption of chiral compounds at a molecular level. We summarize the work published on the adsorption of pure enantiomers, of enantiomeric mixtures, and of prochiral molecules on chiral and achiral model surfaces, especially on well-defined metal single crystals but also on other flat substrates such as highly ordered pyrolytic graphite. Several phenomena are identified, including surface reconstruction and chiral imprinting upon adsorption of chiral agents, and the enhancement or suppression of enantioselectivity seen in some cases upon adsorption of enantiomixtures of chiral compounds. The possibility of enhancing the enantiopurity of adsorbed layers upon the addition of chiral seeds and the so-called "sergeants and soldiers" phenomenon are presented. Examples are provided where the chiral behavior has been associated with either thermodynamic or kinetic driving forces. Two main approaches to the creation of enantioselective surface sites are discussed, namely, via the formation of supramolecular chiral ensembles made out of small chiral adsorbates, and by adsorption of more complex chiral molecules capable of providing suitable chiral environments for reactants by themselves, via the formation of individual adsorbate:modifier adducts on the surface. Finally, a discussion is offered on the additional effects generated by the presence of the liquid phase often required in practical applications such as enantioselective crystallization, chiral chromatography, and enantioselective catalysis.

Spatial atomic layer deposition for coating flexible porous Li-ion battery electrodes

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

Yersak, Alexander S.; Sharma, Kashish; Wallas, Jasmine M.

Ultrathin atomic layer deposition (ALD) coatings on the electrodes of Li-ion batteries can enhance the capacity stability of the Li-ion batteries. To commercialize ALD for Li-ion battery production, spatial ALD is needed to decrease coating times and provide a coating process compatible with continuous roll-to-roll (R2R) processing. The porous electrodes of Li-ion batteries provide a special challenge because higher reactant exposures are needed for spatial ALD in porous substrates. This work utilized a modular rotating cylinder spatial ALD reactor operating at rotation speeds up to 200 revolutions/min (RPM) and substrate speeds up to 200 m/min. The conditions for spatial ALDmore » were adjusted to coat flexible porous substrates. The reactor was initially used to characterize spatial Al2O3 and ZnO ALD on flat, flexible metalized polyethylene terephthalate foils. These studies showed that slower rotation speeds and spacers between the precursor module and the two adjacent pumping modules could significantly increase the reactant exposure. The modular rotating cylinder reactor was then used to coat flexible, model porous anodic aluminum oxide (AAO) membranes. The uniformity of the ZnO ALD coatings on the porous AAO membranes was dependent on the aspect ratio of the pores and the reactant exposures. Larger reactant exposures led to better uniformity in the pores with higher aspect ratios. The reactant exposures were increased by adding spacers between the precursor module and the two adjacent pumping modules. The modular rotating cylinder reactor was also employed for Al2O3 ALD on porous LiCoO2 (LCO) battery electrodes. Uniform Al coverages were obtained using spacers between the precursor module and the two adjacent pumping modules at rotation speeds of 25 and 50 RPM. The LCO electrodes had a thickness of ~49 um and pores with aspect ratios of ~12-25. Coin cells were then constructed using the ALD-coated LCO electrodes and were tested to determine their battery performance. The capacity of the Al2O3 ALD-coated LCO battery electrodes was measured versus the number of charge-discharge cycles. Both temporal and spatial ALD processing methods led to higher capacity stability compared with uncoated LCO battery electrodes. The results for improved battery performance were comparable for temporal and spatial ALD-coated electrodes. The next steps are also presented for scale-up to R2R spatial ALD using the modular rotating cylinder reactor.« less

Development of a PEMFC Power System with Integrated Balance of Plant

NASA Technical Reports Server (NTRS)

Wynne, B.; Diffenderfer, C.; Ferguson, S.; Keyser, J.; Miller, M.; Sievers, B.; Ryan, A.; Vasquez, A.

2012-01-01

Autonomous Underwater Vehicles (AUV s) have received increasing attention in recent years as military and commercial users look for means to maintain a mobile and persistent presence in the undersea world. Compact, neutrally buoyant power systems are needed for both small and large vehicles. Batteries are usually employed in these applications, but the energy density and therefore the mission duration are limited with current battery technology. At a certain energy or mission duration requirement, other means to get long duration power become feasible. For example, above 10 kW-hrs liquid oxygen and hydrogen have better specific energy than batteries and are preferable for energy storage as long as a compact system of about 100 W/liter is achievable to convert the chemical energy in these reactants into power. Other reactant forms are possible, such as high pressure gas, chemical hydrides or oxygen carriers, but it is essential that the power system be small and light weight. Recent fuel cell work, primarily focused on NASA applications, has developed power systems that can meet this target power density. Passive flow-through systems, using ejector driven reactant (EDR) flow, integrated into a compact balance of plant have been developed. These systems are thermally and functionally integrated in much the same way as are automotive, air breathing fuel cell systems. These systems fit into the small volumes required for AUV and future NASA applications. Designs have been developed for both a 21" diameter and a larger diameter (LD) AUV. These fuel cell systems occupy a very small portion of the overall energy system, allowing most of the system volume to be used for the reactants. The fuel cell systems have been optimized to use reactants efficiently with high stack efficiency and low parasitic losses. The resulting compact, highly efficient fuel cell system provides exceptional reactant utilization and energy density. Key design variables and supporting test data are presented. Future development activities are described.

Multiple Ion Binding Equilibria, Reaction Kinetics, and Thermodynamics in Dynamic Models of Biochemical Pathways

PubMed Central

Vinnakota, Kalyan C.; Wu, Fan; Kushmerick, Martin J.; Beard, Daniel A.

2009-01-01

The operation of biochemical systems in vivo and in vitro is strongly influenced by complex interactions between biochemical reactants and ions such as H+, Mg2+, K+, and Ca2+. These are important second messengers in metabolic and signaling pathways that directly influence the kinetics and thermodynamics of biochemical systems. Herein we describe the biophysical theory and computational methods to account for multiple ion binding to biochemical reactants and demonstrate the crucial effects of ion binding on biochemical reaction kinetics and thermodynamics. In simulations of realistic systems, the concentrations of these ions change with time due to dynamic buffering and competitive binding. In turn, the effective thermodynamic properties vary as functions of cation concentrations and important environmental variables such as temperature and overall ionic strength. Physically realistic simulations of biochemical systems require incorporating all of these phenomena into a coherent mathematical description. Several applications to physiological systems are demonstrated based on this coherent simulation framework. PMID:19216922

Combustion of Na 2B 4O 7 + Mg + C to synthesis B 4C powders

NASA Astrophysics Data System (ADS)

Guojian, Jiang; Jiayue, Xu; Hanrui, Zhuang; Wenlan, Li

2009-09-01

Boron carbide powder was fabricated by combustion synthesis (CS) method directly from mixed powders of borax (Na 2B 4O 7), magnesium (Mg) and carbon. The adiabatic temperature of the combustion reaction of Na 2B 4O 7 + 6 Mg + C was calculated. The control of the reactions was achieved by selecting reactant composition, relative density of powder compact and gas pressure in CS reactor. The effects of these different influential factors on the composition and morphologies of combustion products were investigated. The results show that, it is advantageous for more Mg/Na 2B 4O 7 than stoichiometric ratio in Na 2B 4O 7 + Mg + C system and high atmosphere pressure in the CS reactor to increase the conversion degree of reactants to end product. The final product with the minimal impurities' content could be fabricated at appropriate relative density of powder compact. At last, boron carbide without impurities could be obtained after the acid enrichment and distilled water washing.

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

State-to-State Mode Specificity: Energy Sequestration and Flow Gated by Transition State.

PubMed

Zhao, Bin; Sun, Zhigang; Guo, Hua

2015-12-23

Energy flow and sequestration at the state-to-state level are investigated for a prototypical four-atom reaction, H2 + OH → H + H2O, using a transition-state wave packet (TSWP) method. The product state distribution is found to depend strongly on the reactant vibrational excitation, indicating mode specificity at the state-to-state level. From a local-mode perspective, it is shown that the vibrational excitation of the H2O product derives from two different sources, one attributable to the energy flow along the reaction coordinate into the newly formed OH bond and the other due to the sequestration of the vibrational energy in the OH spectator moiety during the reaction. The analysis provided a unified interpretation of some seemingly contradicting experimental observations. It is further shown that the transfer of vibrational energy from the OH reactant to H2O product is gated by the transition state, accomplished coherently by multiple TSWPs with the corresponding OH vibrational excitation.

Analysis and Test of a Proton Exchange Membrane Fuel Cell Power System for Space Power Applications

NASA Technical Reports Server (NTRS)

Vasquez, Arturo; Varanauski, Donald; Clark, Robert, Jr.

2000-01-01

An effort is underway to develop a prototype Proton Exchange Membrane (PEM) Fuel Cell breadboard system for fuhlre space applications. This prototype will be used to develop a comprehensive design basis for a space-rated PEM fuel cell powerplant. The prototype system includes reactant pressure regulators, ejector-based reactant pumps, a 4-kW fuel cell stack and cooling system, and a passive, membranebased oxygen / water separator. A computer model is being developed concurrently to analytically predict fluid flow in the oxidant reactant system. Fuel cells have historically played an important role in human-rated spacecraft. The Gemini and Apollo spacecraft used fuel cells for vehicle electrical power. The Space Shuttle currently uses three Alkaline Fuel Cell Powerplants (AFCP) to generate all of the vehicle's 15-20kW electrical power. Engineers at the Johnson Space Center have leveraged off the development effort ongoing in the commercial arena to develop PEM fuel cel ls for terrestrial uses. The prototype design originated from efforts to develop a PEM fuel cell replacement for the current Space Shuttle AFCP' s. In order to improve on the life and an already excellent hi storical record of reliability and safety, three subsystems were focused on. These were the fuel cell stack itself, the reactant circulation devices, and reactant / product water separator. PEM fuel cell stack performance is already demonstrating the potential for greater than four times the useful life of the current Shuttle's AFCP. Reactant pumping for product water removal has historically been accomplished with mechanical pumps. Ejectors offer an effective means of reactant pumping as well as the potential for weight reduction, control simplification, and long life. Centrifugal water separation is used on the current AFCP. A passive, membrane-based water separator offers compatibility with the micro-gravity environment of space, and the potential for control simplification, elimination of moving parts in an oxygen environment, and long life. The prototype system has been assembled from components that have previously been tested and evaluated at the component level. Preliminary data obtained from tests performed with the prototype system, as well as other published data, has been used to validate the analytical component models. These components have been incorporated into an integrated oxidant fluid system model. Results obtained from both the performance tests and the analytical model are presented.

Fast quench reactor and method

DOEpatents

Detering, B.A.; Donaldson, A.D.; Fincke, J.R.; Kong, P.C.

1998-05-12

A fast quench reactor includes a reactor chamber having a high temperature heating means such as a plasma torch at its inlet and a restrictive convergent-divergent nozzle at its outlet end. Reactants are injected into the reactor chamber. The resulting heated gaseous stream is then rapidly cooled by passage through the nozzle. This ``freezes`` the desired end product(s) in the heated equilibrium reaction stage. 7 figs.

The effect of V/III ratio on the morphology and structure of GaAs nanowires by MOCVD

NASA Astrophysics Data System (ADS)

Liu, Yan; Peng, Yan; Guo, Jingwei; La, Dongsheng; Xu, Zhaopeng

2018-05-01

In this paper, GaAs nanowires with different V/III ratios (70, 140, 280 and 560) were vertically grown from bottom to top on GaAs substrates by using metal organic chemical vapor deposition based on gold assisted vapor-liquid-solid mechanism. It is found that the growth rate of nanowires is inversely proportional to their V/III ratio. And the V/III ratio can also change nanowire growth type. For the nanowire with small V/III ratios (≤280), the reactants are most from those atoms merged in the catalyst. But, for the nanowire with V/III ratio 560, the contribution mainly comes from the diffusions of atoms pyrolyzed on the surface of the nanowire and the substrate. A shrunken neck under the catalyst is observed in TEM characterizations. These results will provide a theoretical basis for potential practical applications of nanowire-based devices.

Space Electrochemical Research and Technology

NASA Technical Reports Server (NTRS)

Wilson, Richard M. (Compiler)

1996-01-01

Individual papers presented at the conference address the following topics: development of a micro-fiber nickel electrode for nickel-hydrogen cell, high performance nickel electrodes for space power application, bending properties of nickel electrodes for nickel-hydrogen batteries, effect of KOH concentration and anions on the performance of a Ni-H2 battery positive plate, advanced dependent pressure vessel nickel hydrogen spacecraft cell and battery design, electrolyte management considerations in modern nickel hydrogen and nickel cadmium cell and battery design, a novel unitized regenerative proton exchange membrane fuel cell, fuel cell systems for first lunar outpost - reactant storage options, the TMI regenerable solid oxide fuel cell, engineering development program of a closed aluminum-oxygen semi-cell system for an unmanned underwater vehicle, SPE OBOGS on-board oxygen generating system, hermetically sealed aluminum electrolytic capacitor, sol-gel technology and advanced electrochemical energy storage materials, development of electrochemical supercapacitors for EMA applications, and high energy density electrolytic capacitor.

Application of physical adsorption thermodynamics to heterogeneous chemistry on polar stratospheric clouds

NASA Technical Reports Server (NTRS)

Elliott, Scott; Turco, Richard P.; Toon, Owen B.; Hamill, Patrick

1991-01-01

Laboratory isotherms for the binding of several nonheterogeneously active atmospheric gases and for HCl to water ice are translated into adsorptive equilibrium constants and surface enthalpies. Extrapolation to polar conditions through the Clausius Clapeyron relation yields coverage estimates below the percent level for N2, Ar, CO2, and CO, suggesting that the crystal faces of type II stratospheric cloud particles may be regarded as clean with respect to these species. For HCl, and perhaps HF and HNO3, estimates rise to several percent, and the adsorbed layer may offer acid or proton sources alternate to the bulk solid for heterogeneous reactions with stratospheric nitrates. Measurements are lacking for many key atmospheric molecules on water ice, and almost entirely for nitric acid trihydrate as substrate. Adsorptive equilibria enter into gas to particle mass flux descriptions, and the binding energy determines rates for desorption of, and encounter between, potential surface reactants.

Pilot scale evaluation of the BABIU process--upgrading of landfill gas or biogas with the use of MSWI bottom ash.

PubMed

Mostbauer, P; Lombardi, L; Olivieri, T; Lenz, S

2014-01-01

Biogas or landfill gas can be converted to a high-grade gas rich in methane with the use of municipal solid waste incineration bottom ash as a reactant for fixation of CO2 and H2S. In order to verify results previously obtained at a laboratory scale with 65-90 kg of bottom ash (BA), several test runs were performed at a pilot scale, using 500-1000 kg of bottom ash and up to 9.2 Nm(3)/h real landfill gas from a landfill in the Tuscany region (Italy). The input flow rate was altered. The best process performance was observed at a input flow rate of 3.7 Nm(3)/(htBA). At this flow rate, the removal efficiencies for H2S were approximately 99.5-99%. Copyright © 2013 Elsevier Ltd. All rights reserved.

Chemical vapor deposition of mullite coatings

DOEpatents

Sarin, Vinod; Mulpuri, Rao

1998-01-01

This invention is directed to the creation of crystalline mullite coatings having uniform microstructure by chemical vapor deposition (CVD). The process comprises the steps of establishing a flow of reactants which will yield mullite in a CVD reactor, and depositing a crystalline coating from the reactant flow. The process will yield crystalline coatings which are dense and of uniform thickness.

Spectral analysis and DFT computations of the hydrogen bonded complex between 2,6-diaminopyridine with 2,6-dichloro-4-nitrophenol in different solvents

NASA Astrophysics Data System (ADS)

Al-Ahmary, Khairia M.; Soliman, Saied M.; Habeeb, Moustafa M.; Al-Obidan, Areej H.

2017-09-01

New hydrogen bonded complex between 2,6-dichloro-4-nitrophenol (DCNP), proton donor with the proton acceptor 2,6-diaminopyridine (DAP) has been synthesized and characterized in solution and solid state by different spectroscopic techniques. Electronic spectra were used to identify the novel proton transfer complex through appearance of new absorption bands in acetonitrile (CH3CN), methanol (CH3OH) and mixture composed from 1:1 methanol and acetonitrile (AN-Me). The complex stoichiometry was determined to be 1:1 by job's method and photometric titrations. The formation constant was determined by applying minimum-maximum absorbances method where it reached high values confirming the complex high stability. A spectroscopic method for determining DAP was presented and validated statistically. The solid complex was characterized by elemental analysis, infrared and 1H NMR studies where the hydrogen bonded reaction occurs between the phenolic OH with the pyridine ring nitrogen as well as one amino group of DNP. The density functional theory DFT (B3LYP) method has been used to energy optimization of the reactants and complex in the ground state using two basis sets 6-31G(d) and 6-31 G+(d,p). The first one led to energy optimized structure through bifurcated hydrogen bond between OH of DCNP with the ring nitrogen and one amino group of DAP with optimization energy -1998.7 Hartree. The second one gave an optimized structure thought hydrogen bonding between OH and one amino group with lowered optimization energy -2018.1 Hartree. Hence, the experimental results will be simulated with the most stable one at DFT/B3LYB 6-31G+ (d,p). The most reactive electrophilic and nucleophilic sites of DCNP and DAP were predicted using the molecular electrostatic potential. The theoretical electronic spectra in the gas phase and the investigated solvents were calculated at TD-DFT/B3LYP 6-31G+ (d,p) and compared with measured electronic spectra where a satisfactory results have been obtained. An important aim of this work is analysis of the interaction energies between the filled natural bond orbitals (NBOs) and the empty ones in order to shed the light on the ease of electron delocalization among bonds in the novel hydrogen bonded complex.

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.

Uranium Isotope Fractionation during Oxidation of Dissolved U(iv) and Synthetic Solid UO2

NASA Astrophysics Data System (ADS)

Wang, X.; Johnson, T. M.; Lundstrom, C. C.

2013-12-01

U isotopes (238U/235U) show promise as a tool for environmental monitoring of U contamination as well as a proxy for paleo-redox conditions. However, the isotopic fractionation mechanisms of U are still poorly understood. In groundwater systems, U(VI), a mobile contaminant, can be reduced to immobile U(IV) and thus remediated. Previous work shows that 238U/235U of the remaining U(VI) changes with the extent of reduction. Therefore, U(VI) isotope composition in groundwater can potentially be used to detect and perhaps quantify the extent of reduction. However, knowing if isotopic fractionation occurs during U(IV) oxidation is equally important. First, the reduced U(IV) (either solid or as dissolved organic complexes) potentially can be reoxidized to U(VI). If isotope fractionation occurs during oxidation, it would complicate the use of U isotope composition as a monitoring technique. Further, in natural weathering processes, U(IV) minerals are oxidized to form dissolved U(VI), which is carried to rivers and eventually to the ocean and deposited in marine sediments. The weathering cycle is thus sensitive to redox conditions, meaning the sedimentary U isotope record may serve as a paleoredox indicator, provided U isotope fractionation during oxidation and reduction are well known. We conducted experiments oxidizing 2 different U(IV) species by O2 and measuring isotopic fractionation factors. In one experiment, dissolved U(IV) in 0.1 N HCl (pH 1) was oxidized by entrained air. As oxidation proceeds at pH 1, the remaining dissolved U(IV) becomes progressively enriched in 238U in a linear trend, while the product U(VI) paralleled, but was offset to 1.0‰ lighter in 238U/235U. This linear progression of both remaining reactant and product suggests equilibrium fractionation during oxidation of dissolved U(IV) by O2. A second experiment oxidized synthetic, solid UO2 (in 20 mM NaHCO3, pH 7) with entrained air. The oxidative fractionation is very weak in this case with product U(VI) ~0.1‰ heavier than the remaining UO2. We attribute the lack of strong fractionation during oxidation of solid UO2 to a 'rind effect', where the surface layer must be completely oxidized before the next layer is exposed to oxidant. Hence, nearly complete, congruent conversion of each layer of U(IV) to U(VI) results in minimal isotope fractionation. A small amount of transient fractionation probably occurs initially, but this is quickly negated as the surface becomes isotopically fractionated. Interestingly, our measured ~0.1‰ U isotope fractionation during oxidation of solid U(IV) agrees with the natural observation that 238U/235U ratios in river water (mainly U(VI)) are ~0.1‰ greater than those in fresh continental rocks (primarily U(IV) minerals). Application of these results to natural settings should be done with caution, however. Oxidation of natural uraninite in continental rocks is a much slower process. If the U(VI) product and the U(IV) reactant remain in contact for long periods of time (e.g., months), they may evolve toward isotopic equilibrium. Measurements of 238U/235U in various natural weathering environments should be undertaken to examine this idea.

Experimental and numerical analysis of parallel reactant flow and transverse mixing with mineral precipitation in homogeneous and heterogeneous porous media

DOE PAGES

Fox, Don T.; Guo, Luanjing; Fujita, Yoshiko; ...

2015-12-17

Formation of mineral precipitates in the mixing interface between two reactant solutions flowing in parallel in porous media is governed by reactant mixing by diffusion and dispersion and is coupled to changes in porosity/permeability due to precipitation. The spatial and temporal distribution of mixing-dependent precipitation of barium sulfate in porous media was investigated with side-by-side injection of barium chloride and sodium sulfate solutions in thin rectangular flow cells packed with quartz sand. The results for homogeneous sand beds were compared to beds with higher or lower permeability inclusions positioned in the path of the mixing zone. In the homogeneous andmore » high permeability inclusion experiments, BaSO 4 precipitate (barite) formed in a narrow deposit along the length and in the center of the solution–solution mixing zone even though dispersion was enhanced within, and downstream of, the high permeability inclusion. In the low permeability inclusion experiment, the deflected BaSO 4 precipitation zone broadened around one side and downstream of the inclusion and was observed to migrate laterally toward the sulfate solution. A continuum-scale fully coupled reactive transport model that simultaneously solves the nonlinear governing equations for fluid flow, transport of reactants and geochemical reactions was used to simulate the experiments and provide insight into mechanisms underlying the experimental observations. Lastly, migration of the precipitation zone in the low permeability inclusion experiment could be explained by the coupling effects among fluid flow, reactant transport and localized mineral precipitation reaction.« less

Carbon deposition and sulfur poisoning during CO2 electrolysis in nickel-based solid oxide cell electrodes

NASA Astrophysics Data System (ADS)

Skafte, Theis Løye; Blennow, Peter; Hjelm, Johan; Graves, Christopher

2018-01-01

Reduction of CO2 to CO and O2 in the solid oxide electrolysis cell (SOEC) has the potential to play a crucial role in closing the CO2 loop. Carbon deposition in nickel-based cells is however fatal and must be considered during CO2 electrolysis. Here, the effect of operating parameters is investigated systematically using simple current-potential experiments. Due to variations of local conditions, it is shown that higher current density and lower fuel electrode porosity will cause local carbon formation at the electrochemical reaction sites despite operating with a CO outlet concentration outside the thermodynamic carbon formation region. Attempts at mitigating the issue by coating the composite nickel/yttria-stabilized zirconia electrode with carbon-inhibiting nanoparticles and by sulfur passivation proved unsuccessful. Increasing the fuel electrode porosity is shown to mitigate the problem, but only to a certain extent. This work shows that a typical SOEC stack converting CO2 to CO and O2 is limited to as little as 15-45% conversion due to risk of carbon formation. Furthermore, cells operated in CO2-electrolysis mode are poisoned by reactant gases containing ppb-levels of sulfur, in contrast to ppm-levels for operation in fuel cell mode.

Numerical analysis on effect of aspect ratio of planar solid oxide fuel cell fueled with decomposed ammonia

NASA Astrophysics Data System (ADS)

Tan, Wee Choon; Iwai, Hiroshi; Kishimoto, Masashi; Brus, Grzegorz; Szmyd, Janusz S.; Yoshida, Hideo

2018-04-01

Planar solid oxide fuel cells (SOFCs) with decomposed ammonia are numerically studied to investigate the effect of the cell aspect ratio. The ammonia decomposer is assumed to be located next to the SOFCs, and the heat required for the endothermic decomposition reaction is supplied by the thermal radiation from the SOFCs. Cells with aspect ratios (ratios of the streamwise length to the spanwise width) between 0.130 and 7.68 are provided with the reactants at a constant mass flow rate. A parametric study is conducted by varying the cell temperature and fuel utility factor to investigate their effects on the cell performance in terms of the voltage efficiency. The effect of the heat supply to the ammonia decomposer is also studied. The developed model shows good agreement, in terms of the current-voltage curve, with the experimental data obtained from a short stack without parameter tuning. The simulation study reveals that the cell with the highest aspect ratio achieves the highest performance under furnace operation. On the other hand, the 0.750 aspect ratio cell with the highest voltage efficiency of 0.67 is capable of thermally sustaining the ammonia decomposers at a fuel utility of 0.80 using the thermal radiation from both sidewalls.

Immunoassay of paralytic shellfish toxins by moving magnetic particles in a stationary liquid-phase lab-on-a-chip.

PubMed

Kim, Myoung-Ho; Choi, Suk-Jung

2015-04-15

In this study, we devised a stationary liquid-phase lab-on-a-chip (SLP LOC), which was operated by moving solid-phase magnetic particles in the stationary liquid phase. The SLP LOC consisted of a sample chamber to which a sample and reactants were added, a detection chamber containing enzyme substrate solution, and a narrow channel connecting the two chambers and filled with buffer. As a model system, competitive immunoassays of saxitoxin (STX), a paralytic shellfish toxin, were conducted in the SLP LOC using protein G-coupled magnetic particles (G-MPs) as the solid phase. Anti-STX antibodies, STX-horseradish peroxidase conjugate, G-MPs, and a STX sample were added to the sample chamber and reacted by shaking. While liquids were in the stationary state, G-MPs were transported from the sample chamber to the detection chamber by moving a magnet below the LOC. After incubation to allow the enzymatic reaction to occur, the absorbance of the detection chamber solution was found to be reciprocally related to the STX concentration of the sample. Thus, the SLP LOC may represent a novel, simple format for point-of-care testing applications of enzyme-linked immunosorbent assays by eliminating complicated liquid handling steps. Copyright © 2014 Elsevier B.V. All rights reserved.

Characterization of Cr poisoning in a solid oxide fuel cell cathode using a high-energy x-ray microbeam.

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

Liu, D. J.; Almer, J.; Cruse, T.

2010-01-01

A key feature of planar solid oxide fuel cells (SOFCs) is the feasibility of using metallic interconnects made of high temperature ferritic stainless steels, which reduce system cost while providing excellent electric conductivity. Such interconnects, however, contain high levels of chromium, which has been found to be associated with SOFC cathode performance degradation at SOFC operating temperatures; a phenomenon known as Cr poisoning. Here, we demonstrate an accurate measurement of the phase and concentration distributions of Cr species in a degraded SOFC, as well as related properties including deviatoric strain, integrated porosity, and lattice parameter variation, using high energy microbeammore » X-ray diffraction and radiography. We unambiguously identify (MnCr){sub 3}O{sub 4} and Cr{sub 2}O{sub 3} as the two main contaminant phases and find that their concentrations correlate strongly with the cathode layer composition. Cr{sub 2}O{sub 3} deposition within the active cathode region reduces porosity and produces compressive residual strains, which hinders the reactant gas percolation and can cause structural breakdown of the SOFC cathode. The information obtained through this study can be used to better understand the Cr-poisoning mechanism and improve SOFC design.« less

System for exchange of hydrogen between liquid and solid phases

DOEpatents

Reilly, James J.; Grohse, Edward W.; Johnson, John R.; Winsche, deceased, Warren E.

1988-01-01

The reversible reaction M+x/2 H.sub.2 .rarw..fwdarw.MH.sub.x, wherein M is a reversible metal hydride former that forms a hydride MH.sub.x in the presence of H.sub.2, generally used to store and recall H.sub.2, is found to proceed under an inert liquid, thereby reducing contamination, providing better temperature control, providing in situ mobility of the reactants, and increasing flexibility in process design. Thus, a slurry of particles of a metal hydride former with an inert solvent is subjected to a temperature and pressure controlled atmosphere containing H.sub.2, to store hydrogen and to release previously stored hydrogen. The direction of the flow of the H.sub.2 through the liquid is dependent upon the H.sub.2 pressure in the gas phase at a given temperature. When the actual H.sub.2 pressure is above the equilibrium absorption pressure of the respective hydride the reaction proceeds to the right, i.e., the metal hydride is formed and hydrogen is stored in the solid particles. When the actual pressure in the gas phase is below the equilibrium dissociation pressure of the respective hydride the reaction proceeds to the left, the metal hydride is decomposed and hydrogen is released into the gas phase.

System for exchange of hydrogen between liquid and solid phases

DOEpatents

Reilly, J.J.; Grohse, E.W.; Johnson, J.R.; Winsche, W.E.

1985-02-22

The reversible reaction M + x/2 H/sub 2/ reversible MH/sub x/, wherein M is a reversible metal hydride former that forms a hydride MH/sub x/ in the presence of H/sub 2/, generally used to store and recall H/sub 2/, is found to proceed under an inert liquid, thereby reducing contamination, providing better temperature control, providing in situ mobility of the reactants, and increasing flexibility in process design. Thus, a slurry of particles of a metal hydride former with an inert solvent is subjected to a temperature and pressure controlled atmosphere containing H/sub 2/, to store hydrogen and to release previously stored hydrogen. The direction of the flow of the H/sub 2/ through the liquid is dependent upon the H/sub 2/ pressure in the gas phase at a given temperature. When the actual H/sub 2/ pressure is above the equilibrium absorption pressure of the respective hydride the reaction proceeds to the right, i.e., the metal hydride is formed and hydrogen is stored in the solid particle. When the actual pressure in the gas phase is below the equilibrium dissociation pressure of the respective hydride the reaction proceeds to the left, the metal hydride is decomposed and hydrogen is released into the gas phase.

Quantitative Evaluation of MDP-Ca Salt and DCPD after Application of an MDP-based One-step Self-etching Adhesive on Enamel and Dentin.

PubMed

Yokota, Yoko; Fujita, Kou Nakajima; Uchida, Ryoichiro; Aida, Etsuko; Aoki, Naoko Tabei; Aida, Masahiro; Nishiyama, Norihiro

To investigate the effects of an experimental 10-methacryloyloxydecyl dihydrogen phosphate (MDP)-based one-step self-etching adhesive (EX adhesive) applied to enamel and dentin on the production of calcium salt of MDP (MDP-Ca salt) and dicalcium phosphate dehydrate (DCPD) at various periods. The EX adhesive was prepared. Bovine enamel and dentin reactants were prepared by varying the application period of the EX adhesive: 0.5, 1, 5, 30, 60 and 1440 min. Enamel and dentin reactants were analyzed using x-ray diffraction and solid-state phosphorus-31 nuclear magnetic resonance (31P NMR). Curvefitting analyses of corresponding 31P NMR spectra were performed. Enamel and dentin developed several types of MDP-Ca salts and DCPDs with amorphous and crystalline phases throughout the application period. The predominant molecular species of MDP-Ca salt was determined as the monocalcium salt of the MDP monomer. Dentin showed a faster production rate and greater produced amounts of MDP-Ca salt than did enamel, since enamel showed a knee-point in the production rate of the MDP-Ca salt at the application period of 5 min. In contrast, enamel developed greater amounts of DCPD than did dentin and two types of DCPDs with different crystalline phases at application periods > 30 min. The amounts of MDP-Ca salt developed during the 30-s application of the EX adhesive on enamel and dentin were 7.3 times and 21.2 times greater than DCPD, respectively. The MDP-based one-step adhesive yielded several types of MDP-Ca salts and DCPD with an amorphous phase during the 30-s application period on enamel and dentin.

Highly Viscous States Affect the Browning of Atmospheric Organic Particulate Matter

PubMed Central

2018-01-01

Initially transparent organic particulate matter (PM) can become shades of light-absorbing brown via atmospheric particle-phase chemical reactions. The production of nitrogen-containing compounds is one important pathway for browning. Semisolid or solid physical states of organic PM might, however, have sufficiently slow diffusion of reactant molecules to inhibit browning reactions. Herein, organic PM of secondary organic material (SOM) derived from toluene, a common SOM precursor in anthropogenically affected environments, was exposed to ammonia at different values of relative humidity (RH). The production of light-absorbing organonitrogen imines from ammonia exposure, detected by mass spectrometry and ultraviolet–visible spectrophotometry, was kinetically inhibited for RH < 20% for exposure times of 6 min to 24 h. By comparison, from 20% to 60% RH organonitrogen production took place, implying ammonia uptake and reaction. Correspondingly, the absorption index k across 280 to 320 nm increased from 0.012 to 0.02, indicative of PM browning. The k value across 380 to 420 nm increased from 0.001 to 0.004. The observed RH-dependent behavior of ammonia uptake and browning was well captured by a model that considered the diffusivities of both the large organic molecules that made up the PM and the small reactant molecules taken up from the gas phase into the PM. Within the model, large-molecule diffusivity was calculated based on observed SOM viscosity and evaporation. Small-molecule diffusivity was represented by the water diffusivity measured by a quartz-crystal microbalance. The model showed that the browning reaction rates at RH < 60% could be controlled by the low diffusivity of the large organic molecules from the interior region of the particle to the reactive surface region. The results of this study have implications for accurate modeling of atmospheric brown carbon production and associated influences on energy balance. PMID:29532020

Highly Viscous States Affect the Browning of Atmospheric Organic Particulate Matter.

PubMed

Liu, Pengfei; Li, Yong Jie; Wang, Yan; Bateman, Adam P; Zhang, Yue; Gong, Zhaoheng; Bertram, Allan K; Martin, Scot T

2018-02-28

Initially transparent organic particulate matter (PM) can become shades of light-absorbing brown via atmospheric particle-phase chemical reactions. The production of nitrogen-containing compounds is one important pathway for browning. Semisolid or solid physical states of organic PM might, however, have sufficiently slow diffusion of reactant molecules to inhibit browning reactions. Herein, organic PM of secondary organic material (SOM) derived from toluene, a common SOM precursor in anthropogenically affected environments, was exposed to ammonia at different values of relative humidity (RH). The production of light-absorbing organonitrogen imines from ammonia exposure, detected by mass spectrometry and ultraviolet-visible spectrophotometry, was kinetically inhibited for RH < 20% for exposure times of 6 min to 24 h. By comparison, from 20% to 60% RH organonitrogen production took place, implying ammonia uptake and reaction. Correspondingly, the absorption index k across 280 to 320 nm increased from 0.012 to 0.02, indicative of PM browning. The k value across 380 to 420 nm increased from 0.001 to 0.004. The observed RH-dependent behavior of ammonia uptake and browning was well captured by a model that considered the diffusivities of both the large organic molecules that made up the PM and the small reactant molecules taken up from the gas phase into the PM. Within the model, large-molecule diffusivity was calculated based on observed SOM viscosity and evaporation. Small-molecule diffusivity was represented by the water diffusivity measured by a quartz-crystal microbalance. The model showed that the browning reaction rates at RH < 60% could be controlled by the low diffusivity of the large organic molecules from the interior region of the particle to the reactive surface region. The results of this study have implications for accurate modeling of atmospheric brown carbon production and associated influences on energy balance.

An Integrated Qualitative and Quantitative Biochemical Model Learning Framework Using Evolutionary Strategy and Simulated Annealing.

PubMed

Wu, Zujian; Pang, Wei; Coghill, George M

2015-01-01

Both qualitative and quantitative model learning frameworks for biochemical systems have been studied in computational systems biology. In this research, after introducing two forms of pre-defined component patterns to represent biochemical models, we propose an integrative qualitative and quantitative modelling framework for inferring biochemical systems. In the proposed framework, interactions between reactants in the candidate models for a target biochemical system are evolved and eventually identified by the application of a qualitative model learning approach with an evolution strategy. Kinetic rates of the models generated from qualitative model learning are then further optimised by employing a quantitative approach with simulated annealing. Experimental results indicate that our proposed integrative framework is feasible to learn the relationships between biochemical reactants qualitatively and to make the model replicate the behaviours of the target system by optimising the kinetic rates quantitatively. Moreover, potential reactants of a target biochemical system can be discovered by hypothesising complex reactants in the synthetic models. Based on the biochemical models learned from the proposed framework, biologists can further perform experimental study in wet laboratory. In this way, natural biochemical systems can be better understood.

Design, fabrication and performance of a mixed-reactant membraneless micro direct methanol fuel cell stack

NASA Astrophysics Data System (ADS)

Abrego-Martínez, J. C.; Moreno-Zuria, A.; Cuevas-Muñiz, F. M.; Arriaga, L. G.; Sun, Shuhui; Mohamedi, Mohamed

2017-12-01

In the present work, we report the design, fabrication and evaluation of a membraneless mixed-reactant and air-breathing microfluidic direct methanol fuel cell (ML-μDMFC) stack operated in passive mode. The operation under mixed-reactant conditions was achieved by using a highly methanol-tolerant Ag/Pt/CP cathode with ultra-low Pt loading in alkaline medium. Prior to the fabrication of the stack, a flow simulation was made in order to study the behavior of the reactants stream in the microchannel through the 2 cells. Subsequently, the device was tested in passive mode using a mixture of 5 M MeOH +0.5 M KOH. The results showed that by connecting the 2 cells in series, it is possible to effectively double the voltage of a single ML-μDMFC, as well as increasing the absolute power by 75% with practically no cost increase. The stack was capable of operate continuously for more than 2 h with a single charge of 40 μL, producing an OCV of 0.89 V and a maximum power density of 3.33 mW mgPt-1. Additionally, the device exhibited good stability throughout a 10 h test.

Towards operating direct methanol fuel cells with highly concentrated fuel

NASA Astrophysics Data System (ADS)

Zhao, T. S.; Yang, W. W.; Chen, R.; Wu, Q. X.

A significant advantage of direct methanol fuel cells (DMFCs) is the high specific energy of the liquid fuel, making it particularly suitable for portable and mobile applications. Nevertheless, conventional DMFCs have to be operated with excessively diluted methanol solutions to limit methanol crossover and the detrimental consequences. Operation with diluted methanol solutions significantly reduces the specific energy of the power pack and thereby prevents it from competing with advanced batteries. In view of this fact, there exists a need to improve conventional DMFC system designs, including membrane electrode assemblies and the subsystems for supplying/removing reactants/products, so that both the cell performance and the specific energy can be simultaneously maximized. This article provides a comprehensive review of past efforts on the optimization of DMFC systems that operate with concentrated methanol. Based on the discussion of the key issues associated with transport of the reactants/products, the strategies to manage the supply/removal of the reactants/products in DMFC operating with highly concentrated methanol are identified. With these strategies, the possible approaches to achieving the goal of concentrated fuel operation are then proposed. Past efforts in the management of the reactants/products for implementing each of the approaches are also summarized and reviewed.

Novel high explosive compositions

DOEpatents

Perry, D.D.; Fein, M.M.; Schoenfelder, C.W.

1968-04-16

This is a technique of preparing explosive compositions by the in-situ reaction of polynitroaliphatic compounds with one or more carboranes or carborane derivatives. One or more polynitroaliphatic reactants are combined with one or more carborane reactants in a suitable container and mixed to a homogeneous reaction mixture using a stream of inert gas or conventional mixing means. Ordinarily the container is a fissure, crack, or crevice in which the explosive is to be implanted. The ratio of reactants will determine not only the stoichiometry of the system, but will effect the quality and quantity of combustion products, the explosive force obtained as well as the impact sensitivity. The test values can shift with even relatively slight changes or modifications in the reaction conditions. Eighteen illustrative examples accompany the disclosure. (46 claims)

Chemical-Vapor Deposition Of Silicon Carbide

NASA Technical Reports Server (NTRS)

Cagliostro, D. E.; Riccitiello, S. R.; Ren, J.; Zaghi, F.

1993-01-01

Report describes experiments in chemical-vapor deposition of silicon carbide by pyrolysis of dimethyldichlorosilane in hydrogen and argon carrier gases. Directed toward understanding chemical-kinetic and mass-transport phenomena affecting infiltration of reactants into, and deposition of SiC upon, fabrics. Part of continuing effort to develop method of efficient and more nearly uniform deposition of silicon carbide matrix throughout fabric piles to make improved fabric/SiC-matrix composite materials.

Self-assembly of a superparamagnetic raspberry-like silica/iron oxide nanocomposite using epoxy-amine coupling chemistry.

PubMed

Cano, Manuel; de la Cueva-Méndez, Guillermo

2015-02-28

The fabrication of colloidal nanocomposites would benefit from controlled hetero-assembly of ready-made particles through covalent bonding. Here we used epoxy-amine coupling chemistry to promote the self-assembly of superparamagnetic raspberry-like nanocomposites. This adaptable method induced the covalent attachment of iron oxide nanoparticles sparsely coated with amine groups onto epoxylated silica cores in the absence of other reactants.

Catalytic and reactive polypeptides and methods for their preparation and use

DOEpatents

Schultz, Peter

1994-01-01

Catalytic and reactive polypeptides include a binding site specific for a reactant or reactive intermediate involved in a chemical reaction of interest. The polypeptides further include at least one active functionality proximate the binding site, where the active functionality is capable of catalyzing or chemically participating in the chemical reaction in such a way that the reaction rate is enhanced. Methods for preparing the catalytic peptides include chemical synthesis, site-directed mutagenesis of antibody and enzyme genes, covalent attachment of the functionalities through particular amino acid side chains, and the like.

Method of producing a high pressure gas

DOEpatents

Bingham, Dennis N.; Klingler, Kerry M.; Zollinger, William T.

2006-07-18

A method of producing a high pressure gas is disclosed and which includes providing a container; supplying the container with a liquid such as water; increasing the pressure of the liquid within the container; supplying a reactant composition such as a chemical hydride to the liquid under pressure in the container and which chemically reacts with the liquid to produce a resulting high pressure gas such as hydrogen at a pressure of greater than about 100 pounds per square inch of pressure; and drawing the resulting high pressure gas from the container.

Non-OH chemistry in oxidation flow reactors for the study of atmospheric chemistry systematically examined by modeling

NASA Astrophysics Data System (ADS)

Peng, Z.; Day, D. A.; Ortega, A. M.; Palm, B. B.; Hu, W. W.; Stark, H.; Li, R.; Tsigaridis, K.; Brune, W. H.; Jimenez, J. L.

2015-09-01

Oxidation flow reactors (OFRs) using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D), O(3P), and O3. In this study, we investigate the relative importance of other reactants to OH for the fate of reactant species in OFR under a wide range of conditions via box modeling. The relative importance of non-OH species is less sensitive to UV light intensity than to relative humidity (RH) and external OH reactivity (OHRext), as both non-OH reactants and OH scale roughly proportional to UV intensity. We show that for field studies in forested regions and also the urban area of Los Angeles, reactants of atmospheric interest are predominantly consumed by OH. We find that O(1D), O(3P), and O3 have relative contributions to VOC consumption that are similar or lower than in the troposphere. The impact of O atoms can be neglected under most conditions in both OFR and troposphere. Under "pathological OFR conditions" of low RH and/or high OHRext, the importance of non-OH reactants is enhanced because OH is suppressed. Some biogenics can have substantial destructions by O3, and photolysis at non-tropospheric wavelengths (185 and 254 nm) may also play a significant role in the degradation of some aromatics under pathological conditions. Working under low O2 with the OFR185 mode allows OH to completely dominate over O3 reactions even for the biogenic species most reactive with O3. Non-tropospheric VOC photolysis may have been a problem in some laboratory and source studies, but can be avoided or lessened in future studies by diluting source emissions and working at lower precursor concentrations in lab studies, and by humidification. SOA photolysis is shown to be insignificant for most functional groups, except for nitrates and especially aromatics, which may be photolyzed at high UV flux settings. Our work further establishes the OFR's usefulness as a tool to study atmospheric chemistry and enables better experiment design and interpretation, as well as improved future reactor design.

Non-OH Chemistry in Oxidation Flow Reactors for the Study of Atmospheric Chemistry Systematically Examined by Modeling

NASA Technical Reports Server (NTRS)

Peng, Zhe; Day, Douglas A.; Ortega, Amber M.; Palm, Brett B.; Hu, Weiwei; Stark, Harald; Li, Rui; Tsigaridis, Kostas; Brune, William H.; Jimenez, Jose L.

2016-01-01

Oxidation flow reactors (OFRs) using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D), O(3P), and O3. In this study, we investigate the relative importance of other reactants to OH for the fate of reactant species in OFR under a wide range of conditions via box modeling. The relative importance of non-OH species is less sensitive to UV light intensity than to relative humidity (RH) and external OH reactivity (OHRext), as both non-OH reactants and OH scale roughly proportional to UV intensity. We show that for field studies in forested regions and also the urban area of Los Angeles, reactants of atmospheric interest are predominantly consumed by OH. We find that O(1D), O(3P), and O3 have relative contributions to VOC consumption that are similar or lower than in the troposphere. The impact of O atoms can be neglected under most conditions in both OFR and troposphere. Under pathological OFR conditions of low RH and/or high OHRext, the importance of non-OH reactants is enhanced because OH is suppressed. Some biogenics can have substantial destructions by O3, and photolysis at non-tropospheric wavelengths (185 and 254 nm) may also play a significant role in the degradation of some aromatics under pathological conditions. Working under low O2 with the OFR185 mode allows OH to completely dominate over O3 reactions even for the biogenic species most reactive with O3. Non-tropospheric VOC photolysis may have been a problem in some laboratory and source studies, but can be avoided or lessened in future studies by diluting source emissions and working at lower precursor concentrations in lab studies, and by humidification. SOA photolysis is shown to be insignificant for most functional groups, except for nitrates and especially aromatics, which may be photolyzed at high UV flux settings. Our work further establishes the OFR's usefulness as a tool to study atmospheric chemistry and enables better experiment design and interpretation, as well as improved future reactor design.

Accessible triple-phase boundary length: A performance metric to account for transport pathways in heterogeneous electrochemical materials

NASA Astrophysics Data System (ADS)

Nakajo, A.; Cocco, A. P.; DeGostin, M. B.; Peracchio, A. A.; Cassenti, B. N.; Cantoni, M.; Van herle, J.; Chiu, W. K. S.

2016-09-01

The performance of materials for electrochemical energy conversion and storage depends upon the number of electrocatalytic sites available for reaction and their accessibility by the transport of reactants and products. For solid oxide fuel/electrolysis cell materials, standard 3-D measurements such as connected triple-phase boundary (TPB) length and effective transport properties partially inform on how local geometry and network topology causes variability in TPB accessibility. A new measurement, the accessible TPB, is proposed to quantify these effects in detail and characterize material performance. The approach probes the reticulated pathways to each TPB using an analytical electrochemical fin model applied to a 3-D discrete representation of the heterogeneous structure provided by skeleton-based partitioning. The method is tested on artificial and real structures imaged by 3-D x-ray and electron microscopy. The accessible TPB is not uniform and the pattern varies depending upon the structure. Connected TPBs can be even passivated. The sensitivity to manipulations of the local 3-D geometry and topology that standard measurements cannot capture is demonstrated. The clear presence of preferential pathways showcases a non-uniform utilization of the 3-D structure that potentially affects the performance and the resilience to alterations due to degradation phenomena. The concepts presented also apply to electrochemical energy storage and conversion devices such as other types of fuel cells, electrolyzers, batteries and capacitors.

CdTe1-x S x (x  ⩽  0.05) thin films synthesized by aqueous solution deposition and annealing

NASA Astrophysics Data System (ADS)

Pruzan, Dennis S.; Hahn, Carina E.; Misra, Sudhajit; Scarpulla, Michael A.

2017-11-01

While CdS thin films are commonly deposited from aqueous solutions, CdTe thin films are extremely difficult to deposit directly from aqueous solution. In this work, we report on polycrystalline CdTe1-x S x thin films synthesized via deposition from aqueous precursor solutions followed by annealing treatments and on their physical properties. The deposition method uses spin-coating of alternating Cd2+ and Te2- aqueous solutions and rinse steps to allow formation of the films but to shear off excess reactants and poorly-bonded solids. Films are then annealed in the presence of CdCl2 as is commonly done for CdTe photovoltaic absorber layers deposited by any means. Scanning electron microscopy (SEM) reveals low void fractions and grain sizes up to 4 µm and x-ray diffraction (XRD) shows that the films are primarily cubic CdTe1-x S x (x  ⩽  0.05) with random crystallographic orientation. Optical transmission yields bandgap absorption consistent with a CdTe1-x S x dilute alloy and low-temperature photoluminescence (PL) consists of an emission band centered at 1.35 eV consistent with donor-acceptor pair (DAP) transitions in CdTe1-x S x . Together, the crystalline quality and PL yield from films produced by this method represent an important step towards electroless, ligand-free solution processed CdTe and related alloy thin films suitable for optoelectronic device applications such as thin film heterojunction or nanodipole-based photovoltaics.

Ti2Al(C, N) Solid Solution Reinforcing TiAl-Based Composites: Evolution of a Core-Shell Structure, Interfaces, and Mechanical Properties.

PubMed

Song, Xiaojie; Cui, Hongzhi; Han, Ye; Ding, Lei; Song, Qiang

2018-05-16

In this work, Ti 2 Al(C, N) solid solution with lamellar structure-enhanced TiAl matrix composites was synthesized by vacuum arc melting, using bulk g-C 3 N 4 , Ti, and Al powders as raw materials. The phases, microstructures, interfaces, and mechanical properties were investigated. MAX phase of Ti 2 Al(C, N) solid solution with lamellar structure was formed. During the melting process, first, C 3 N 4 reacted with Ti to form Ti(C, N) by Ti + C 3 N 4 → Ti(C, N). Then Ti 2 Al(C, N) was formed by a peritectic reaction of TiAl(l) + Ti(C, N)(s) → Ti 2 Al(C, N). C 3 N 4 is the single reactant that provides C and N simultaneously to final product of Ti 2 Al(C, N). The interfaces of TiAl//Ti 2 Al(C, N) and Ti 2 Al(C, N)//Ti(C, N) display perfect orientation relationships with low misfit values. The microhardness, compressive strength, and strain of best-performing TiAl-10 mol % Ti 2 Al(C, N) composite were improved by 45%, 55.7%, and 50% compared with the TiAl alloy, respectively. Uniformly distributed Ti 2 Al(C, N) and unreacted Ti(C, N) particles contributed to the grain refinement and reinforcement of the TiAl matrix. Laminated tearing, particle pull-out, and the crack-arresting of Ti 2 Al(C, N) are crucial for the improvement in compressive strength and plasticity of the composites.

Transport Reactor Facility

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

Berry, D.A.; Shoemaker, S.A.

1996-12-31

The Morgantown Energy Technology Center (METC) is currently evaluating hot gas desulfurization (HGD)in its on-site transport reactor facility (TRF). This facility was originally constructed in the early 1980s to explore advanced gasification processes with an entrained reactor, and has recently been modified to incorporate a transport riser reactor. The TRF supports Integrated Gasification Combined Cycle (IGCC) power systems, one of METC`s advanced power generation systems. The HGD subsystem is a key developmental item in reducing the cost and increasing the efficiency of the IGCC concept. The TRF is a unique facility with high-temperature, high-pressure, and multiple reactant gas composition capability.more » The TRF can be configured for reacting a single flow pass of gas and solids using a variety of gases. The gas input system allows six different gas inputs to be mixed and heated before entering the reaction zones. Current configurations allow the use of air, carbon dioxide, carbon monoxide, hydrogen, hydrogen sulfide, methane, nitrogen, oxygen, steam, or any mixture of these gases. Construction plans include the addition of a coal gas input line. This line will bring hot coal gas from the existing Fluidized-Bed Gasifier (FBG) via the Modular Gas Cleanup Rig (MGCR) after filtering out particulates with ceramic candle filters. Solids can be fed either by a rotary pocket feeder or a screw feeder. Particle sizes may range from 70 to 150 micrometers. Both feeders have a hopper that can hold enough solid for fairly lengthy tests at the higher feed rates, thus eliminating the need for lockhopper transfers during operation.« less