Structure-reactivity modeling using mixture-based representation of chemical reactions.

PubMed

Polishchuk, Pavel; Madzhidov, Timur; Gimadiev, Timur; Bodrov, Andrey; Nugmanov, Ramil; Varnek, Alexandre

2017-09-01

We describe a novel approach of reaction representation as a combination of two mixtures: a mixture of reactants and a mixture of products. In turn, each mixture can be encoded using an earlier reported approach involving simplex descriptors (SiRMS). The feature vector representing these two mixtures results from either concatenated product and reactant descriptors or the difference between descriptors of products and reactants. This reaction representation doesn't need an explicit labeling of a reaction center. The rigorous "product-out" cross-validation (CV) strategy has been suggested. Unlike the naïve "reaction-out" CV approach based on a random selection of items, the proposed one provides with more realistic estimation of prediction accuracy for reactions resulting in novel products. The new methodology has been applied to model rate constants of E2 reactions. It has been demonstrated that the use of the fragment control domain applicability approach significantly increases prediction accuracy of the models. The models obtained with new "mixture" approach performed better than those required either explicit (Condensed Graph of Reaction) or implicit (reaction fingerprints) reaction center labeling.

Etherification process

DOEpatents

Smith, L.A. Jr.; Hearn, D.; Jones, E.M. Jr.

1990-08-21

A liquid phase process is described for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled. 2 figs.

Reactor for exothermic reactions

DOEpatents

Smith, Jr., Lawrence A.; Hearn, Dennis; Jones, Jr., Edward M.

1993-01-01

A liquid phase process for oligomerization of C.sub.4 and C.sub.5 isoolefins or the etherification thereof with C.sub.1 to C.sub.6 alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120.degree. to 300.degree. F. Wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

Method for conducting exothermic reactions

DOEpatents

Smith, L. Jr.; Hearn, D.; Jones, E.M. Jr.

1993-01-05

A liquid phase process for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F. wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

Method for conducting exothermic reactions

DOEpatents

Smith, Jr., Lawrence; Hearn, Dennis; Jones, Jr., Edward M.

1993-01-01

A liquid phase process for oligomerization of C.sub.4 and C.sub.5 isoolefins or the etherification thereof with C.sub.1 to C.sub.6 alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120.degree. to 300.degree. F. wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

Reactor for exothermic reactions

DOEpatents

Smith, L.A. Jr.; Hearn, D.; Jones, E.M. Jr.

1993-03-02

A liquid phase process is described for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F. Wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

Oligomerization process

DOEpatents

Smith, L.A. Jr.; Hearn, D.; Jones, E.M. Jr.

1991-03-26

A liquid phase process is described for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled. 2 figures.

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.

Liquid injection plasma deposition method and apparatus

DOEpatents

Kong, P.C.; Watkins, A.D.

1999-05-25

A liquid injection plasma torch deposition apparatus for depositing material onto a surface of a substrate may comprise a plasma torch for producing a jet of plasma from an outlet nozzle. A plasma confinement tube having an inlet end and an outlet end and a central bore therethrough is aligned with the outlet nozzle of the plasma torch so that the plasma jet is directed into the inlet end of the plasma confinement tube and emerges from the outlet end of the plasma confinement tube. The plasma confinement tube also includes an injection port transverse to the central bore. A liquid injection device connected to the injection port of the plasma confinement tube injects a liquid reactant mixture containing the material to be deposited onto the surface of the substrate through the injection port and into the central bore of the plasma confinement tube. 8 figs.

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.

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.

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)

Ternary liquid mixtures control the multiplicity, shape and internal structure of emulsion droplets

NASA Astrophysics Data System (ADS)

Haase, Martin F.; Brujic, Jasna

2014-03-01

It is important to control the shape, internal structure and stability of emulsion droplets for drug delivery, biochemical assays, and the design of materials with novel physical properties. Successful methods involve the mechanical manipulation of the flow of oil in water using complex microfluidic devices to make multiple emulsions with a sequential introduction of specific reactants. Instead, here we show how the thermodynamics of immiscible liquid mixtures tailor emulsions using a single dripping instability. For example, the initial composition and choice of surfactant govern the multiplicity of concentric alternating oil and water layers inside the droplets. Stabilizing ternary droplets using nanoparticles gives rise to a plethora of shapes whose geometry is defined by the deformability of the shell and the flow rate. Another option is to incorporate lipids to the multiple emulsion droplet, which form vesicles upon expulsion of the inner water droplets. Depending on the number of initial water droplets, these vesicles eventually form complex hollow topologies, which can be used as junctions or scaffolds for the self-assembly of colloidal particles in the future.

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.

Effects of Doping and/or Atmosphere on the Electrical Conductivity of Li4Ti5O12

DTIC Science & Technology

2008-11-01

materials were ground with an alumina mortar and pestle with enough methanol to form a slurry. The dried and mixed reactant mixture was pelletized...N. V.; Chaban, N. G.; Petrov, K. I. Inorg. Mater. 1982, 18, 1066. 21. Hayashi, S.; Hatano, H. J. Ceram. Soc. Japan 1994,102, 378. 11 22...with an alumina mortar and pestle with enough methanol to form a slurry. The dried and mixed reactant mixture was pelletized and then heated at 800

System and process for biomass treatment

DOEpatents

Dunson, Jr., James B; Tucker, III, Melvin P; Elander, Richard T; Lyons, Robert C

2013-08-20

A system including an apparatus is presented for treatment of biomass that allows successful biomass treatment at a high solids dry weight of biomass in the biomass mixture. The design of the system provides extensive distribution of a reactant by spreading the reactant over the biomass as the reactant is introduced through an injection lance, while the biomass is rotated using baffles. The apparatus system to provide extensive assimilation of the reactant into biomass using baffles to lift and drop the biomass, as well as attrition media which fall onto the biomass, to enhance the treatment process.

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.

Reactor for tracking catalyst nanoparticles in liquid at high temperature under a high-pressure gas phase with X-ray absorption spectroscopy.

PubMed

Nguyen, Luan; Tao, Franklin Feng

2018-02-01

Structure of catalyst nanoparticles dispersed in liquid phase at high temperature under gas phase of reactant(s) at higher pressure (≥5 bars) is important for fundamental understanding of catalytic reactions performed on these catalyst nanoparticles. Most structural characterizations of a catalyst performing catalysis in liquid at high temperature under gas phase at high pressure were performed in an ex situ condition in terms of characterizations before or after catalysis since, from technical point of view, access to the catalyst nanoparticles during catalysis in liquid phase at high temperature under high pressure reactant gas is challenging. Here we designed a reactor which allows us to perform structural characterization using X-ray absorption spectroscopy including X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy to study catalyst nanoparticles under harsh catalysis conditions in terms of liquid up to 350 °C under gas phase with a pressure up to 50 bars. This reactor remains nanoparticles of a catalyst homogeneously dispersed in liquid during catalysis and X-ray absorption spectroscopy characterization.

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.

Interfacing supercritical fluid reaction apparatus with on-line liquid chromatography: monitoring the progress of a synthetic organic reaction performed in supercritical fluid solution.

PubMed

Ramsey, Edward D; Li, Ben; Guo, Wei; Liu, Jing Y

2015-04-03

An interface has been developed that connects a supercritical fluid reaction (SFR) vessel directly on-line to a liquid chromatograph. The combined SFR-LC system has enabled the progress of the esterification reaction between phenol and benzoyl chloride to synthesize phenyl benzoate in supercritical fluid carbon dioxide solution to be dynamically monitored. This was achieved by the periodic SFR-LC analysis of samples directly withdrawn from the esterification reaction mixture. Using the series of SFR-LC analysis results obtained for individual esterification reactions, the reaction progress profile for each esterification reaction was obtained by expressing the measured yield of phenyl benzoate as a function of reaction time. With reaction temperature fixed at 75°C, four sets (n=3) of SFR-LC reaction progress profiles were obtained at four different SFR pressures ranging from 13.79 to 27.58 MPa. The maximum SFR yield obtained for phenyl benzoate using a standard set of reactant concentrations was 85.2% (R.S.D. 4.2%) when the reaction was performed at 13.79 MPa for 90 min. In comparison, a phenyl benzoate yield of less than 0.3% was obtained using the same standard reactant concentrations after 90 min reaction time at 75°C using either: heptane, ethyl acetate or acetonitrile as conventional organic reaction solvents. Copyright © 2015 Elsevier B.V. All rights reserved.

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

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

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.

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.

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.

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.

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.

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.

A novel crystallization technique of hydroxyapatite utilizing contact reaction of minute droplet with atmospheric plasmas: Effects of the liquid source composition on the produced crystal properties

NASA Astrophysics Data System (ADS)

Wada, Y.; Kobayashi, T.; Matsumoto, M.; Onoe, K.

2017-10-01

To develop the technique for the control of the crystal composition and properties such as size distribution and morphology utilizing the contact reaction field around the minute droplets in atmospheric pressure plasma, fine spherical particles of hydroxyapatite ((Ca10(PO4)6(OH)2); HAp) were synthesized by a new plasma crystallization method. In this work, to elucidate the effects of the production region and crystal properties of hydroxyapatite for the liquid source composition, Ca2+ concentration and the Ca/P molar ratio in minute droplets were varied. The following results were obtained: (1) fine spherical HAp particles can be produced by the introduction of minute droplets with the initial Ca2+ concentration ((CCa)0) of 0.50 mol/l and the Ca/P molar ratio of 1.67. (2) When the (CCa)0 is set in the range higher than 1.00 mol/l at the constant Ca/P molar ratio of 1.67, fine spherical particles of β-TCP and HAp mixture are crystallized. (3) For the Ca/P molar ratio below 1.67, α-TCP and HAp co-precipitated. (4) The composition of the produced particles depends on both the reactant concentration and Ca/P molar ratio in the HAp source solution. (5) The dependence of the reactant concentration on the average size of the produced HAp particles is large compared with droplet size.

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).

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.

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.

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.

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.

The influence of reactive side products on the electrooxidation of methanol--a combined in situ infrared spectroscopy and online mass spectrometry study.

PubMed

Reichert, R; Schnaidt, J; Jusys, Z; Behm, R J

2014-07-21

Aiming at a better understanding of the impact of reaction intermediates and reactive side products on electrocatalytic reactions under conditions characteristic for technical applications, i.e., at high reactant conversions, we have investigated the electrooxidation of methanol on a Pt film electrode in mixtures containing defined concentrations of the reaction intermediates formaldehyde or formic acid. Employing simultaneous in situ infrared spectroscopy and online mass spectrometry in parallel to voltammetric measurements, we examined the effects of the latter molecules on the adlayer build-up and composition and on the formation of volatile reaction products CO2 and methylformate, as well as on the overall reaction rate. To assess the individual contributions of each component, we used isotope labeling techniques, where one of the two C1 components in the mixtures of methanol with either formaldehyde or formic acid was (13)C-labeled. The data reveal pronounced effects of the additional components formaldehyde and formic acid on the reaction, although their concentration was much lower (10%) than that of the main reactant methanol. Most important, the overall Faradaic current responses and the amounts of CO2 formed upon oxidation of the mixtures are always lower than the sums of the contributions from the individual components, indicative of a non-additive behavior of both Faradaic current and CO2 formation in the mixtures. Mechanistic reasons and consequences for reactions in a technical reactor, with high reactant conversion, are discussed.

EXPEDITIOUS SYNTHESIS OF IONIC LIQUIDS USING ULTRASOUND AND MICROWAVE IRRADIATION

EPA Science Inventory

Environmentally friendlier preparations of ionic liquids have been developed that proceed expeditiously under the influence of microwave or ultrasound irradiation conditions using neat reactants, alkylimidazoles and alkyl halides. A number of useful ionic liquids have been prepar...

Nanopore reactive adsorbents for the high-efficiency removal of waste species

DOEpatents

Yang, Arthur Jing-Min; Zhang, Yuehua

2005-01-04

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 ions, as the reactant particles (10). The column can be regenerated by backwashing with the liquid effluent containing, for example, acetic acid.

Organic non-aqueous cation-based redox flow batteries

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

Zhang, Lu; Huang, Jinhua; Burrell, Anthony

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 comprises a tetrafluorohydroquinone ether compound or a tetrafluorocatechol ether compound.« less

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

Thermal Behavior of Fe2O3/Al Thermite Mixtures in Air and Vacuum Environments

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

Duraes, L.; Santos, R.; Correia, A.

2006-07-28

In this work, the thermal behavior of Fe2O3/Al thermite mixtures, in air and vacuum, is studied. The individual reactants and three mixtures - stoichiometric and over aluminized - are tested, by Simultaneous Thermal Analysis (STA) and heating microscopy, with a heating rate of 10 deg. C/min. The STA results show that the presence of O2 from air, or from residual air in vacuum, influenced the reaction scheme. The Al oxidation by this oxygen was extensive, making the thermite reaction with Fe2O3 unviable. There was also evidence of significant conversion of the Fe2O3 into Fe3O4, supporting the previous conclusion. So, themore » STA curves for the three mixtures were similar and displayed features of the individual reactants' curves. The heating microscopy images confirmed the STA conclusions, with one exception: the thermal explosion of the Al sample close to 550 deg. C. The absence of this phenomenon in STA results was explained by the limited amount of material used in each sample.« less

The Role of Carbohydrates at the Origin of Homochirality in Biosystems

NASA Astrophysics Data System (ADS)

Toxvaerd, Søren

2013-10-01

Pasteur has demonstrated that the chiral components in a racemic mixture can separate in homochiral crystals. But with a strong chiral discrimination the chiral components in a concentrated mixture can also phase separate into homochiral fluid domains, and the isomerization kinetics can then perform a symmetry breaking into one thermodynamical stable homochiral system. Glyceraldehyde has a sufficient chiral discrimination to perform such a symmetry breaking. The requirement of a high concentration of the chiral reactant(s) in an aqueous solution in order to perform and maintain homochirality; the appearance of phosphorylation of almost all carbohydrates in the central machinery of life; the basic ideas that the biochemistry and the glycolysis and gluconeogenesis contain the trace of the biochemical evolution, all point in the direction of that homochirality was obtained just after- or at a phosphorylation of the very first products of the formose reaction, at high concentrations of the reactants in phosphate rich compartments in submarine hydrothermal vents. A racemic solution of D,L-glyceraldehyde-3-phosphate could be the template for obtaining homochiral D-glyceraldehyde-3-phosphate(aq) as well as L-amino acids.

Mechanistic investigations on dimethyl carbonate formation by oxidative carbonylation of methanol over a CuY zeolite: an operando SSITKA/DRIFTS/MS study.

PubMed

Engeldinger, Jana; Richter, Manfred; Bentrup, Ursula

2012-02-21

The simultaneous combination of steady state isotopic transient kinetic analysis (SSITKA) with diffuse reflectance Fourier transform spectroscopy (DRIFTS) and mass spectrometric (MS) analysis was applied to study the oxidative carbonylation of methanol (MeOH) to dimethyl carbonate (DMC) on a CuY zeolite catalyst prepared by incipient-wetness impregnation of commercial zeolite NH(4)-Y. The interaction of the catalyst with different reactants and reactant mixtures (O(2), CO, CO/O(2), MeOH/O(2), MeOH/CO, and MeOH/CO/O(2)) was studied in detail using (16)O(2)/(18)O(2) as well as (12)CO/(13)CO containing gas mixtures. DMC is produced via a monodentate monomethyl carbonate (MMC) species as intermediate which is formed by the concerted action of adsorbed methoxide and CO with gas phase MeOH. Adsorbed bidentate MMC species were found to be inactive. Lattice oxygen supplied by CuO(x) species is involved in the formation of MMC. Gas phase oxygen is needed to re-oxidize the catalyst but favours also the oxidation of CO to CO(2) and unselective oxidation reactions of MeOH to methyl formate, dimethoxymethane, and CO(2). The appropriate choice of reaction temperature and of the oxygen content in the reactant gas mixture was found to be indispensable for reaching high DMC selectivities.

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.

An overview of Ball Aerospace cryogen storage and delivery systems

NASA Astrophysics Data System (ADS)

Marquardt, J.; Keller, J.; Mills, G.; Schmidt, J.

2015-12-01

Starting on the Gemini program in the 1960s, Beech Aircraft (now Ball Aerospace) has been designing and manufacturing dewars for a variety of cryogens including liquid hydrogen and oxygen. These dewars flew on the Apollo, Skylab and Space Shuttle spacecraft providing fuel cell reactants resulting in over 150 manned spaceflights. Since Space Shuttle, Ball has also built the liquid hydrogen fuel tanks for the Boeing Phantom Eye unmanned aerial vehicle. Returning back to its fuel cell days, Ball has designed, built and tested a volume-constrained liquid hydrogen and oxygen tank system for reactant delivery to fuel cells on unmanned undersea vehicles (UUVs). Herein past history of Ball technology is described. Testing has been completed on the UUV specific design, which will be described.

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

Hunting liquid micro-pockets in snow and ice: Phase transition in salt solutions at the bulk and interface with X-ray photoelectron spectroscopy.

NASA Astrophysics Data System (ADS)

Bartels-Rausch, Thorsten; Orlando, Fabrizio; Kong, Xiangrui; Waldner, Astrid; Artiglia, Luca; Ammann, Markus; Huthwelker, Thomas

2016-04-01

Sea salt, and in particular chloride, is an important reactant in the atmosphere. Chloride in air-borne sea salt aerosol is - once chemically converted to a molecular halogen (Cl2, BrCl) and released to the atmosphere - well known as important atmospheric reactant, driving large-scale changes to the atmospheric composition and in particular to ozone levels in remote areas, but also in coastal mega cities. Similar chemistry has been proposed for sea salt deposits in polar snow covers. A crucial factor determining the overall reactivity is the local physical environment of the chloride ion. For example, the reactivity of liquid aerosols decreases significantly upon crystallization. Surprisingly, the phases of NaCl-containing systems are still under debate, partially due to the limited availability of in situ measurements directly probing the local environment at the surface of frozen NaCl-water binary systems. Using core electron spectroscopy of the oxygen atoms in water, we previously showed that these systems follow the phase rules at the air-ice interface. This finding contrasts some earlier observations, where the presence of liquid below the eutectic point of bulk solutions was postulated. In the present study, we present new electron yield near-edge X-ray absorption fine structure spectroscopy (NEXAFS) data obtained at near-ambient pressures up to 20 mbar of NaCl frozen solutions. The method is sensitive to small changes in the local environment of the chlorine atom. The measurements were performed at the PHOENIX beamline at SLS. The study indicates frapant differences in the phases of NaCl - water mixtures at temperatures blow the freezing point for the surface of the ice vs. the bulk. This has significant impact on modelling chemical reactions in snow or ice and it's environmental consequences.

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.

Effects of Radiative Emission and Absorption on the Propagation and Extinction of Premixed Gas Flames

NASA Technical Reports Server (NTRS)

Ju, Yiguang; Masuya, Goro; Ronney, Paul D.

1998-01-01

Premixed gas flames in mixtures of CH4, O2, N2, and CO2 were studied numerically using detailed chemical and radiative emission-absorption models to establish the conditions for which radiatively induced extinction limits may exist independent of the system dimensions. It was found that reabsorption of emitted radiation led to substantially higher burning velocities and wider extinction limits than calculations using optically thin radiation models, particularly when CO2, a strong absorber, is present in the unburned gas, Two heat loss mechanisms that lead to flammability limits even with reabsorption were identified. One is that for dry hydrocarbon-air mixtures, because of the differences in the absorption spectra of H2O and CO2, most of the radiation from product H2O that is emitted in the upstream direction cannot be absorbed by the reactants. The second is that the emission spectrum Of CO2 is broader at flame temperatures than ambient temperature: thus, some radiation emitted near the flame front cannot be absorbed by the reactants even when they are seeded with CO2 Via both mechanisms, some net upstream heat loss due to radiation will always occur, leading to extinction of sufficiently weak mixtures. Downstream loss has practically no influence. Comparison with experiment demonstrates the importance of reabsorption in CO2 diluted mixtures. It is concluded that fundamental flammability limits can exist due to radiative heat loss, but these limits are strongly dependent on the emission-absorption spectra of the reactant and product -gases and their temperature dependence and cannot be predicted using gray-gas or optically thin model parameters. Applications to practical flames at high pressure, in large combustion chambers, and with exhaust-gas or flue-gas recirculation are discussed.

Comparative Methylation of 1,8-Dihydroxy-9,10-Anthraquinone: Chemoselectivity in the Organic Chemistry Laboratory

ERIC Educational Resources Information Center

Sereda, Grigori A.

2005-01-01

A study has shown that methylation of 1,8-dihydroxy-9,10-anthraquinone (1) with methyl tosylate is highly dependent upon reaction conditions. When the reaction is carried out by a simple heating of the reaction mixture without solvent it yields dimethyl product in a nearly quantitative yield and refluxing the same mixture of reactants in…

Mechanistic Studies of Combustion and Structure Formation During Synthesis of Advanced Materials

NASA Technical Reports Server (NTRS)

Varma, A.; Lau, C.; Mukasyan, A. S.

2001-01-01

Combustion in a variety of heterogeneous systems, leading to the synthesis of advanced materials, is characterized by high temperatures (2000-3500 K) and heating rates (up to 10(exp 6) K/s) at and ahead of the reaction front. These high temperatures generate liquids and gases which are subject to gravity-driven flow. The removal of such gravitational effects is likely to provide increased control of the reaction front, with a consequent improvement in control of the microstructure of the synthesized products. Thus, microgravity (mu-g) experiments lead to major advances in the understanding of fundamental aspects of combustion and structure formation under the extreme conditions of the combustion synthesis (CS) wave. In addition, the specific features of microgravity environment allow one to produce unique materials, which cannot be obtained under terrestrial conditions. The current research is a logic continuation of our previous work on investigations of the fundamental phenomena of combustion and structure formation that occur at the high temperatures achieved in a CS wave. Our research is being conducted in three main directions: 1) Microstructural Transformations during Combustion Synthesis of Metal-Ceramic Composites. The studies are devoted to the investigation of particle growth during CS of intermetallic-ceramic composites, synthesized from nickel, aluminum, titanium, and boron metal reactants. To determine the mechanisms of particle growth, the investigation varies the relative amount of components in the initial mixture to yield combustion wave products with different ratios of solid and liquid phases, under 1g and mu-g conditions; 2) Mechanisms of Heat Transfer during Reactions in Heterogeneous Media. Specifically, new phenomena of gasless combustion wave propagation in heterogeneous media with porosity higher than that achievable in normal gravity conditions, are being studied. Two types of mixtures are investigated: clad powders, where contact between reactants occurs within each particle, and mixtures of elemental powders, where interparticle contacts are important for the reaction; and 3) Mechanistic Studies of Phase Separation in Combustion of Thermite Systems. Studies are devoted to experiments on thermite systems (metal oxide-reducing metal) where phase separation processes occur to produce alloys with tailored compositions and properties. The separation may be either gravity-driven or due to surface forces, and systematic studies to elucidate the true mechanism are being conducted. The knowledge obtained will be used to find the most promising ways of controlling the microstructure and properties of combustion-synthesized materials. Low-gravity experiments are essential to create idealized an environment for insights into the physics and chemistry of advanced material synthesis processes.

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

ERIC Educational Resources Information Center

Wright, Stephen W.

2002-01-01

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

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.

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.

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.

Status review of PMR polyimides. [Polymerization of Monomer Reactants

NASA Technical Reports Server (NTRS)

Serafini, T. T.

1979-01-01

In the NASA developed PMR (polymerization of monomer reactants) the reinforcing fibers are impregnated with a solution containing a mixture of monomers dissolved in a low boiling point alkyl alcohol solvent, with the monomers reacting in situ at elevated temperatures to form a thermo-oxidatively stable polyimide matrix. The current status of first and second generation PMR polyimides is reviewed, considering synthesis and properties, processing, and applications. It is concluded that the PMR approach offers various significant advantages, especially superior high temperature properties and processing versatility, to fabricators and users of polyimide/fiber composites.

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)

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.

Ionizable side chains at catalytic active sites of enzymes.

PubMed

Jimenez-Morales, David; Liang, Jie; Eisenberg, Bob

2012-05-01

Catalytic active sites of enzymes of known structure can be well defined by a modern program of computational geometry. The CASTp program was used to define and measure the volume of the catalytic active sites of 573 enzymes in the Catalytic Site Atlas database. The active sites are identified as catalytic because the amino acids they contain are known to participate in the chemical reaction catalyzed by the enzyme. Acid and base side chains are reliable markers of catalytic active sites. The catalytic active sites have 4 acid and 5 base side chains, in an average volume of 1,072 Å(3). The number density of acid side chains is 8.3 M (in chemical units); the number density of basic side chains is 10.6 M. The catalytic active site of these enzymes is an unusual electrostatic and steric environment in which side chains and reactants are crowded together in a mixture more like an ionic liquid than an ideal infinitely dilute solution. The electrostatics and crowding of reactants and side chains seems likely to be important for catalytic function. In three types of analogous ion channels, simulation of crowded charges accounts for the main properties of selectivity measured in a wide range of solutions and concentrations. It seems wise to use mathematics designed to study interacting complex fluids when making models of the catalytic active sites of enzymes.

Ionizable Side Chains at Catalytic Active Sites of Enzymes

PubMed Central

Jimenez-Morales, David; Liang, Jie

2012-01-01

Catalytic active sites of enzymes of known structure can be well defined by a modern program of computational geometry. The CASTp program was used to define and measure the volume of the catalytic active sites of 573 enzymes in the Catalytic Site Atlas database. The active sites are identified as catalytic because the amino acids they contain are known to participate in the chemical reaction catalyzed by the enzyme. Acid and base side chains are reliable markers of catalytic active sites. The catalytic active sites have 4 acid and 5 base side chains, in an average volume of 1072 Å3. The number density of acid side chains is 8.3 M (in chemical units); the number density of basic side chains is 10.6 M. The catalytic active site of these enzymes is an unusual electrostatic and steric environment in which side chains and reactants are crowded together in a mixture more like an ionic liquid than an ideal infinitely dilute solution. The electrostatics and crowding of reactants and side chains seems likely to be important for catalytic function. In three types of analogous ion channels, simulation of crowded charges accounts for the main properties of selectivity measured in a wide range of solutions and concentrations. It seems wise to use mathematics designed to study interacting complex fluids when making models of the catalytic active sites of enzymes. PMID:22484856

Photochemical processes on Titan: Irradiation of mixtures of gases that simulate Titan's atmosphere

NASA Astrophysics Data System (ADS)

Tran, Buu N.; Joseph, Jeffrey C.; Force, Michael; Briggs, Robert G.; Vuitton, Veronique; Ferris, James P.

2005-09-01

Photochemical reaction pathways in Titan's atmosphere were investigated by irradiation of the individual components and the mixture containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene. The quantum yields for the loss of the reactants and the formation of products were determined. Photolysis of ethylene yields mainly saturated compounds (ethane, propane, and butane) while photolysis of acetylene yields the same saturated compounds as well as ethylene and diacetylene. Irradiation of cyanoacetylene yields mainly hydrogen cyanide and small amounts of acetonitrile. When an amount of methane corresponding to its mixing ratio on Titan was added to these mixtures the quantum yields for the loss of reactants decreased and the quantum yields for hydrocarbon formation increased indicative of a hydrogen atom abstraction from methane by the photochemically generated radicals. GC/MS analysis of the products formed by irradiation of mixtures of all these gases generated over 120 compounds which were mainly aliphatic hydrocarbons containing double and triple bonds along with much smaller amounts of aromatic compounds like benzene, toluene and phenylacetylene. The reaction pathways were investigated by the use of 13C acetylene in these gas mixtures. No polycyclic aromatic compounds were detected. Vapor pressures of these compounds under conditions present in Titan's atmosphere were calculated. The low molecular weight compounds likely to be present in the atmosphere and aerosols of Titan as a result of photochemical processes are proposed.

Terascale High-Fidelity Simulations of Turbulent Combustion with Detailed Chemistry: Spray Simulations

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

Rutland, Christopher J.

2009-04-26

The Terascale High-Fidelity Simulations of Turbulent Combustion (TSTC) project is a multi-university collaborative effort to develop a high-fidelity turbulent reacting flow simulation capability utilizing terascale, massively parallel computer technology. The main paradigm of the approach is direct numerical simulation (DNS) featuring the highest temporal and spatial accuracy, allowing quantitative observations of the fine-scale physics found in turbulent reacting flows as well as providing a useful tool for development of sub-models needed in device-level simulations. Under this component of the TSTC program the simulation code named S3D, developed and shared with coworkers at Sandia National Laboratories, has been enhanced with newmore » numerical algorithms and physical models to provide predictive capabilities for turbulent liquid fuel spray dynamics. Major accomplishments include improved fundamental understanding of mixing and auto-ignition in multi-phase turbulent reactant mixtures and turbulent fuel injection spray jets.« less

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.

Combustion characteristics of nanoaluminum, liquid water, and hydrogen peroxide mixtures

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

Sabourin, J.L.; Yetter, R.A.; Risha, G.A.

2008-08-15

An experimental investigation of the combustion characteristics of nanoaluminum (nAl), liquid water (H{sub 2}O{sub (l)}), and hydrogen peroxide (H{sub 2}O{sub 2}) mixtures has been conducted. Linear and mass-burning rates as functions of pressure, equivalence ratio ({phi}), and concentration of H{sub 2}O{sub 2} in H{sub 2}O{sub (l)} oxidizing solution are reported. Steady-state burning rates were obtained at room temperature using a windowed pressure vessel over an initial pressure range of 0.24 to 12.4 MPa in argon, using average nAl particle diameters of 38 nm, {phi} from 0.5 to 1.3, and H{sub 2}O{sub 2} concentrations between 0 and 32% by mass. Atmore » a nominal pressure of 3.65 MPa, under stoichiometric conditions, mass-burning rates per unit area ranged between 6.93 g/cm{sup 2} s (0% H{sub 2}O{sub 2}) and 37.04 g/cm{sup 2} s (32% H{sub 2}O{sub 2}), which corresponded to linear burning rates of 9.58 and 58.2 cm/s, respectively. Burning rate pressure exponents of 0.44 and 0.38 were found for stoichiometric mixtures at room temperature containing 10 and 25% H{sub 2}O{sub 2}, respectively, up to 5 MPa. Burning rates are reduced above {proportional_to}5 MPa due to the pressurization of interstitial spaces of the packed reactant mixture with argon gas, diluting the fuel and oxidizer mixture. Mass burning rates were not measured above {proportional_to}32% H{sub 2}O{sub 2} due to an anomalous burning phenomena, which caused overpressurization within the quartz sample holder, leading to tube rupture. High-speed imaging displayed fingering or jetting ahead of the normal flame front. Localized pressure measurements were taken along the sample length, determining that the combustion process proceeded as a normal deflagration prior to tube rupture, without significant pressure buildup within the tube. In addition to burning rates, chemical efficiencies of the combustion reaction were determined to be within approximately 10% of the theoretical maximum under all conditions studied. (author)« less

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

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.

On the possibility of life on early Mars

NASA Technical Reports Server (NTRS)

Oberbeck, V. R.; Fogleman, G.

1990-01-01

Prebiotic reactants, liquid water, and temperatures low enough for organic compounds to be stable are requirements for the origination of life as we know it. Prebiotic reactants and sufficiently low temperatures were present on Mars before liquid water vanished. Early in this time period, however, large planetesimal impacts may have periodically sterilized Mars, pyrolyzed organic compounds, and interrupted chemical origination of life. However, the calculated time interval between such impacts on Mars was larger just before liquid water vanished 3.8 Gyr (billion years) ago than it was on earth just before life originated. Therefore, there should have been sufficient time for life to originate on Mars. Ideal sites to search for microfossils are in the heavily cratered terrain of Upper Noachian age. Craters and channels in this terrain may have been the sites of ancient lakes and streams that could have provided habitats for the first microorganisms.

Development of a Pulsed Combustion Actuator For High-Speed Flow Control

NASA Technical Reports Server (NTRS)

Cutler, Andrew D.; Beck, B. Terry; Wilkes, Jennifer A.; Drummond, J. Philip; Alderfer, David W.; Danehy, Paul M.

2005-01-01

This paper describes the flow within a prototype actuator, energized by pulsed combustion or detonations, that provides a pulsed jet suitable for flow control in high-speed applications. A high-speed valve, capable of delivering a pulsed stream of reactants a mixture of H2 and air at rates of up to 1500 pulses per second, has been constructed. The reactants burn in a resonant chamber, and the products exit the device as a pulsed jet. High frequency pressure transducers have been used to monitor the pressure fluctuations in the device at various reactant injection frequencies, including both resonant and off-resonant conditions. The combustion chamber has been constructed with windows, and the flow inside it has been visualized using Planar Laser-Induced Fluorescence (PLIF). The pulsed jet at the exit of the device has been observed using schlieren.

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.

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.

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.

Hydrogen generation systems 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 reactant materials and aqueous solutions to generate hydrogen. 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. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One systemmore » operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.« less

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.

Hydrogen generation systems utilizing sodium silicide and sodium silica gel materials

DOEpatents

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

2015-07-14

Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. 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. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One system operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.

Method of making metal oxide ceramic powders by using a combustible amino acid compound

DOEpatents

Pederson, L.R.; Chick, L.A.; Exarhos, G.J.

1992-05-19

This invention is directed to the formation of homogeneous, aqueous precursor mixtures of at least one substantially soluble metal salt and a substantially soluble, combustible co-reactant compound, typically an amino acid. This produces, upon evaporation, a substantially homogeneous intermediate material having a total solids level which would support combustion. The homogeneous intermediate material essentially comprises highly dispersed or solvated metal constituents and the co-reactant compound. The intermediate material is quite flammable. A metal oxide powder results on ignition of the intermediate product which combusts same to produce the product powder.

Method of making metal oxide ceramic powders by using a combustible amino acid compound

DOEpatents

Pederson, Larry R.; Chick, Lawrence A.; Exarhos, Gregory J.

1992-01-01

This invention is directed to the formation of homogeneous, aqueous precursor mixtures of at least one substantially soluble metal salt and a substantially soluble, combustible co-reactant compound, typically an amino acid. This produces, upon evaporation, a substantially homogeneous intermediate material having a total solids level which would support combustion. The homogeneous intermediate material essentially comprises highly dispersed or solvated metal constituents and the co-reactant compound. The intermediate material is quite flammable. A metal oxide powder results on ignition of the intermediate product which combusts same to produce the product powder.

PHOTOCHEMICAL REACTIONS AMONG FORMALDEHYDE, CHLORINE, AND NITROGEN DIOXIDE IN AIR

EPA Science Inventory

Photochemical reactions among chlorine, nitrogen dioxide, and formaldehyde were studied, using parts-per-million concentrations in 1 atm of air. The reactant mixtures were irradiated by ultraviolet fluorescent lamps and simultaneously analyzed by the Fourier transform infrared te...

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.

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.

Power Reactant Storage Assembly (PRSA) (Space Shuttle). PRSA hydrogen and oxygen DVT tank refurbishment

NASA Technical Reports Server (NTRS)

1993-01-01

The Power Reactant Storage Assembly (PRSA) liquid hydrogen Development Verification Test (H2 DVT) tank assembly (Beech Aircraft Corporation P/N 15548-0116-1, S/N 07399000SHT0001) and liquid oxygen (O2) DVT tank assembly (Beech Aircraft Corporation P/N 15548-0115-1, S/N 07399000SXT0001) were refurbished by Ball Electro-Optics and Cryogenics Division to provide NASA JSC, Propulsion and Power Division, the capability of performing engineering tests. The refurbishments incorporated the latest flight configuration hardware and avionics changes necessary to make the tanks function like flight articles. This final report summarizes these refurbishment activities. Also included are up-to-date records of the pressure time and cycle histories.

Modeling the ignition of a copper oxide aluminum thermite

NASA Astrophysics Data System (ADS)

Lee, Kibaek; Stewart, D. Scott; Clemenson, Michael; Glumac, Nick; Murzyn, Christopher

2017-01-01

An experimental "striker confinement" shock compression experiment was developed in the Glumac-group at the University of Illinois to study ignition and reaction in composite reactive materials. These include thermitic and intermetallic reactive powders. Sample of materials such as a thermite mixture of copper oxide and aluminum powders are initially compressed to about 80 percent full density. Two RP-80 detonators simultaneously push steel bars into the reactive material and the resulting compression causes shock compaction of the material and rapid heating. At that point one observes significant reaction and propagation of fronts. But the fronts are peculiar in that they are comprised of reactive events that can be traced to the reaction of the initially separated reactants of copper oxide and aluminum that react at their mutual interfaces, that nominally make copper liquid and aluminum oxide products. We discuss our model of the ignition of the copper oxide aluminum thermite in the context of the striker experiment and how a Gibbs formulation model [1], that includes multi-components for liquid and solid phases of aluminum, copper oxide, copper and aluminum oxide, can predict the events observed at the particle scale in the experiments.

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.

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.

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.

Modeling of the reactant conversion rate in a turbulent shear flow

NASA Technical Reports Server (NTRS)

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

1992-01-01

Results are presented of direct numerical simulations (DNS) of spatially developing shear flows under the influence of infinitely fast chemical reactions of the type A + B yields Products. The simulation results are used to construct the compositional structure of the scalar field in a statistical manner. The results of this statistical analysis indicate that the use of a Beta density for the probability density function (PDF) of an appropriate Shvab-Zeldovich mixture fraction provides a very good estimate of the limiting bounds of the reactant conversion rate within the shear layer. This provides a strong justification for the implementation of this density in practical modeling of non-homogeneous turbulent reacting flows. However, the validity of the model cannot be generalized for predictions of higher order statistical quantities. A closed form analytical expression is presented for predicting the maximum rate of reactant conversion in non-homogeneous reacting turbulence.

PROCESS FOR PRODUCTION OF URANIUM

DOEpatents

Crawford, J.W.C.

1959-09-29

A process is described for the production of uranium by the autothermic reduction of an anhydrous uranium halide with an alkaline earth metal, preferably magnesium One feature is the initial reduction step which is brought about by locally bringing to reaction temperature a portion of a mixture of the reactants in an open reaction vessel having in contact with the mixture a lining of substantial thickness composed of calcium fluoride. The lining is prepared by coating the interior surface with a plastic mixture of calcium fluoride and water and subsequently heating the coating in situ until at last the exposed surface is substantially anhydrous.

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.

Technique for the polymerization of monomers for PPQ/graphite fiber composites

NASA Technical Reports Server (NTRS)

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

1973-01-01

Impregnation of fiber prior to appreciable polymerization completely eliminates impregnation problems encountered with use of high viscosity high molecular weight polyphenylquinoxalines (PPQ) solutions. Major part of polymerization of reactant mixture is conducted on fiber during solvent removal and final curing stages.

Process for the deposition of high temperature stress and oxidation resistant coatings on silicon-based substrates

DOEpatents

Sarin, V.K.

1991-07-30

A process is disclosed for depositing a high temperature stress and oxidation resistant coating on a silicon nitride- or silicon carbide-based substrate body. A gas mixture is passed over the substrate at about 900--1500 C and about 1 torr to about ambient pressure. The gas mixture includes one or more halide vapors with other suitable reactant gases. The partial pressure ratios, flow rates, and process times are sufficient to deposit a continuous, fully dense, adherent coating. The halide and other reactant gases are gradually varied during deposition so that the coating is a graded coating of at least two layers. Each layer is a graded layer changing in composition from the material over which it is deposited to the material of the layer and further to the material, if any, deposited thereon, so that no clearly defined compositional interfaces exist. The gases and their partial pressures are varied according to a predetermined time schedule and the halide and other reactant gases are selected so that the layers include (a) an adherent, continuous intermediate layer about 0.5-20 microns thick of an aluminum nitride or an aluminum oxynitride material, over and chemically bonded to the substrate body, and (b) an adherent, continuous first outer layer about 0.5-900 microns thick including an oxide of aluminum or zirconium over and chemically bonded to the intermediate layer.

Process for the deposition of high temperature stress and oxidation resistant coatings on silicon-based substrates

DOEpatents

Sarin, Vinod K.

1991-01-01

A process for depositing a high temperature stress and oxidation resistant coating on a silicon nitride- or silicon carbide-based substrate body. A gas mixture is passed over the substrate at about 900.degree.-1500.degree. C. and about 1 torr to about ambient pressure. The gas mixture includes one or more halide vapors with other suitable reactant gases. The partial pressure ratios, flow rates, and process times are sufficient to deposit a continuous, fully dense, adherent coating. The halide and other reactant gases are gradually varied during deposition so that the coating is a graded coating of at least two layers. Each layer is a graded layer changing in composition from the material over which it is deposited to the material of the layer and further to the material, if any, deposited thereon, so that no clearly defined compositional interfaces exist. The gases and their partial pressures are varied according to a predetermined time schedule and the halide and other reactant gases are selected so that the layers include (a) an adherent, continuous intermediate layer about 0.5-20 microns thick of an aluminum nitride or an aluminum oxynitride material, over and chemically bonded to the substrate body, and (b) an adherent, continuous first outer layer about 0.5-900 microns thick including an oxide of aluminum or zirconium over and chemically bonded to the intermediate layer.

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.

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.

Miscible viscous fingering with chemical reaction involving precipitation.

NASA Astrophysics Data System (ADS)

Bae, Si-Kyun; Nagatsu, Yuichiro; Kato, Yoshihito; Tada, Yutaka

2007-11-01

When a reactive and miscible less-viscous liquid displaces a more-viscous liquid in a Hele-Shaw cell, reactive miscible viscous fingering takes place. The present study has experimentally examined how precipitation produced by chemical reaction affects miscible viscous fingering pattern. A 97 wt % glycerin solution containing iron(III) nitrate (yellow) and a solution containing potassium hexacyano ferrate(II) (colorless) were used as the more- and less-viscous liquids, respectively. In this case, the chemical reaction instantaneously takes place and produces the precipitation being dark blue in color. The experiments were done by varying reactant concentrations, the cell's gap width, and the displacement speed. We compared the patterns involving the precipitation reaction with those in the non-reactive cases. We have found fylfot-like pattern is observed, depending on the experimental condition, which has never been formed in the non-reactive experiments. As the reactant concentrations are increased or the displacement speed is decreased, the effects of the precipitation on the patterns are more pronounced.

Recent developments in biocatalysis in multiphasic ionic liquid reaction systems.

PubMed

Meyer, Lars-Erik; von Langermann, Jan; Kragl, Udo

2018-06-01

Ionic liquids are well known and frequently used 'designer solvents' for biocatalytic reactions. This review highlights recent achievements in the field of multiphasic ionic liquid-based reaction concepts. It covers classical biphasic systems including supported ionic liquid phases, thermo-regulated multi-component solvent systems (TMS) and polymerized ionic liquids. These powerful concepts combine unique reaction conditions with a high potential for future applications on a laboratory and industrial scale. The presence of a multiphasic system simplifies downstream processing due to the distribution of the catalyst and reactants in different phases.

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

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.

Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds

DOEpatents

Jackson, James E.; Lam, Chun Ho; Saffron, Christopher M.; Miller, Dennis J.

2018-04-24

A process and related electrode composition are disclosed for the electrocatalytic hydrogenation and/or hydrodeoxygenation of organic substrates such as biomass-derived bio-oil components by the production of hydrogen atoms on a catalyst surface followed by the reaction of the hydrogen atoms with the organic reactants. Biomass fast pyrolysis-derived bio-oil is a liquid mixture containing hundreds of organic compounds with chemical functionalities that are corrosive to container materials and are prone to polymerization. A high surface area skeletal metal catalyst material such as Raney Nickel can be used as the cathode. Electrocatalytic hydrogenation and/or hydrodeoxygenation convert the organic substrates under mild conditions to reduce coke formation and catalyst deactivation. The process converts oxygen-containing functionalities and unsaturated bonds into chemically reduced forms with an increased hydrogen content. The process is operated at mild conditions, which enables it to be a good means for stabilizing bio-oil to a form that can be stored and transported using metal containers and pipes.

Liquid class predictor for liquid handling of complex mixtures

DOEpatents

Seglke, Brent W [San Ramon, CA; Lekin, Timothy P [Livermore, CA

2008-12-09

A method of establishing liquid classes of complex mixtures for liquid handling equipment. The mixtures are composed of components and the equipment has equipment parameters. The first step comprises preparing a response curve for the components. The next step comprises using the response curve to prepare a response indicator for the mixtures. The next step comprises deriving a model that relates the components and the mixtures to establish the liquid classes.

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.

Effect of oxygen compounds addition on the hydrocracking of coal derived liquid

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

Sato, Yoshiki; Kodera, Yoichi; Kamo, Tohru

1998-12-31

Coal derived liquid from liquefaction, coking and low temperature pyrolysis contains considerable amounts of alkylphenols with alkylbenzenes and alkylnaphthalenes. To produce and purify useful chemicals from coal-derived liquid, hydrocracking and hydrotreating of alkylphenol mixture is a very important process. In this study the effects of oxygen compounds such as dimethylcarbonate (DMC) addition on the hydrocracking of alkylphenols and coal-derived liquid were investigated to decrease hydrogen consumption due to the production of water from the removal of OH group. From the hydrocracking of 3,5-dimethylphenol (3,5-DMP) without DMC at 700 C, residence time of 3--10 sec under hydrogen-to-reactant molar ratio of moremore » than 10 using atmospheric flow apparatus with quartz reactor, m-xylene and m-cresol were produced with the production ratio of 1:1.8. However the dehydroxylation to produce m-xylene was decreased by the addition of 10% DMC with the 50% increased production ratio of 1:2.7. These are considered due to the strong interaction between OH group and DMC. Similar reaction behavior was observed in the hydrocracking of 2,5-DMP and the production ratio of (o-cresol + m-cresol)/p-xylene slightly increased from 3.0 to 3.5 by the addition of DMC. On the other hand, the products distribution did not change with and without DMC in the case of 2,6-DMP. This indicates the interaction is hindered by steric effect by the neighboring CH{sub 3} group. The effect of other oxygen compounds on the hydrocracking and the products distribution from the hydrocracking of coal-derived liquids is also discussed.« less

Plexcitonics: Coupled and Plasmon-Exciton Systems with Tailorable Properties

DTIC Science & Technology

2013-11-14

demonstrated efficient steam generation from aqueous nanoparticles solutions without heating the bulk volume of the liquid. Application in ethanol ...solutions without heating the bulk volume of the liquid. Applications in ethanol distillation and sanitation have been demonstrated. Key Accomplishments...nanoparticle surface. This state-selective population of adsorbate resonances could be exploited to prepare reactants in specific states on nanoparticle

Combustion synthesis of ceramic and metal-matrix composites

NASA Technical Reports Server (NTRS)

Moore, John J.; Feng, Heng J.; Hunter, Kevin J.; Wirth, David G.

1993-01-01

Combustion synthesis or self-propagating high temperature synthesis (SHS) is effected by heating a reactant mixture, to above the ignition temperature (Tig) whereupon an exothermic reaction is initiated which produces a maximum or combustion temperature, Tc. These SHS reactions are being used to produce ceramics, intermetallics, and composite materials. One of the major limitations of this process is that relatively high levels of porosity, e.g., 50 percent, remain in the product. Conducting these SHS reactions under adiabatic conditions, the maximum temperature is the adiabatic temperature, Tad, and delta H (Tad) = 0, Tad = Tc. If the reactants or products go through a phase change, the latent heat of transformation needs to be taken into account.

Modeling the Shock Ignition of a Copper Oxide Aluminum Thermite

NASA Astrophysics Data System (ADS)

Lee, Kibaek; Stewart, D. Scott; Clemenson, Michael; Glumac, Nick; Murzyn, Christopher

2015-06-01

An experimental ``striker confinement'' shock compression test was developed in the Glumac-group at the University of Illinois to study ignition and reaction in composite reactive materials. These include thermitic and intermetallic reactive powders. The test places a sample of materials such as a thermite mixture of copper oxide and aluminum powders that are initially compressed to about 80 percent full density. Two RP-80 detonators simultaneously push steel bars into reactive material and the resulting compression causes shock compaction of the material and rapid heating. At that point one observes significant reaction and propagation of fronts. But the fronts are peculiar in that they are comprised of reactive events that can be traced to the reaction/diffusion of the initially separated reactants of copper oxide and aluminum that react at their mutual interfaces that nominally make copper liquid and aluminum oxide products. We discuss our model of the shock ignition of the copper oxide aluminum thermite in the context of the striker experiment and how a Gibbs formulation model, that includes multi-components for liquid and solid phases of aluminum, copper oxide, copper and aluminum oxide can predict the events observed at the particle scale in the experiments. Supported by HDTRA1-10-1-0020 (DTRA), N000014-12-1-0555 (ONR).

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.

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.

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.

Thermal hydrocracking of coal derived liquid from mild gasification (production of phenols, BTX and naphthalenes)

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

Sato, Yoshiki; Kodera, Yoichi; Kamo, Tohru

1997-12-31

Coal derived liquid from mild gasification contains more than 40% of alkylphenols with alkylnaphthalenes and a small amount of benzofuran, naphthol and condensed aromatic derivatives. In this study, thermal hydrocracking of the coal derived liquid, and related model compounds have been investigated using a small atmospheric flow apparatus at temperatures of 700--770 C with residence time of 3--10 sec, and hydrogen-to-reactant molar ratio of about 3--10. In the experiments using m-cresol and 2,5-dimethylphenol, dealkylation and dehydroxylation proceeded concurrently with high selectivity in the presence of excess hydrogen. The rates of hydrocracking of m-cresol and 2,5-dimethylphenol were in accordance with first-ordermore » rate law with respect to reactant. This indicates that the same kinetic equation for the demethylation of alkylbenzenes can be applied. Rates of demethylation and dehydroxylation for cresols and dimethylphenols have been measured at 700 C by using toluene as an internal reference, and discussed in terms of chemical structure. Thermal hydrocracking of the coal derived liquid produced 20--40 wt% gases and 60--80 wt% liquids. Gaseous products mainly consisted of carbon monoxide and methane with small amounts of C{sub 2} and C{sub 3} hydrocarbon gases. Liquid products, obtained at 770 C, contained 24 wt% of BTX, 40 wt% of phenol and cresols, and 12 wt% of naphthalene and methylnaphthalenes. Yield of useful chemicals, having simple aromatic structure in the liquid product increased with temperature and residence time.« less

Effect of fuel stratification on detonation wave propagation

NASA Astrophysics Data System (ADS)

Masselot, Damien; Fievet, Romain; Raman, Venkat

2016-11-01

Rotating detonation engines (RDEs) form a class of pressure-gain combustion systems of higher efficiency compared to conventional gas turbine engines. One of the key features of the design is the injection system, as reactants need to be continuously provided to the detonation wave to sustain its propagation speed. As inhomogeneities in the reactant mixture can perturb the detonation wave front, premixed fuel jet injectors might seem like the most stable solution. However, this introduces the risk of the detonation wave propagating through the injector, causing catastrophic failure. On the other hand, non-premixed fuel injection will tend to quench the detonation wave near the injectors, reducing the likelihood of such failure. Still, the effects of such non-premixing and flow inhomogeneities ahead of a detonation wave have yet to be fully understood and are the object of this study. A 3D channel filled with O2 diluted in an inert gas with circular H2 injectors is simulated as a detonation wave propagates through the system. The impact of key parameters such as injector spacing, injector size, mixture composition and time variations will be discussed. PhD Candidate.

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.

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.

Numerical Simulation of the Detonation of Condensed Explosives

NASA Astrophysics Data System (ADS)

Wang, Cheng; Ye, Ting; Ning, Jianguo

Detonation process of a condensed explosive was simulated using a finite difference method. Euler equations were applied to describe the detonation flow field, an ignition and growth model for the chemical reaction and Jones-Wilkins-Lee (JWL) equations of state for the state of explosives and detonation products. Based on the simple mixture rule that assumes the reacting explosives to be a mixture of the reactant and product components, 1D and 2D codes were developed to simulate the detonation process of high explosive PBX9404. The numerical results are in good agreement with the experimental results, which demonstrates that the finite difference method, mixture rule and chemical reaction proposed in this paper are adequate and feasible.

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.

Prediction of vapour-liquid and vapour-liquid-liquid equilibria of nitrogen-hydrocarbon mixtures used in J-T refrigerators

NASA Astrophysics Data System (ADS)

Narayanan, Vineed; Venkatarathnam, G.

2018-03-01

Nitrogen-hydrocarbon mixtures are widely used as refrigerants in J-T refrigerators operating with mixtures, as well as in natural gas liquefiers. The Peng-Robinson equation of state has traditionally been used to simulate the above cryogenic process. Multi parameter Helmholtz energy equations are now preferred for determining the properties of natural gas. They have, however, been used only to predict vapour-liquid equilibria, and not vapour-liquid-liquid equilibria that can occur in mixtures used in cryogenic mixed refrigerant processes. In this paper the vapour-liquid equilibrium of binary mixtures of nitrogen-methane, nitrogen-ethane, nitrogen-propane, nitrogen-isobutane and three component mixtures of nitrogen-methane-ethane and nitrogen-methane-propane have been studied with the Peng-Robinson and the Helmholtz energy equations of state of NIST REFPROP and compared with experimental data available in the literature.

Dispersion Polymerization of Polystyrene Particles Using Alcohol as Reaction Medium

NASA Astrophysics Data System (ADS)

Cho, Young-Sang; Shin, Cheol Hwan; Han, Sujin

2016-02-01

In this study, monodisperse polystyrene nanospheres were prepared by dispersion polymerization using alcohol as reaction medium to prepare colloidal clusters of the latex beads. Polyvinylpyrrolidone (PVP) and 2-(methacryloyloxy)ethyltrimethylammonium chloride (MTC) were used as dispersion stabilizer and comonomer, respectively. The particle size could be controlled by adjusting the reactant compositions such as the amount of stabilizer, comonomer, and water in the reactant mixture. The size and monodispersity of the polymeric particles could be also controlled by changing the reaction medium with different alcohols other than ethanol or adjusting the polymerization temperature. The synthesized particles could be self-organized inside water-in-oil emulsion droplets by evaporation-driven self-assembly to produce colloidal clusters of the polymeric nanospheres.

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

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

Doktorov, Alexander B., E-mail: doktorov@kinetics.nsc.ru

Manifestations of the “cage” effect at the encounters of reactants have been theoretically treated on the example of multistage reactions (including bimolecular exchange reactions as elementary stages) proceeding from different active sites in liquid solutions. It is shown that for reactions occurring near the contact of reactants, consistent consideration of quasi-stationary kinetics of such multistage reactions (possible in the framework of the encounter theory only) can be made on the basis of chemical concepts of the “cage complex,” just as in the case of one-site model described in the literature. Exactly as in the one-site model, the presence of themore » “cage” effect gives rise to new channels of reactant transformation that cannot result from elementary event of chemical conversion for the given reaction mechanism. Besides, the multisite model demonstrates new (as compared to one-site model) features of multistage reaction course.« less

The influence of the "cage" effect on the mechanism of reversible bimolecular multistage chemical reactions proceeding from different sites in solutions.

PubMed

Doktorov, Alexander B

2016-08-28

Manifestations of the "cage" effect at the encounters of reactants have been theoretically treated on the example of multistage reactions (including bimolecular exchange reactions as elementary stages) proceeding from different active sites in liquid solutions. It is shown that for reactions occurring near the contact of reactants, consistent consideration of quasi-stationary kinetics of such multistage reactions (possible in the framework of the encounter theory only) can be made on the basis of chemical concepts of the "cage complex," just as in the case of one-site model described in the literature. Exactly as in the one-site model, the presence of the "cage" effect gives rise to new channels of reactant transformation that cannot result from elementary event of chemical conversion for the given reaction mechanism. Besides, the multisite model demonstrates new (as compared to one-site model) features of multistage reaction course.

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.

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.

The slowly reacting mode of combustion of gaseous mixtures in spherical vessels. Part 1: Transient analysis and explosion limits

NASA Astrophysics Data System (ADS)

Liñán, Amable; Moreno-Boza, Daniel; Iglesias, Immaculada; Sánchez, Antonio L.; Williams, Forman A.

2016-11-01

Frank-Kamenetskii's analysis of thermal explosions is revisited, using also a single-reaction model with an Arrhenius rate having a large activation energy, to describe the transient combustion of initially cold gaseous mixtures enclosed in a spherical vessel with a constant wall temperature. The analysis shows two modes of combustion. There is a flameless slowly reacting mode for low wall temperatures or small vessel sizes, when the temperature rise resulting from the heat released by the reaction is kept small by the heat-conduction losses to the wall, so as not to change significantly the order of magnitude of the reaction rate. In the other mode, the slow reaction rates occur only in an initial ignition stage, which ends abruptly when very large reaction rates cause a temperature runaway, or thermal explosion, at a well-defined ignition time and location, thereby triggering a flame that propagates across the vessel to consume the reactant rapidly. Explosion limits are defined, in agreement with Frank-Kamenetskii's analysis, by the limiting conditions for existence of the slowly reacting mode of combustion. In this mode, a quasi-steady temperature distribution is established after a transient reaction stage with small reactant consumption. Most of the reactant is burnt, with nearly uniform mass fraction, in a subsequent long stage during which the temperature follows a quasi-steady balance between the rates of heat conduction to the wall and of chemical heat release. The changes in the explosion limits caused by the enhanced heat-transfer rates associated with buoyant motion are described in an accompanying paper.

A temperature-controlled photoelectrochemical cell for quantitative product analysis.

PubMed

Corson, Elizabeth R; Creel, Erin B; Kim, Youngsang; Urban, Jeffrey J; Kostecki, Robert; McCloskey, Bryan D

2018-05-01

In this study, we describe the design and operation of a temperature-controlled photoelectrochemical cell for analysis of gaseous and liquid products formed at an illuminated working electrode. This cell is specifically designed to quantitatively analyze photoelectrochemical processes that yield multiple gas and liquid products at low current densities and exhibit limiting reactant concentrations that prevent these processes from being studied in traditional single chamber electrolytic cells. The geometry of the cell presented in this paper enables front-illumination of the photoelectrode and maximizes the electrode surface area to electrolyte volume ratio to increase liquid product concentration and hence enhances ex situ spectroscopic sensitivity toward them. Gas is bubbled through the electrolyte in the working electrode chamber during operation to maintain a saturated reactant concentration and to continuously mix the electrolyte. Gaseous products are detected by an in-line gas chromatograph, and liquid products are analyzed ex situ by nuclear magnetic resonance. Cell performance was validated by examining carbon dioxide reduction on a silver foil electrode, showing comparable results both to those reported in the literature and identical experiments performed in a standard parallel-electrode electrochemical cell. To demonstrate a photoelectrochemical application of the cell, CO 2 reduction experiments were carried out on a plasmonic nanostructured silver photocathode and showed different product distributions under dark and illuminated conditions.

A temperature-controlled photoelectrochemical cell for quantitative product analysis

NASA Astrophysics Data System (ADS)

Corson, Elizabeth R.; Creel, Erin B.; Kim, Youngsang; Urban, Jeffrey J.; Kostecki, Robert; McCloskey, Bryan D.

2018-05-01

In this study, we describe the design and operation of a temperature-controlled photoelectrochemical cell for analysis of gaseous and liquid products formed at an illuminated working electrode. This cell is specifically designed to quantitatively analyze photoelectrochemical processes that yield multiple gas and liquid products at low current densities and exhibit limiting reactant concentrations that prevent these processes from being studied in traditional single chamber electrolytic cells. The geometry of the cell presented in this paper enables front-illumination of the photoelectrode and maximizes the electrode surface area to electrolyte volume ratio to increase liquid product concentration and hence enhances ex situ spectroscopic sensitivity toward them. Gas is bubbled through the electrolyte in the working electrode chamber during operation to maintain a saturated reactant concentration and to continuously mix the electrolyte. Gaseous products are detected by an in-line gas chromatograph, and liquid products are analyzed ex situ by nuclear magnetic resonance. Cell performance was validated by examining carbon dioxide reduction on a silver foil electrode, showing comparable results both to those reported in the literature and identical experiments performed in a standard parallel-electrode electrochemical cell. To demonstrate a photoelectrochemical application of the cell, CO2 reduction experiments were carried out on a plasmonic nanostructured silver photocathode and showed different product distributions under dark and illuminated conditions.

Laser flash photolysis studies of atmospheric free radical chemistry using optical diagnostic techniques

NASA Technical Reports Server (NTRS)

Wine, Paul H.; Nicovich, J. M.; Hynes, Anthony J.; Stickel, Robert E.; Thorn, R. P.; Chin, Mian; Cronkhite, Jeffrey A.; Shackelford, Christie J.; Zhao, Zhizhong; Daykin, Edward P.

1993-01-01

Some recent studies carried out in our laboratory are described where laser flash photolytic production of reactant free radicals has been combined with reactant and/or product detection using time-resolved optical techniques to investigate the kinetics and mechanisms of important atmospheric chemical reactions. Discussed are (1) a study of the radical-radical reaction O + BrO yields Br + O2 where two photolysis lasers are employed to prepare the reaction mixture and where the reactants O and BrO are monitored simultaneously using atomic resonance fluorescence to detect O and multipass UV absorption to detect BrO; (2) a study of the reaction of atomic chlorine with dimethylsulfide (CH3SCH3) where atomic resonance fluorescence detection of Cl is employed to elucidate the kinetics and tunable diode laser absorption spectroscopy is employed to investigate the HCl product yield; and (3) a study of the aqueous phase chemistry of Cl2(-) radicals where longpath UV absorption spectroscopy is employed to investigate the kinetics of the Cl2(-) + H2O reaction.

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.

Method to produce water-soluble sugars from biomass using solvents containing lactones

DOEpatents

Dumesic, James A.; Luterbacher, Jeremy S.

2015-06-02

A process to produce an aqueous solution of carbohydrates that contains C6-sugar-containing oligomers, C6 sugar monomers, C5-sugar-containing oligomers, C5 sugar monomers, or any combination thereof is presented. The process includes the steps of reacting biomass or a biomass-derived reactant with a solvent system including a lactone and water, and an acid catalyst. The reaction yields a product mixture containing water-soluble C6-sugar-containing oligomers, C6-sugar monomers, C5-sugar-containing oligomers, C5-sugar monomers, or any combination thereof. A solute is added to the product mixture to cause partitioning of the product mixture into an aqueous layer containing the carbohydrates and a substantially immiscible organic layer containing the lactone.

Method to produce water-soluble sugars from biomass using solvents containing lactones

DOEpatents

Dumesic, James A.; Luterbacher, Jeremy S.

2017-08-08

A process to produce an aqueous solution of carbohydrates that contains C6-sugar-containing oligomers, C6 sugar monomers, C5-sugar-containing oligomers, C5 sugar monomers, or any combination thereof is presented. The process includes the steps of reacting biomass or a biomass-derived reactant with a solvent system including a lactone and water, and an acid catalyst. The reaction yields a product mixture containing water-soluble C6-sugar-containing oligomers, C6-sugar monomers, C5-sugar-containing oligomers, C5-sugar monomers, or any combination thereof. A solute is added to the product mixture to cause partitioning of the product mixture into an aqueous layer containing the carbohydrates and a substantially immiscible organic layer containing the lactone.

Wick-and-pool electrodes for electrochemical cell

DOEpatents

Roche, Michael F.; Faist, Suzan M.; Eberhart, James G.; Ross, Laurids E.

1977-01-01

An electrode system includes a reservoir of liquid-metal reactant, and a wick extending from a submersed location within the reservoir into the molten electrolyte of an electrochemical cell structure. The wick is flooded with the liquid metal and thereby serves as one electrode within the cell. This electrode system has application in high-temperature batteries employing molten alkali metals or their alloys as active material within an electrode submersed within a molten salt electrolyte. It also can be used in electrochemical cells where the purification, separation or electrowinning of liquid metals is accomplished.

Wick-and-pool electrodes for electrochemical cell

DOEpatents

Roche, Michael F.; Faist, Suzan M.; Eberhart, James G.; Ross, Laurids E.

1980-01-01

An electrode system includes a reservoir of liquid-metal reactant, and a wick extending from a submersed location within the reservoir into the molten electrolyte of an electrochemical cell structure. The wick is flooded with the liquid metal and thereby serves as one electrode within the cell. This electrode system has application in high-temperature batteries employing molten alkali metals or their alloys as active material within an electrode submersed within a molten salt electrolyte. It also can be used in electrochemical cells where the purification, separation or electrowinning of liquid metals is accomplished.

Immobilization of organic radioactive and non-radioactive liquid waste in a composite matrix

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

Galkin, Anatoliy; Gelis, Artem V.; Castiglioni, Andrew J.

A method for immobilizing liquid radioactive waste is provided, the method having the steps of mixing waste with polymer to form a non-liquid waste; contacting the non-liquid waste with a solidifying agent to create a mixture, heating the mixture to cause the polymer, waste, and filler to irreversibly bind in a solid phase, and compressing the solid phase into a monolith. The invention also provides a method for immobilizing liquid radioactive waste containing tritium, the method having the steps of mixing liquid waste with polymer to convert the liquid waste to a non-liquid waste, contacting the non-liquid waste with amore » solidifying agent to create a mixture, heating the mixture to form homogeneous, chemically stable solid phase, and compressing the chemically stable solid phase into a final waste form, wherein the polymer comprises approximately a 9:1 weight ratio mixture of styrene block co-polymers and cross linked co-polymers of acrylamides.« less

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.

Measurement of tritium in natural water

NASA Astrophysics Data System (ADS)

Li, Meifen

1985-06-01

A detergent-scintillation liquid mixture applied to measure low specific activity of tritium in natural water was studied. The DYS-1 low level liquid scintillation counter designed and manufactured by our institute was employed. In comparing the Triton X-100 scintillation liquid mixture with the dioxane-based-scintillation liquid, a better formula for Triton X-100 scintillation liquid mixture was determined, the mixture possesses the quality of high water content; high efficiency and low back-ground in measuring tritium in water. Chemiluminescence of the Triton X-100 scintillation liquid mixture can be totally de-excited in short time. It can be employed at ambient temperature 11 28°C. For 20ml sample in quartz vials, counting efficiency is 15% with a background 2.17 cpm, Y=31 TU (t=30 min).

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/.

Effect of stirring on the safety of flammable liquid mixtures.

PubMed

Liaw, Horng-Jang; Gerbaud, Vincent; Chen, Chan-Cheng; Shu, Chi-Min

2010-05-15

Flash point is the most important variable employed to characterize fire and explosion hazard of liquids. The models developed for predicting the flash point of partially miscible mixtures in the literature to date are all based on the assumption of liquid-liquid equilibrium. In real-world environments, however, the liquid-liquid equilibrium assumption does not always hold, such as the collection or accumulation of waste solvents without stirring, where complete stirring for a period of time is usually used to ensure the liquid phases being in equilibrium. This study investigated the effect of stirring on the flash-point behavior of binary partially miscible mixtures. Two series of partially miscible binary mixtures were employed to elucidate the effect of stirring. The first series was aqueous-organic mixtures, including water+1-butanol, water+2-butanol, water+isobutanol, water+1-pentanol, and water+octane; the second series was the mixtures of two flammable solvents, which included methanol+decane, methanol+2,2,4-trimethylpentane, and methanol+octane. Results reveal that for binary aqueous-organic solutions the flash-point values of unstirred mixtures were located between those of the completely stirred mixtures and those of the flammable component. Therefore, risk assessment could be done based on the flammable component flash-point value. However, for the assurance of safety, it is suggested to completely stir those mixtures before handling to reduce the risk. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Influence of excess diamine on properties of PMR polyimide resins and composites

NASA Technical Reports Server (NTRS)

Hurwitz, F. I.

1980-01-01

By varying the stoichiometry of the reactants in the preparation of PMR polyimide resin, changes occur in molecular weight distribution which influence the rheological properties and thus the processability of the resin, as well as the mechanical properties of the composite. The influence of 1-10 percent molar excess MDA on the molecular weight distribution and rheological properties of an imidized PMR system were exposed. Molecular weight distribution is characterized by gel permeation chromatography of the imidized molding compound; shear viscosity is related to changes in average molecular weight. The thermo-oxidative stability at 600 F, glass transition temperature, flexural and interlaminar shear properties of PMR polyimide/Celion 6000 graphite fiber composites are compared as a function of the percent excess MDA in the monomer reactant mixture.

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.

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

Analysis of Trihalomethanes in Soft Drinks: An Instrumental Analysis Experiment.

ERIC Educational Resources Information Center

Graham, Richard C.; Robertson, John K.

1988-01-01

Describes an experimental procedure for determining trihalomethanes (THMs) in liquids by gas chromatography. Provides recommendations for reactants and supplies to obtain acceptable results. Discusses the analysis of water from various sources: pools, lakes, and drinking water; compares these to three cola drinks. (ML)

Novel anisole mixture and gasoline containing the same

DOEpatents

Singerman, Gary M.

1982-01-26

A novel anisole mixture containing anisole and a mixture of alkyl anisoles and liquid hydrocarbon fuels containing said novel anisole mixture in an amount sufficient to increase the octane number of said liquid fuel composition.

Self-diffusion Coefficient and Structure of Binary n-Alkane Mixtures at the Liquid-Vapor Interfaces.

PubMed

Chilukoti, Hari Krishna; Kikugawa, Gota; Ohara, Taku

2015-10-15

The self-diffusion coefficient and molecular-scale structure of several binary n-alkane liquid mixtures in the liquid-vapor interface regions have been examined using molecular dynamics simulations. It was observed that in hexane-tetracosane mixture hexane molecules are accumulated in the liquid-vapor interface region and the accumulation intensity decreases with increase in a molar fraction of hexane in the examined range. Molecular alignment and configuration in the interface region of the liquid mixture change with a molar fraction of hexane. The self-diffusion coefficient in the direction parallel to the interface of both tetracosane and hexane in their binary mixture increases in the interface region. It was found that the self-diffusion coefficient of both tetracosane and hexane in their binary mixture is considerably higher in the vapor side of the interface region as the molar fraction of hexane goes lower, which is mostly due to the increase in local free volume caused by the local structure of the liquid in the interface region.

Electric Field Effects in Self-Propagating High-Temperature Synthesis under Microgravity Conditions

NASA Technical Reports Server (NTRS)

Unuvar, C.; Frederick, D. M.; Shaw, B. D.; Munir, Z. A.

2003-01-01

Self-propagating high-temperature synthesis (SHS) has been used to form many materials. SHS generally involves mixing reactants together (e.g., metal powders) and igniting the mixture such that a combustion (deflagration) wave passes though the mixture. The imposition of an electric field (AC or DC) across SHS reactants has been shown to have a marked effect on the dynamics of wave propagation and on the nature, composition, and homogeneity of the product . The use of an electric field with SHS has been termed "field-assisted SHS". Combustion wave velocities and temperatures are directly affected by the field, which is typically perpendicular to the average wave velocity. The degree of activation by the field (e.g., combustion rate) is related to the current density distribution within the sample, and is therefore related to the temperature-dependent spatial distribution of the effective electrical conductivity of reactants and products. Furthermore, the field can influence other important SHS-related phenomena including capillary flow, mass-transport in porous media, and Marangoni flows. These phenomena are influenced by gravity in conventional SHS processes (i.e., without electric fields). As a result the influence of the field on SHS under reduced gravity is expected to be different than under normal gravity. It is also known that heat loss rates from samples, which can depend significantly on gravity, can influence final products in SHS. This research program is focused on studying field-assisted SHS under reduced gravity conditions. The broad objective of this research program is to understand the role of an electric field in SHS reactions under conditions where gravity-related effects are suppressed. The research will allow increased understanding of fundamental aspects of field-assisted SHS processes as well as synthesis of materials that cannot be formed in normal gravity.

Anisotropic and Electro-Optical Effects in Liquid Crystals.

DTIC Science & Technology

1981-08-01

alkylphenols and p-alkoxybenzoyl chlorides. Most of the reactants are obtained commercially from either Aldrich Chemical, Frinton, or Eastman Organic. The...phenol intermediates for the R-OOCpR’ compounds are prepared by refluxing the 4- alkylphenol with 4-hydroxybenzoic acid in toluene with sulfuric and

Method of CO and/or CO.sub.2 hydrogenation to higher hydrocarbons using doped mixed-metal oxides

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

Shekhawat, Dushyant; Berry, David A.; Haynes, Daniel J.

2017-03-21

A method of hydrogenation utilizing a reactant gas mixture comprising a carbon oxide and a hydrogen agent, and a hydrogenation catalyst comprising a mixed-metal oxide containing metal sites supported and/or incorporated into the lattice. The mixed-metal oxide comprises a pyrochlore, a brownmillerite, or mixtures thereof doped at the A-site or the B-site. The metal site may comprise a deposited metal, where the deposited metal is a transition metal, an alkali metal, an alkaline earth metal, or mixtures thereof. Contact between the carbon oxide, hydrogen agent, and hydrogenation catalyst under appropriate conditions of temperature, pressure and gas flow rate generate amore » hydrogenation reaction and produce a hydrogenated product made up of carbon from the carbon oxide and some portion of the hydrogen agent. The carbon oxide may be CO, CO.sub.2, or mixtures thereof and the hydrogen agent may be H.sub.2. In a particular embodiment, the hydrogenated product comprises olefins, paraffins, or mixtures thereof.« less

A Variational Statistical-Field Theory for Polar Liquid Mixtures

NASA Astrophysics Data System (ADS)

Zhuang, Bilin; Wang, Zhen-Gang

Using a variational field-theoretic approach, we derive a molecularly-based theory for polar liquid mixtures. The resulting theory consists of simple algebraic expressions for the free energy of mixing and the dielectric constant as functions of mixture composition. Using only the dielectric constants and the molar volumes of the pure liquid constituents, the theory evaluates the mixture dielectric constants in good agreement with the experimental values for a wide range of liquid mixtures, without using adjustable parameters. In addition, the theory predicts that liquids with similar dielectric constants and molar volumes dissolve well in each other, while sufficient disparity in these parameters result in phase separation. The calculated miscibility map on the dielectric constant-molar volume axes agrees well with known experimental observations for a large number of liquid pairs. Thus the theory provides a quantification for the well-known empirical ``like-dissolves-like'' rule. Bz acknowledges the A-STAR fellowship for the financial support.

Statistics of wormlike chains. II. Phase transition of polymer liquid crystals and its mixture with low molecular weight liquid crystals

NASA Astrophysics Data System (ADS)

Zhang, W. X.; Zhao, S. R.; Sun, C. P.

1997-02-01

A general self-consistent field (SCF) for the mixture of polymer and low molecular weight (LMW) molecules has been derived by variation principle. Considering a Maier-Saupe type of interaction, the analytical expressions of the SCF for polymer liquid crystals (PLCs) and the mixture of PLCs and LMW liquid crystals are obtained, from which the phase behaviors of PLCs as well as the mixture are studied. The theoretical results are in agreement with experimental results by adjusting a parameter.

Combustion synthesis of low exothermic component rich composites

DOEpatents

Halverson, Danny C.; Lum, Beverly Y.; Munir, Zuhair A.

1991-01-01

A self-sustaining combustion synthesis process for producing hard, tough, lightweight, low exothermic potential product (LEPP)/high exothermic potential product (HEPP) composites is based on the thermodynamic dependence of adiabatic temperature and product composition on the stoichiometry of the LEPP and HEPP reactants. For lightweight products the composition must be relatively rich in the LEPP component. LEPP rich composites are obtained by varying the initial temperature of the reactants. The product is hard, porous material whose toughness can be enhanced by filling the pores with aluminum or other metal phases using a liquid metal infiltration process. The process can be extended to the formation of other composites having a low exothermic component.

Catalytic, hollow, refractory spheres, conversions with them

NASA Technical Reports Server (NTRS)

Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

1989-01-01

Improved, heterogeneous, refractory catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitable formed of a shell (12) of refractory such as alumina having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be itself catalytic or a catalytically active material coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

Catalytic, hollow, refractory spheres

NASA Technical Reports Server (NTRS)

Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

1987-01-01

Improved, heterogeneous, refractory catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitable formed of a shell (12) of refractory such as alumina having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be itself catalytic or a catalytically active material coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

Catalytic hollow spheres

NASA Technical Reports Server (NTRS)

Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

1989-01-01

The improved, heterogeneous catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitably formed of a shell (12) of metal such as aluminum having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be, itself, catalytic or the catalyst can be coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

Catalytic hollow spheres

NASA Technical Reports Server (NTRS)

Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

1986-01-01

The improved, heterogeneous catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitably formed of a shell (12) of metal such as aluminum having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be, itself, catalytic or the catalyst can be coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

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…

Diffusion Limited Supercritical Water Oxidation (SCWO) in Microgravity Environments

NASA Technical Reports Server (NTRS)

Hicks, M. C.; Lauver, R. W.; Hegde, U. G.; Sikora, T. J.

2006-01-01

Tests designed to quantify the gravitational effects on thermal mixing and reactant injection in a Supercritical Water Oxidation (SCWO) reactor have recently been performed in the Zero Gravity Facility (ZGF) at NASA s Glenn Research Center. An artificial waste stream, comprising aqueous mixtures of methanol, was pressurized to approximately 250 atm and then heated to 450 C. After uniform temperatures in the reactor were verified, a controlled injection of air was initiated through a specially designed injector to simulate diffusion limited reactions typical in most continuous flow reactors. Results from a thermal mapping of the reaction zone in both 1-g and 0-g environments are compared. Additionally, results of a numerical model of the test configuration are presented to illustrate first order effects on reactant mixing and thermal transport in the absence of gravity.

Membrane permeation process for dehydration of organic liquid mixtures using sulfonated ion-exchange polyalkene membranes

DOEpatents

Cabasso, Israel; Korngold, Emmanuel

1988-01-01

A membrane permeation process for dehydrating a mixture of organic liquids, such as alcohols or close boiling, heat sensitive mixtures. The process comprises causing a component of the mixture to selectively sorb into one side of sulfonated ion-exchange polyalkene (e.g., polyethylene) membranes and selectively diffuse or flow therethrough, and then desorbing the component into a gas or liquid phase on the other side of the membranes.

Change of hydrogen bonding structure in ionic liquid mixtures by anion type

NASA Astrophysics Data System (ADS)

Cha, Seoncheol; Kim, Doseok

2018-05-01

Ionic liquid mixtures have gained attention as a way of tuning material properties continuously with composition changes. For some mixture systems, physicochemical properties such as excess molar volume have been found to be significantly different from the value expected by linear interpolation, but the origin of this deviation is not well understood yet. The microstructure of the mixture, which can range from an ideal mixture of two initial consisting ionic liquids to a different structure from those of pure materials, has been suggested as the origin of the observed deviation. The structures of several different ionic liquid mixtures are studied by IR spectroscopy to confirm this suggestion, as a particular IR absorption band (νC(2)-D) for the moiety participating in the hydrogen bonding changes sensitively with the change of the anion in the ionic liquid. The absorbance of νC(2)-D changes proportionally with the composition, and a relatively small excess molar volume is observed for the mixtures containing an electronegative halide anion. By contrast, the absorbance changes nonlinearly, and the excess molar volumes are larger for the mixtures of which one of the anions has multiple interaction sites.

Floating liquid phase in sedimenting colloid-polymer mixtures.

PubMed

Schmidt, Matthias; Dijkstra, Marjolein; Hansen, Jean-Pierre

2004-08-20

Density functional theory and computer simulation are used to investigate sedimentation equilibria of colloid-polymer mixtures within the Asakura-Oosawa-Vrij model of hard sphere colloids and ideal polymers. When the ratio of buoyant masses of the two species is comparable to the ratio of differences in density of the coexisting bulk (colloid) gas and liquid phases, a stable "floating liquid" phase is found, i.e., a thin layer of liquid sandwiched between upper and lower gas phases. The full phase diagram of the mixture under gravity shows coexistence of this floating liquid phase with a single gas phase or a phase involving liquid-gas equilibrium; the phase coexistence lines meet at a triple point. This scenario remains valid for general asymmetric binary mixtures undergoing bulk phase separation.

Combined centrifugal force/gravity gas/liquid separator system

NASA Astrophysics Data System (ADS)

Lema, Luis E.

1993-04-01

A gas/liquid separator system has an outer enclosing tank filled with a demisting packing material. The tank has a gas outlet port and a liquid outlet port located at its top and bottom, respectively. At least one cylindrical, centrifugal force gas/liquid separator is vertically aligned and centrally located within the tank and is surrounded by the packing material. The cylindrical separator receives a gas/liquid mixture, separates the mixture into respective substantially gas and substantially liquid components, and allows the substantially gas components to exit its gas escape port. It also allows the substantially liquid components to exit its liquid escape port. The packing material in the tank further separates the substantially gas and liquid components as they rise and fall, respectively, through the packing material. An inflow line introduces the mixture into the cylindrical separator. The inflow line is upwardly inclined in a direction of flow of the mixture at a point where the inflow line communicates with the cylindrical separator.

Toughening reinforced epoxy composites with brominated polymeric additives

NASA Technical Reports Server (NTRS)

Nir, Z. (Inventor); Gilwee, W. J., Jr. (Inventor)

1985-01-01

Cured polyfunctional epoxy resins including tris(hydroxyphenyl)methane triglycidyl ether are toughened by addition of polybrominated polymeric additives having an EE below 1500 to the pre-cure composition. Carboxy-terminated butadiene-acrylonitrile rubber is optionally present in the pre-cure mixture as such or as a pre-formed copolymer with other reactants. Reinforced composites, particularly carbon-reinforced composites, of these resins are disclosed and shown to have improved toughness.

Toughening reinforced epoxy composites with brominated polymeric additives

NASA Technical Reports Server (NTRS)

Nir, Z.; Gilwee, W. J., Jr. (Inventor)

1985-01-01

Cured polyfunctional epoxy resins including tris (hydroxyphenyl) methane triglycidyl ether are toughened by addition of polybrominated polymeric additives having an EE below 1500 to the pre-cure composition. Carboxy terminated butadiene acrylonitrile rubber is optionally present in the precure mixture as such or as a pre-formed copolymer with other reactants. Reinforced composites, particularly carbon reinforced composites, of these resins are disclosed and shown to have improved toughness.

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.

Surface modification of active material structures in battery electrodes

DOEpatents

Erickson, Michael; Tikhonov, Konstantin

2016-02-02

Provided herein are methods of processing electrode active material structures for use in electrochemical cells or, more specifically, methods of forming surface layers on these structures. The structures are combined with a liquid to form a mixture. The mixture includes a surface reagent that chemically reacts and forms a surface layer covalently bound to the structures. The surface reagent may be a part of the initial liquid or added to the mixture after the liquid is combined with the structures. In some embodiments, the mixture may be processed to form a powder containing the structures with the surface layer thereon. Alternatively, the mixture may be deposited onto a current collecting substrate and dried to form an electrode layer. Furthermore, the liquid may be an electrolyte containing the surface reagent and a salt. The liquid soaks the previously arranged electrodes in order to contact the structures with the surface reagent.

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.

A computational study of syngas auto-ignition characteristics at high-pressure and low-temperature conditions with thermal inhomogeneities

NASA Astrophysics Data System (ADS)

Pal, Pinaki; Mansfield, Andrew B.; Arias, Paul G.; Wooldridge, Margaret S.; Im, Hong G.

2015-09-01

A computational study was conducted to investigate the characteristics of auto-ignition in a syngas mixture at high-pressure and low-temperature conditions in the presence of thermal inhomogeneities. Highly resolved one-dimensional numerical simulations incorporating detailed chemistry and transport were performed. The temperature inhomogeneities were represented by a global sinusoidal temperature profile and a local Gaussian temperature spike (hot spot). Reaction front speed and front Damköhler number analyses were employed to characterise the propagating ignition front. In the presence of a global temperature gradient, the ignition behaviour shifted from spontaneous propagation (strong) to deflagrative (weak), as the initial mean temperature of the reactant mixture was lowered. A predictive Zel'dovich-Sankaran criterion to determine the transition from strong to weak ignition was validated for different parametric sets. At sufficiently low temperatures, the strong ignition regime was recovered due to faster passive scalar dissipation of the imposed thermal fluctuations relative to the reaction timescale, which was quantified by the mixing Damköhler number. In the presence of local hot spots, only deflagrative fronts were observed. However, the fraction of the reactant mixture consumed by the propagating front was found to increase as the initial mean temperature was lowered, thereby leading to more enhanced compression-heating of the end-gas. Passive scalar mixing was not found to be important for the hot spot cases considered. The parametric study confirmed that the relative magnitude of the Sankaran number translates accurately to the quantitative strength of the deflagration front in the overall ignition advancement.

Chemical thermodynamics of ultrasound speed in solutions and liquid mixtures.

PubMed

Reis, João Carlos R; Santos, Angela F S; Lampreia, Isabel M S

2010-02-01

A comprehensive formalism is developed to treat thermodynamically speed of ultrasound data for solutions and liquid mixtures. For solutions, the apparent speed of ultrasound of a solute is introduced and proposed to take the place of empirically defined quantities. The partial speed of ultrasound of a solute is defined and related to the partial molar volume and partial molar isentropic compression. For liquid mixtures, the concept of speed of sound before mixing pure liquids is presented and used to define the change in speed of ultrasound upon ideal mixing, which is predicted to be generally a negative quantity. A new thermodynamic equation is derived linking the values for excess speed of ultrasound, excess molar volume and excess molar isentropic compression of a mixture, and its applications are discussed. Ideal and excess apparent speeds of ultrasound, as well as ideal and excess partial speeds of ultrasound, are defined for substances making up a liquid mixture. Accurate speeds of ultrasound in 31 mixtures of water with the amphiphile 2-(ethylamino)ethanol at 293.15 K are reported. These data are used to demonstrate the ability of the apparent speed of ultrasound to describe the impact of solutes on sonic properties of solutions and the advantages of analysing thermodynamic properties of binary liquid mixtures in terms of the dependence on composition of Balankina's ratios between excess and ideal values. It is concluded that the new thermodynamic functions defined for speeds of ultrasound in solutions and liquid mixtures give, at the least, equivalent information on molecular aspects to the usual functions related to the isentropic compressibility, without needing density data for this purpose.

Transport Properties of Ionic Liquid Mixtures Containing Heterodications

DOE PAGES

Lall-Ramnarine, S.; Fernandez, E.; Rodriguez, C.; ...

2016-08-30

This report discusses the transport properties of ionic liquid mixtures that incorporate a series of asymmetrical dications, including heterodications. The dicationic ILs combine either triphenylphosphonium and trimethylammonium cationic sites that are bridged to methylimidazolium or methylpyrrolidinium cationic sites. Mixtures were made of the dicationic bis(trifluoromethylsulfonyl)amide ionic liquids with N-ethoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide. The IL mixtures were characterized for their transport properties (temperature dependent conductivity and viscosity) and thermal properties (melting point and glass transition point).

Understanding the solution phase chemistry and solid state thermodynamic behavior of pharmaceutical cocrystals

NASA Astrophysics Data System (ADS)

Maheshwari, Chinmay

Cocrystals have drawn a lot of research interest in the last decade due to their potential to favorably alter the physicochemical and biopharmaceutical properties of active pharmaceutical ingredients. This dissertation focuses on the thermodynamic stability and solubility of pharmaceutical cocrystals. Specifically, the objectives are to; (i) investigate the influence of coformer properties such as solubility and ionization characteristics on cocrystal solubility and stability as a function of pH, (ii) to measure the thermodynamic solubility of metastable cocrystals, and study the solubility differences measured by kinetic and equilibrium methods, (iii) investigate the role of surfactants on the solubility and synthesis of cocrystals, (iv) investigate the solid state phase transformation of reactants to cocrystals and the factors that influence the reaction kinetics and, (v) provide models that enable the prediction of cocrystal formation by calculating the free energy of formation for a solid to solid transformation of reactants to cocrystals. Cocrystal solubilities were measured directly when cocrystals were thermodynamically stable, while solubilities were calculated from eutectic concentration measurements when cocrystals were of higher solubility than its components. Cocrystal solubility was highly dependent on coformer solubilities for gabapentin-lactam and lamotrigine cocrystals. It was found that melting point is not a good indicator of cocrystal solubility as solute-solvent interactions quantified by the activity coefficient play a huge role in the observed solubility. Similar to salts, cocrystals also exhibit pHmax, however the salts and cocrystals have different dependencies on the parameters that govern the value of pHmax. It is also shown that cocrystals could provide solubility advantage over salts as lamotrigine-nicotinamide cocrystal hydrate has about 6 fold higher solubility relative to lamotrigine-saccharin salt. In the case of mixtures of solid reactants, it was observed that cocrystals can form spontaneously when the reactants are in physical contact and that temperature, relative humidity, and disorder in the reactants caused by mechanical stress such as milling can enhance the reaction rates. Prediction of spontaneous cocrystal formation was investigated by developing models to calculate the Gibbs free energy of formation. Thermal behavior of cocrystal reactants was investigated by calorimetry and the interaction between the reactants is explained by investigating the heats of mixing in the melt. These principles are applied on cocrystals that are divided into two categories; (i) Where the cocrystal melting point is between that of its reactants and, (ii) where the cocrystal melting point is below that of its components. Generalized equations were developed that enable the calculation of Gibbs free energy of formation from fusion temperatures, enthalpy and entropy of fusion.

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

PubMed Central

Perosa, Alvise; Guidi, Sandro; Cattelan, Lisa

2016-01-01

Summary The use of ionic liquids (ILs) as organocatalysts is reviewed for transesterification reactions, specifically for the conversion of nontoxic compounds such as dialkyl carbonates to both linear mono-transesterification products or alkylene carbonates. An introductory survey compares pros and cons of classic catalysts based on both acidic and basic systems, to ionic liquids. Then, innovative green syntheses of task-specific ILs and their representative applications are introduced to detail the efficiency and highly selective outcome of ILs-catalyzed transesterification reactions. A mechanistic hypothesis is discussed by the concept of cooperative catalysis based on the dual (electrophilic/nucleophilic) activation of reactants. PMID:27829898

Combustion synthesis of boride and other composites

DOEpatents

Halverson, Danny C.; Lum, Beverly Y.; Munir, Zuhair A.

1989-01-01

A self-sustaining combustion synthesis process for producing hard, tough, lightweight B.sub.4 C/TiB.sub.2 composites is based on the thermodynamic dependence of adiabatic temperature and product composition on the stoichiometry of the B.sub.4 C and TiB.sub.2 reactants. For lightweight products the composition must be relatively rich in the B.sub.4 C component. B.sub.4 C-rich composites are obtained by varying the initial temperature of the reactants. The product is hard, porous material whose toughness can be enhanced by filling the pores with aluminum or other metal phases using a liquid metal infiltration process. The process can be extended to the formation of other composites having a low exothermic component.

Mechanically robust, electrically conductive ultralow-density carbon nanotube-based aerogels

DOEpatents

Worsley, Marcus A; Baumann, Theodore F; Satcher, Jr., Joe H

2014-04-01

A method of making a mechanically robust, electrically conductive ultralow-density carbon nanotube-based aerogel, including the steps of dispersing nanotubes in an aqueous media or other media to form a suspension, adding reactants and catalyst to the suspension to create a reaction mixture, curing the reaction mixture to form a wet gel, drying the wet gel to produce a dry gel, and pyrolyzing the dry gel to produce the mechanically robust, electrically conductive ultralow-density carbon nanotube-based aerogel. The aerogel is mechanically robust, electrically conductive, and ultralow-density, and is made of a porous carbon material having 5 to 95% by weight carbon nanotubes and 5 to 95% carbon binder.

Mechanically robust, electrically conductive ultralow-density carbon nanotube-based aerogels

DOEpatents

Worsley, Marcus A.; Baumann, Theodore F.; Satcher, Jr, Joe H.

2016-07-05

A method of making a mechanically robust, electrically conductive ultralow-density carbon nanotube-based aerogel, including the steps of dispersing nanotubes in an aqueous media or other media to form a suspension, adding reactants and catalyst to the suspension to create a reaction mixture, curing the reaction mixture to form a wet gel, drying the wet gel to produce a dry gel, and pyrolyzing the dry gel to produce the mechanically robust, electrically conductive ultralow-density carbon nanotube-based aerogel. The aerogel is mechanically robust, electrically conductive, and ultralow-density, and is made of a porous carbon material having 5 to 95% by weight carbon nanotubes and 5 to 95% carbon binder.

Composition and method for polymer moderated catalytic water formation

DOEpatents

Shepodd, Timothy Jon

1999-01-01

A composition suitable for safely removing hydrogen from gaseous mixtures containing hydrogen and oxygen, particularly those mixtures wherein the hydrogen concentration is within the explosive range. The composition comprises a hydrogenation catalyst, preferably Pd dispersed on carbon, wherein the concentration of Pd is from about 1-10 wt %, dispersed in a polymeric material matrix. As well as serving as a matrix to contain the hydrogenation catalyst, the polymeric material, which is substantially unreactive to hydrogen, provides both a diffusion restriction to hydrogen and oxygen, thereby limiting the rate at which the reactants (hydrogen and oxygen) can diffuse to the catalyst surface and thus, the production of heat from the recombination reaction and as a heat sink.

Acceleration of a ground-state reaction by selective femtosecond-infrared-laser-pulse excitation

NASA Astrophysics Data System (ADS)

Stensitzki, Till; Yang, Yang; Kozich, Valeri; Ahmed, Ashour A.; Kössl, Florian; Kühn, Oliver; Heyne, Karsten

2018-02-01

Infrared (IR) excitation of vibrations that participate in the reaction coordinate of an otherwise thermally driven chemical reaction are believed to lead to its acceleration. Attempts at the practical realization of this concept have been hampered so far by competing processes leading to sample heating. Here we demonstrate, using femtosecond IR-pump IR-probe experiments, the acceleration of urethane and polyurethane formation due to vibrational excitation of the reactants for 1:1 mixtures of phenylisocyanate and cyclohexanol, and toluene-2,4-diisocyanate and 2,2,2-trichloroethane-1,1-diol, respectively. We measured reaction rate changes upon selective vibrational excitation with negligible heating of the sample and observed an increase of the reaction rate up to 24%. The observation is rationalized using reactant and transition-state structures obtained from quantum chemical calculations. We subsequently used IR-driven reaction acceleration to write a polyurethane square on sample windows using a femtosecond IR pulse.

A non-ideal model for predicting the effect of dissolved salt on the flash point of solvent mixtures.

PubMed

Liaw, Horng-Jang; Wang, Tzu-Ai

2007-03-06

Flash point is one of the major quantities used to characterize the fire and explosion hazard of liquids. Herein, a liquid with dissolved salt is presented in a salt-distillation process for separating close-boiling or azeotropic systems. The addition of salts to a liquid may reduce fire and explosion hazard. In this study, we have modified a previously proposed model for predicting the flash point of miscible mixtures to extend its application to solvent/salt mixtures. This modified model was verified by comparison with the experimental data for organic solvent/salt and aqueous-organic solvent/salt mixtures to confirm its efficacy in terms of prediction of the flash points of these mixtures. The experimental results confirm marked increases in liquid flash point increment with addition of inorganic salts relative to supplementation with equivalent quantities of water. Based on this evidence, it appears reasonable to suggest potential application for the model in assessment of the fire and explosion hazard for solvent/salt mixtures and, further, that addition of inorganic salts may prove useful for hazard reduction in flammable liquids.

Widom Lines in Binary Mixtures of Supercritical Fluids.

PubMed

Raju, Muralikrishna; Banuti, Daniel T; Ma, Peter C; Ihme, Matthias

2017-06-08

Recent experiments on pure fluids have identified distinct liquid-like and gas-like regimes even under supercritical conditions. The supercritical liquid-gas transition is marked by maxima in response functions that define a line emanating from the critical point, referred to as Widom line. However, the structure of analogous state transitions in mixtures of supercritical fluids has not been determined, and it is not clear whether a Widom line can be identified for binary mixtures. Here, we present first evidence for the existence of multiple Widom lines in binary mixtures from molecular dynamics simulations. By considering mixtures of noble gases, we show that, depending on the phase behavior, mixtures transition from a liquid-like to a gas-like regime via distinctly different pathways, leading to phase relationships of surprising complexity and variety. Specifically, we show that miscible binary mixtures have behavior analogous to a pure fluid and the supercritical state space is characterized by a single liquid-gas transition. In contrast, immiscible binary mixture undergo a phase separation in which the clusters transition separately at different temperatures, resulting in multiple distinct Widom lines. The presence of this unique transition behavior emphasizes the complexity of the supercritical state to be expected in high-order mixtures of practical relevance.

Prebiotic selection and assembly of proteinogenic amino acids and natural nucleotides from complex mixtures

NASA Astrophysics Data System (ADS)

Islam, Saidul; Bučar, Dejan-Krešimir; Powner, Matthew W.

2017-06-01

A central problem for the prebiotic synthesis of biological amino acids and nucleotides is to avoid the concomitant synthesis of undesired or irrelevant by-products. Additionally, multistep pathways require mechanisms that enable the sequential addition of reactants and purification of intermediates that are consistent with reasonable geochemical scenarios. Here, we show that 2-aminothiazole reacts selectively with two- and three-carbon sugars (glycolaldehyde and glyceraldehyde, respectively), which results in their accumulation and purification as stable crystalline aminals. This permits ribonucleotide synthesis, even from complex sugar mixtures. Remarkably, aminal formation also overcomes the thermodynamically favoured isomerization of glyceraldehyde into dihydroxyacetone because only the aminal of glyceraldehyde separates from the equilibrating mixture. Finally, we show that aminal formation provides a novel pathway to amino acids that avoids the synthesis of the non-proteinogenic α,α-disubstituted analogues. The common physicochemical mechanism that controls the proteinogenic amino acid and ribonucleotide assembly from prebiotic mixtures suggests that these essential classes of metabolite had a unified chemical origin.

Enzymatic synthesis of 6-O-glucosyl-poly(3-hydroxyalkanoate) in organic solvents and their binary mixture.

PubMed

Gumel, A M; Annuar, M S M; Heidelberg, T

2013-04-01

The effects of organic solvents and their binary mixture in the glucose functionalization of bacterial poly-3-hydroxyalkanoates catalyzed by Lecitase™ Ultra were studied. Equal volume binary mixture of DMSO and chloroform with moderate polarity was more effective for the enzyme catalyzed synthesis of the carbohydrate polymer at ≈38.2 (±0.8)% reactant conversion as compared to the mono-phasic and other binary solvents studied. The apparent reaction rate constant as a function of medium water activity (aw) was observed to increase with increasing solvent polarity, with optimum aw of 0.2, 0.4 and 0.7 (±0.1) observed in hydrophilic DMSO, binary mixture DMSO:isooctane and hydrophobic isooctane, respectively. Molecular sieve loading between 13 to 15gL(-1) (±0.2) and reaction temperature between 40 to 50°C were found optimal. Functionalized PHA polymer showed potential characteristics and biodegradability. Copyright © 2012 Elsevier B.V. All rights reserved.

A physicochemical investigation of ionic liquid mixtures† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc02931c Click here for additional data file.

PubMed Central

Clough, Matthew T.; Crick, Colin R.; Gräsvik, John; Niedermeyer, Heiko; Whitaker, Oliver P.

2015-01-01

Ionic liquids have earned the reputation of being ‘designer solvents’ due to the wide range of accessible properties and the degree of fine-tuning afforded by varying the constituent ions. Mixtures of ionic liquids offer the opportunity for further fine-tuning of properties. A broad selection of common ionic liquid cations and anions are employed to create a sample of binary and reciprocal binary ionic liquid mixtures, which are analysed and described in this paper. Physical properties such as the conductivity, viscosity, density and phase behaviour (glass transition temperatures) are examined. In addition, thermal stabilities of the mixtures are evaluated. The physical properties examined for these formulations are found to generally adhere remarkably closely to ideal mixing laws, with a few consistent exceptions, allowing for the facile prediction and control of properties of ionic liquid mixtures. PMID:29560198

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.

Method of CO and/or CO.sub.2 hydrogenation using doped mixed-metal oxides

DOEpatents

Shekhawat, Dushyant; Berry, David A.; Haynes, Daniel J.; Abdelsayed, Victor; Smith, Mark W.; Spivey, James J.

2015-10-06

A method of hydrogenation utilizing a reactant gas mixture comprising a carbon oxide and a hydrogen agent, and a hydrogenation catalyst comprising a mixed-metal oxide containing metal sites supported and/or incorporated into the lattice. The mixed-metal oxide comprises a perovskite, a pyrochlore, a fluorite, a brownmillerite, or mixtures thereof doped at the A-site or the B-site. The metal site may comprise a deposited metal, where the deposited metal is a transition metal, an alkali metal, an alkaline earth metal, or mixtures thereof. Contact between the carbon oxide, hydrogen agent, and hydrogenation catalyst under appropriate conditions of temperature, pressure and gas flow rate generate a hydrogenation reaction and produce a hydrogenated product made up of carbon from the carbon oxide and some portion of the hydrogen agent. The carbon oxide may be CO, CO.sub.2, or mixtures thereof and the hydrogen agent may be H.sub.2. In a particular embodiment, the hydrogenated product comprises an alcohol, an olefin, an aldehyde, a ketone, an ester, an oxo-product, or mixtures thereof.

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 influence of the "cage effect" on the mechanism of reversible bimolecular multistage chemical reactions in solutions.

PubMed

Doktorov, Alexander B

2015-08-21

Manifestations of the "cage effect" at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a "cage complex." Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the "cage effect" leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants.

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

Doktorov, Alexander B., E-mail: doktorov@kinetics.nsc.ru

Manifestations of the “cage effect” at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a “cage complex.” Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the “cage effect” leads to somemore » important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants.« less

Composition inversion in mixtures of binary colloids and polymer

NASA Astrophysics Data System (ADS)

Zhang, Isla; Pinchaipat, Rattachai; Wilding, Nigel B.; Faers, Malcolm A.; Bartlett, Paul; Evans, Robert; Royall, C. Patrick

2018-05-01

Understanding the phase behaviour of mixtures continues to pose challenges, even for systems that might be considered "simple." Here, we consider a very simple mixture of two colloidal and one non-adsorbing polymer species, which can be simplified even further to a size-asymmetrical binary mixture, in which the effective colloid-colloid interactions depend on the polymer concentration. We show that this basic system exhibits surprisingly rich phase behaviour. In particular, we enquire whether such a system features only a liquid-vapor phase separation (as in one-component colloid-polymer mixtures) or whether, additionally, liquid-liquid demixing of two colloidal phases can occur. Particle-resolved experiments show demixing-like behaviour, but when combined with bespoke Monte Carlo simulations, this proves illusory, and we reveal that only a single liquid-vapor transition occurs. Progressive migration of the small particles to the liquid phase as the polymer concentration increases gives rise to composition inversion—a maximum in the large particle concentration in the liquid phase. Close to criticality, the density fluctuations are found to be dominated by the larger colloids.

Separation Of Liquid And Gas In Zero Gravity

NASA Technical Reports Server (NTRS)

Howard, Frank S.; Fraser, Wilson S.

1991-01-01

Pair of reports describe scheme for separating liquid from gas so liquid could be pumped. Designed to operate in absence of gravitation. Jet of liquid, gas, or liquid/gas mixture fed circumferentially into cylindrical tank filled with liquid/gas mixture. Jet starts liquid swirling. Swirling motion centrifugally separates liquid from gas. Liquid then pumped from tank at point approximately diametrically opposite point of injection of jet. Vortex phase separator replaces such devices as bladders and screens. Requires no components inside tank. Pumps for gas and liquid outside tank and easily accessible for maintenance and repairs.

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.

Morphology and Optical Properties of Mixed Aerosol Particles

NASA Astrophysics Data System (ADS)

Fard, Mehrnoush M.; Krieger, Ulrich; Rudich, Yinon; Marcolli, Claudia; Peter, Thomas

2015-04-01

Experiments and modeling studies have shown that deliquesced aerosols can be present not only as one-phase system containing organics, inorganic salts and water, but often as two-phase systems consisting of a predominantly organic and a predominantly inorganic aqueous phase 1,2. Recent laboratory studies conducted with model mixtures representing tropospheric aerosols1,2,3, secondary organic aerosol (SOA) from smog chamber experiments4, and field measurements5 suggest that liquid- liquid phase separations (LLPS) is indeed a common phenomenon in mixed organic/ ammonium sulfate (AS) particles. During LLPS, particles may adopt different morphologies mainly core- shell and partially engulfed. A core- shell configuration will have consequences for heterogeneous chemistry and hygroscopicity and as a result will alter the optical properties of the particles since the aqueous inorganic-rich phase will be totally enclosed by a probably highly viscous organic coating with low diffusivity for reactants and water. The primary objective of this project is to establish a method for investigating the morphology of mixed inorganic and absorbing organic compounds of atmospheric relevance and study their radiative properties before, during, and after phase transitions mainly during LLPS. This will be the first study looking into the radiative effect of LLPS in detail. In this first experiment, the behavior of single droplets of carminic acid (CA)/ AS/ H2O mixture was monitored during relative humidity (RH) cycles using optical microscopy. The same mixture particle was levitated in an electrodynamic balance (EDB) and the change in its absorption properties was measured at varying RH. We also intend to determine the occurrence of LLPS in accumulation- sized particles and the change in their absorption using a cavity ring down aerosol spectrometer. If LLPS alters the absorptive properties of the suggested model aerosols significantly, absorption measurements of accumulation mode particles of the same composition would allow proving that LLPS indeed occurs in particles of atmospheric relevant size ranges. Up to now this prove is missing. References: 1. Bertram, et al. Atmos. Chem & Phys, 11(21), 10995-11006, 2011. 2. Krieger, et al. Chemical Society Reviews, 41(19), 6631-6662, 2012 3. Song, M. et al. Geophys Res Lett, 39(19), 2012b 4. Smith et al. Atmos Chem & Phys, 12(20), 9613- 9628, 2012. 5. You, Y. et al. Proceedings of the National Academy of Sciences, 109(33), 13188-13193, 2012.

Flash evaporation of liquid monomer particle mixture

DOEpatents

Affinito, John D.; Darab, John G.; Gross, Mark E.

1999-01-01

The present invention is a method of making a first solid composite polymer layer. The method has the steps of (a) mixing a liquid monomer with particles substantially insoluble in the liquid monomer forming a monomer particle mixture; (b) flash evaporating the particle mixture and forming a composite vapor; and (c) continuously cryocondensing said composite vapor on a cool substrate and cross-linking the cryocondensed film thereby forming the polymer layer.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G.; Eckert, Charles A.; Liotta, Charles L.; Heldebrant, David J.

2013-08-20

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G [Kingston, CA; Eckert, Charles A [Atlanta, GA; Liotta, Charles L [Atlanta, GA; Heldebrant, David J [Richland, WA

2011-07-19

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G; Eckert, Charles A; Liotta, Charles L; Heldebrant, David J

2014-04-29

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Communication: Control of chemical reactions using electric field gradients.

PubMed

Deshmukh, Shivaraj D; Tsori, Yoav

2016-05-21

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

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

Deshmukh, Shivaraj D.; Tsori, Yoav, E-mail: tsori@bgu.ac.il

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

Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)

NASA Astrophysics Data System (ADS)

Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)' providing data from direct measurement of pressure and mole fraction in vapor phase at variable mole fraction in liquid phase and constant temperature.

Unsteady Diffusion Flames: Ignition, Travel, and Burnout (SUBCORE Project: Simplified Unsteady Burning of Contained Reactants)

NASA Technical Reports Server (NTRS)

Fendell, Francis; Rungaldier, Harald

1999-01-01

An experimental apparatus for the examination of a planar, virtually strain-rate-free diffusion flame in microgravity has been designed and fabricated. Such a diffusion flame is characterized by relatively large spatial scale and high symmetry (to facilitate probing), and by relatively long fluid-residence time (to facilitate investigation of rates associated with sooting phenomena). Within the squat rectangular apparatus, with impervious, noncatalytic isothermal walls of stainless steel, a thin metallic splitter plate subdivides the contents into half-volumes. One half-volume initially contains fuel vapor diluted with an inert gas, and the other, oxidizer diluted with another inert gas-so that the two domains have equal pressure, density, and temperature. As the separator is removed, by translation in its own plane, through a tightly fitting slit in one side wall, a line ignitor in the opposite side wall initiates a triple-flame propagation across the narrow layer of combustible mixture formed near midheight in the chamber. The planar diffusion flame so emplaced is quickly disrupted in earth gravity. In microgravity, the planar flame persists, and travels ultimately into the half-volume containing the stoichiometrically deficient reactant; the flame eventually becomes extinguished owing to reactant depletion and heat loss to the walls.

Capture and release of mixed acid gasses with binding organic liquids

DOEpatents

Heldebrant, David J.; Yonker, Clement R.

2010-09-21

Reversible acid-gas binding organic liquid systems that permit separation and capture of one or more of several acid gases from a mixed gas stream, transport of the liquid, release of the acid gases from the ionic liquid and reuse of the liquid to bind more acid gas with significant energy savings compared to current aqueous systems. These systems utilize acid gas capture compounds made up of strong bases and weak acids that form salts when reacted with a selected acid gas, and which release these gases when a preselected triggering event occurs. The various new materials that make up this system can also be included in various other applications such as chemical sensors, chemical reactants, scrubbers, and separators that allow for the specific and separate removal of desired materials from a gas stream such as flue gas.

Flash evaporation of liquid monomer particle mixture

DOEpatents

Affinito, J.D.; Darab, J.G.; Gross, M.E.

1999-05-11

The present invention is a method of making a first solid composite polymer layer. The method has the steps of (a) mixing a liquid monomer with particles substantially insoluble in the liquid monomer forming a monomer particle mixture; (b) flash evaporating the particle mixture and forming a composite vapor; and (c) continuously cryocondensing said composite vapor on a cool substrate and cross-linking the cryocondensed film thereby forming the polymer layer. 3 figs.

Segregation of liquid crystal mixtures in topological defects

DOE PAGES

Rahimi, Mohammad; Ramezani-Dakhel, Hadi; Zhang, Rui; ...

2017-04-28

The structure and physical properties of liquid crystal (LC) mixtures are a function of composition, and small changes can have pronounced effects on observables, such as phase-transition temperatures. Traditionally, LC mixtures have been assumed to be compositionally homogenous. The results of chemically detailed simulations presented here show that this is not the case; pronounced deviations of the local order from that observed in the bulk at defects and interfaces lead to significant compositional segregation effects. More specifically, two disclination lines are stabilized in this work by introducing into a nematic liquid crystal mixture a cylindrical body that exhibits perpendicular anchoring.more » Here, it is found that the local composition deviates considerably from that of the bulk at the interface with the cylinder and in the defects, thereby suggesting new assembly and synthetic strategies that may capitalize on the unusual molecular environment provided by liquid crystal mixtures.« less

Combustion synthesis of boride and other composites

DOEpatents

Halverson, D.C.; Lum, B.Y.; Munir, Z.A.

1988-07-28

A self-sustaining combustion synthesis process for producing hard, tough, lightweight B/sub 4/C/TiB/sub 2/ composites is described. It is based on the thermodynamic dependence of adiabatic temperature and product composition on the stoichiometry of the B/sub 4/C and TiB/sub 2/ reactants. For lightweight products the composition must be relatively rich in the B/sub 4/C component. B/sub 4/C-rich composites are obtained by varying the initial temperature of the reactants. The product is hard, porous material whose toughness can be enhanced by filling the pores with aluminum or other metal phases using a liquid metal infiltration process. The process can be extended to the formation of other composites having a low exothermic component. 9 figs., 4 tabs.

Development of a Novel Leak-Free Constant-Pressure Cylinder for Certified Reference Materials of Liquid Hydrocarbon Mixtures.

PubMed

Kim, Yong Doo; Kang, Ji Hwan; Bae, Hyun Kil; Kang, Namgoo; Oh, Sang Hyub; Lee, Jin-Hong; Woo, Jin Chun; Lee, Sangil

2017-11-21

Liquid hydrocarbon mixtures such as liquefied petroleum gas and liquefied natural gas are becoming integral parts of the world's energy system. Certified reference materials (CRMs) of liquid hydrocarbon mixtures are necessary to allow assessment of the accuracy and traceability of the compositions of such materials. A piston-type constant-pressure cylinder (PCPC) comprising chambers for a pressurizing gas (helium) and liquid (hydrocarbons) separated by a piston can be used to develop accurate and traceable liquid hydrocarbon mixture CRMs. The development of accurate CRMs relies on the maintenance of their composition. However, a PCPC might allow hydrocarbons to leak owing to the imperfect seal of the piston. In this study, a novel leak-free bellows-type constant-pressure cylinder (BCPC) is designed and evaluated by comparison with PCPCs. Liquid hydrocarbon mixtures consisting of ethane, propane, propene, isobutane, n-butane, 1-butene, and isopentane were prepared in both types of constant pressure cylinders and then monitored to check leakages between the gas and liquid chambers. Overall, notable leakage occurred from and into both chambers in the PCPCs, whereas no leakage occurred in the BCPCs in the three months after their gravimetric preparation. The BCPCs maintained no leakage even 10 months after their preparation, whereas the PCPCs showed significantly increasing leakage during the same period.

Solidification phenomena of binary organic mixtures

NASA Technical Reports Server (NTRS)

Chang, K.

1982-01-01

The coalescence rates and motion of liquid bubbles in binary organic mixtures were studied. Several factors such as temperature gradient, composition gradient, interfacial tension, and densities of the two phases play important roles in separation of phases of immiscible liquids. An attempt was made to study the effect of initial compositions on separation rates of well-dispersed organic mixtures at different temperatures and, ultimately, on the homogeneity of solidification of the immiscible binary organic liquids. These organic mixtures serve as models for metallic pseudo binary systems under study. Two specific systems were investigated: ethyl salicylate - diethyl glycol and succinonitrile - water.

Liquid-assisted grinding and ion pairing regulates percentage conversion and diastereoselectivity of the Wittig reaction under mechanochemical conditions.

PubMed

Denlinger, Kendra Leahy; Ortiz-Trankina, Lianna; Carr, Preston; Benson, Kingsley; Waddell, Daniel C; Mack, James

2018-01-01

Mechanochemistry is maturing as a discipline and continuing to grow, so it is important to continue understanding the rules governing the system. In a mechanochemical reaction, the reactants are added into a vessel along with one or more grinding balls and the vessel is shaken at high speeds to facilitate a chemical reaction. The dielectric constant of the solvent used in liquid-assisted grinding (LAG) and properly chosen counter-ion pairing increases the percentage conversion of stilbenes in a mechanochemical Wittig reaction. Utilizing stepwise addition/evaporation of ethanol in liquid-assisted grinding also allows for the tuning of the diastereoselectivity in the Wittig reaction.

Composite bipolar plate for electrochemical cells

DOEpatents

Wilson, Mahlon S.; Busick, Deanna N.

2001-01-01

A bipolar separator plate for fuel cells consists of a molded mixture of a vinyl ester resin and graphite powder. The plate serves as a current collector and may contain fluid flow fields for the distribution of reactant gases. The material is inexpensive, electrically conductive, lightweight, strong, corrosion resistant, easily mass produced, and relatively impermeable to hydrogen gas. The addition of certain fiber reinforcements and other additives can improve the properties of the composite material without significantly increasing its overall cost.

Comparison of OH reactivity instruments in the atmosphere simulation chamber SAPHIR

NASA Astrophysics Data System (ADS)

Fuchs, Hendrik

2016-04-01

OH reactivity measurement has become an important measurement to constrain the total OH loss frequency in field experiments. Different techniques have been developed by various groups. They can be based on flow-tube or pump and probe techniques, which include direct OH detection by fluorescence, or on a comparative method, in which the OH loss of a reference species competes with the OH loss of trace gases in the sampled air. In order to ensure that these techniques deliver equivalent results, a comparison exercise was performed under controlled conditions. Nine OH reactivity instruments measured together in the atmosphere simulation chamber SAPHIR (volume 270 m3) during ten daylong experiments in October 2015 at ambient temperature (5 to 10° C) and pressure (990-1010 hPa). The chemical complexity of air mixtures in these experiments varied from CO in pure synthetic air to emissions from real plants and VOC/NOx mixtures representative of urban atmospheres. Potential differences between measurements were systematically investigated by changing the amount of reactants (including isoprene, monoterpenes and sesquiterpenes), water vapour, and nitrogen oxides. Some of the experiments also included the oxidation of reactants with ozone or hydroxyl radicals, in order to elaborate, if the presence of oxidation products leads to systematic differences between measurements of different instruments. Here we present first results of this comparison exercise.

Wetting phenomenon in the liquid-vapor phase coexistence of a partially miscible Lennard-Jones binary mixture

NASA Astrophysics Data System (ADS)

Ramírez-Santiago, Guillermo; Díaz-Herrera, Enrique; Moreno Razo, José A.

2004-03-01

We have carried out extensive equilibrium MD simulations to study wetting phenomena in the liquid-vapor phase coexistence of a partially miscible binary LJ mixture. We find that in the temperature range 0.60 ≤ T^* < 0.80, the system separates forming a liquid A-liquid B interface in coexistence with the vapor phase. At higher temperatures, 0.80 ≤ T^* < 1.25 the liquid phases are wet by the vapor phase. By studying the behavior of the surface tension as a function of temperature we estimate the wetting transition temperature (WTT) to be T^*_w≃ 0.80. The adsorption of molecules at the liquid-liquid interface shows a discontinuity at about T^*≃ 0.79 suggesting that the wetting transition is a first order phase transition. These results are in agreement with some experiments carried out in fluid binary mixtures. In addition, we estimated the consolute temperature to be T^* _cons≃ 1.25. The calculated phase diagram of the mixture suggest the existence of a tricritical point.

Influence of Polar Organic Solvents in an Ionic Liquid Containing Lithium Bis(fluorosulfonyl)amide: Effect on the Cation-Anion Interaction, Lithium Ion Battery Performance, and Solid Electrolyte Interphase.

PubMed

Lahiri, Abhishek; Li, Guozhu; Olschewski, Mark; Endres, Frank

2016-12-14

Ionic liquid-organic solvent mixtures have recently been investigated as potential battery electrolytes. However, contradictory results with these mixtures have been shown for battery performance. In this manuscript, we studied the influence of the addition of polar organic solvents into the ionic liquid electrolyte 1 M lithium bis(fluorosulfonyl)amide (LiFSI)-1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)amide ([Py 1,4 ]FSI) and tested it for lithium ion battery applications. From infrared and Raman spectroscopy, clear changes in the lithium solvation and cation-anion interactions in the ionic liquid were observed on addition of organic solvents. From the lithiation/delithiation studies on electrodeposited Ge, the storage capacity for the ionic liquid-highly polar organic solvent (acetonitrile) mixture was found to be the highest at low C-rates (0.425 C) compared to using an ionic liquid alone and ionic liquid-less polar solvent (dimethyl carbonate) mixtures. Furthermore, XPS and AFM were used to evaluate the solid electrolyte interphase (SEI) and to correlate its stability with Li storage capacity.

Reactivity induced at 25 K by low-energy electron irradiation of condensed NH3-CH3COOD (1 : 1) mixture.

PubMed

Lafosse, Anne; Bertin, Mathieu; Domaracka, Alicja; Pliszka, Damian; Illenberger, Eugen; Azria, Roger

2006-12-21

Chemical reactivity is observed following electron irradiation of a binary mixture of ammonia (NH(3)) and acetic acid (CH(3)COOD) at 25 K, without any subsequent thermal activation, as evidenced by vibrational high resolution electron energy loss spectroscopy (HREELS). Analysis of the HREEL spectra and comparison with infrared and Raman data of different molecules are compatible with glycine formation in its zwitterionic form. The onset for electron induced reaction is found to be at about approximately 13 eV. The mechanisms may involve NH radicals interaction with CH(3)COOD molecules. Then glycine formation does not imply any displacement of reactants, so that it involves only NH(3) and CH(3)COOD neighboring molecules.

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.

Probing Intermolecular Interactions in Binary Liquid Mixtures Using Femtosecond Laser-Induced Self-Defocusing.

PubMed

Maurya, Sandeep Kumar; Das, Dhiman; Goswami, Debabrata

2016-06-13

Photo-thermal behavior of binary liquid mixtures has been studied by high repetition rate (HRR) Z-scan technique with femtosecond laser pulses. Changes in the peak-valley difference in transmittance (ΔT P-V ) for closed aperture Z-scan experiments are indicative of thermal effects induced by HRR femtosecond laser pulses. We show such indicative results can have a far-reaching impact on molecular properties and intermolecular interactions in binary liquid mixtures. Spectroscopic parameters derived from this experimental technique show that the combined effect of physical and molecular properties of the constituent binary liquids can be related to the components of the binary liquid. © The Author(s) 2016.

Exposure of Mammalian Cells to Air-Pollutant Mixtures at the Air-Liquid Interface

EPA Science Inventory

It has been widely accepted that exposure of mammalian cells to air-pollutant mixtures at the air-liquid interface is a more realistic approach than exposing cell under submerged conditions. The VITROCELL systems, are commercially available systems for air-liquid interface expo...

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

Socha, Aaron; Singh, Seema; Simmons, Blake A.

Methods and compositions are provided for synthesizing ionic liquids from lignin derived compounds comprising: contacting a starting material comprising lignin with a depolymerization agent to depolymerize the lignin and form a mixture of aldehyde containing compounds; contacting the mixture of aldehyde containing compounds with an amine under conditions suitable to convert the mixture of aldehyde containing compounds to a mixture of amine containing compounds; and contacting the mixture of amine containing compounds with an acid under conditions suitable to form an ammonium salt, thereby preparing the ionic liquid.

Method and system to directly produce electrical power within the lithium blanket region of a magnetically confined, deuterium-tritium (DT) fueled, thermonuclear fusion reactor

DOEpatents

Woolley, Robert D.

1999-01-01

A method for integrating liquid metal magnetohydrodynamic power generation with fusion blanket technology to produce electrical power from a thermonuclear fusion reactor located within a confining magnetic field and within a toroidal structure. A hot liquid metal flows from a liquid metal blanket region into a pump duct of an electromagnetic pump which moves the liquid metal to a mixer where a gas of predetermined pressure is mixed with the pressurized liquid metal to form a Froth mixture. Electrical power is generated by flowing the Froth mixture between electrodes in a generator duct. When the Froth mixture exits the generator the gas is separated from the liquid metal and both are recycled.

Dip-in Indicators for Visual Differentiation of Fuel Mixtures Based on Wettability of Fluoroalkylchlorosilane-Coated Inverse Opal Films.

PubMed

Sedighi, Abootaleb; Qiu, Shuang; Wong, Michael C K; Li, Paul C H

2015-12-30

We have developed the dip-in indicator based on the inverse opal film (IOF) for visual differentiation of organic liquid mixtures, such as oil/gasoline or ethanol/gasoline fuel mixtures. The IOF consists of a three-dimensional porous structure with a highly ordered periodic arrangement of nanopores. The specularly reflected light at the interface of the nanopores and silica walls contributes to the structural color of the IOF film. This color disappears when the nanopores are infiltrated by a liquid with a similar refractive index to silica. The disappearance of the structural color provides a means to differentiate various liquid fuel mixtures based on their wettability of the nanopores in the IOF-based indicators. For differentiation of various liquid mixtures, we tune the wettability threshold of the indicator in such a way that it is wetted (color disappears) by one liquid but is not wetted by the other (color remains). Although colorimetric differentiation of liquids based on IOF wettability has been reported, differentiation of highly similar liquid mixtures require complicated readout approaches. It is known that the IOF wettability is controlled by multiple surface properties (e.g., oleophobicity) and structural properties (e.g., neck angle and film thickness) of the nanostructure. Therefore, we aim to exploit the combined tuning of these properties for differentiation of fuel mixtures with close compositions. In this study, we have demonstrated that, for the first time, the IOF-based dip-in indicator is able to detect a slight difference in the fuel mixture composition (i.e., 0.4% of oil content). Moreover, the color/no-color differentiation platform is simple, powerful, and easy-to-read. This platform makes the dip-in indicator a promising tool for authentication and determination of fuel composition at the point-of-purchase or point-of-use.

Chemical composition and heterogeneous reactivity of soot generated in the combustion of diesel and GTL (Gas-to-Liquid) fuels and amorphous carbon Printex U with NO2 and CF3COOH gases

NASA Astrophysics Data System (ADS)

Tapia, A.; Salgado, S.; Martín, P.; Villanueva, F.; García-Contreras, R.; Cabañas, B.

2018-03-01

The heterogeneous reactions of nitrogen dioxide (NO2) and trifluoroacetic acid (CF3COOH) with soot produced by diesel and GTL (gas-to-liquid) fuels were investigated using a Knudsen flow reactor with mass spectrometry as a detection system for gas phase species. Soot was generated with a 4 cylinder diesel engine working under steady-state like urban operation mode. Heterogeneous reaction of the mentioned gases with a commercial carbon, Printex U, used as reference, was also analyzed. The initial and the steady-state uptake coefficients, γ0 and γss, respectively, were measured indicating that GTL soot reacts faster than diesel soot and Printex U carbon for NO2 gas reactant. According to the number of reacted molecules on the surface, Printex U soot presents more reducing sites than diesel and GTL soot. Initial uptake coefficients for GTL and diesel soot for the reaction with CF3COOH gas reactant are very similar and no clear conclusions can be obtained related to the initial reactivity. The number of reacted molecules calculated for CF3COOH reactions shows values two orders of magnitude higher than the corresponding to NO2 reactions, indicating a greater presence of basic functionalities in the soot surfaces. More information of the surface composition has been obtained using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) before and after the reaction of soot samples with gas reactants. As conclusion, the interface of diesel and GTL soot before reaction mainly consists of polycyclic aromatic hydrocarbons (PAHs), nitro-compounds as well as ether functionalities. After reaction with gas reactant, it was observed that PAHs and nitro-compounds remain on the soot surface and new spectral bands such as carbonyl groups (carboxylic acids, aldehydes, esters and ketones) are observed. Physical properties of soot from both fuels studied such as BET surface isotherm and SEM analysis were also developed and related to the observed reactivity.

Ion Conduction in Perfectly Aligned Block Copolymer-Ionic Liquid Mixtures

NASA Astrophysics Data System (ADS)

Choi, Jae-Hong; Elabd, Yossef A.; Winey, Karen I.

2011-03-01

Our earlier work to correlate the transport measurements in diblock copolymer-ionic liquid mixtures was limited by our bulk samples that have only partial alignment. Here, thin films with perfect alignment of lamellar microdomains from mixtures of a poly(methyl methacrylate- b -styrene) diblock copolymer and an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, have been studied. The morphologies will be characterized by cross-sectional transmission electron microscopy. Ion conduction will be presented within and through the thin film.

Liquid over-feeding air conditioning system and method

DOEpatents

Mei, Viung C.; Chen, Fang C.

1993-01-01

A refrigeration air conditioning system utilizing a liquid over-feeding operation is described. A liquid refrigerant accumulator-heat exchanger is placed in the system to provide a heat exchange relationship between hot liquid refrigerant discharged from condenser and a relatively cool mixture of liquid and vaporous refrigerant discharged from the evaporator. This heat exchange relationship substantially sub-cools the hot liquid refrigerant which undergoes little or no evaporation across the expansion device and provides a liquid over-feeding operation through the evaporator for effectively using 100 percent of evaporator for cooling purposes and for providing the aforementioned mixture of liquid and vaporous refrigerant.

Investigation of thermal and optical properties of some quartet mixed hydrogen-bonded liquid crystals

NASA Astrophysics Data System (ADS)

Okumuş, Mustafa

2017-11-01

In this study, the thermal and optical properties of quartet mixtures formed at different weight ratios (1:1:1:1 and 1.5:1:1:1) from liquid crystals 4-octyloxy-4‧-cyanobiphenyl (8OCB), 4-hexylbenzoic acid, 4-(octyloxy)benzoic acid and 4-(decyloxy)benzoic acid were investigated by differential scanning calorimeter (DSC) and polarized optic microscopy (POM). The phase transition temperatures of the novel quartet mixtures measured in the DSC experiments are in line with the POM experiments. The experimental results clearly show that the novel liquid crystal mixtures have displayed pure liquid crystalline properties. According to the phase diagram drawn from DSC results, the nematic range of the novel mixture at the eutectic point is larger than the nematic ranges of the components. The mesomorphic structures of produced homolog complex mixtures are found to be smectic and nematic phases. But the smectic phase cannot be observed in the novel complex 1.5:1:1:1 mixture during continuous cooling. The nematic range of the novel complex 1.5:1:1:1 mixture is bigger than the nematic range of the novel complex 1:1:1:1 mixture with increasing 8OCB. Also, the nematic-to-isotropic phase transition temperature decreases with increasing the weight ratio of 8OCB in the complex quartet mixture. Another interesting result is that the produced mixtures are to be like a medical cream at room temperatures. Furthermore, order parameter and thermal stability factor of the transitions are also calculated.

Controlled Shape Memory Behavior of a Smectic Main-Chain Liquid Crystalline Elastomer

DOE PAGES

Li, Yuzhan; Pruitt, Cole; Rios, Orlando; ...

2015-04-10

Here, we describe how a smectic main-chain liquid crystalline elastomer (LCE), with controlled shape memory behavior, is synthesized by polymerizing a biphenyl-based epoxy monomer with an aliphatic carboxylic acid curing agent. Microstructures of the LCEs, including their liquid crystallinity and cross-linking density, are modified by adjusting the stoichiometric ratio of the reactants to tailor the thermomechanical properties and shape memory behavior of the material. Thermal and liquid crystalline properties of the LCEs, characterized using differential scanning calorimetry and dynamic mechanical analysis, and structural analysis, performed using small-angle and wide-angle X-ray scattering, show that liquid crystallinity, cross-linking density, and network rigiditymore » are strongly affected by the stoichiometry of the curing reaction. With appropriate structural modifications it is possible to tune the thermal, dynamic mechanical, and thermomechanical properties as well as the shape memory and thermal degradation behavior of LCEs.« less

Controlled Shape Memory Behavior of a Smectic Main-Chain Liquid Crystalline Elastomer

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

Li, Yuzhan; Pruitt, Cole; Rios, Orlando

Here, we describe how a smectic main-chain liquid crystalline elastomer (LCE), with controlled shape memory behavior, is synthesized by polymerizing a biphenyl-based epoxy monomer with an aliphatic carboxylic acid curing agent. Microstructures of the LCEs, including their liquid crystallinity and cross-linking density, are modified by adjusting the stoichiometric ratio of the reactants to tailor the thermomechanical properties and shape memory behavior of the material. Thermal and liquid crystalline properties of the LCEs, characterized using differential scanning calorimetry and dynamic mechanical analysis, and structural analysis, performed using small-angle and wide-angle X-ray scattering, show that liquid crystallinity, cross-linking density, and network rigiditymore » are strongly affected by the stoichiometry of the curing reaction. With appropriate structural modifications it is possible to tune the thermal, dynamic mechanical, and thermomechanical properties as well as the shape memory and thermal degradation behavior of LCEs.« less

Liquid Water Saturation and Oxygen Transport Resistance in Polymer Electrolyte Membrane Fuel Cell Gas Diffusion Layers

NASA Astrophysics Data System (ADS)

Muirhead, Daniel

In this thesis, the relative humidity (RH) of the cathode reactant gas was investigated as a factor which influences gas diffusion layer (GDL) liquid water accumulation and mass transport-related efficiency losses over a range of operating current densities in a polymer electrolyte membrane (PEM) fuel cell. Limiting current measurements were used to characterize fuel cell oxygen transport resistance while simultaneous measurements of liquid water accumulation were conducted using synchrotron X-ray radiography. GDL porosity distributions were characterized with micro-computed tomography (microCT). The work presented here can be used by researchers to develop improved numerical models to predict GDL liquid water accumulation and to inform the design of next-generation GDL materials to mitigate mass transport-related efficiency losses. This work also contributes an extensive set of concurrent performance and liquid water visualization data to the PEM fuel cell field that can be used for validating multiphase transport models.

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

Statistical effects related to low numbers of reacting molecules analyzed for a reversible association reaction A + B = C in ideally dispersed systems: An apparent violation of the law of mass action

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

Szymanski, R., E-mail: rszymans@cbmm.lodz.pl; Sosnowski, S.; Maślanka, Ł.

2016-03-28

Theoretical analysis and computer simulations (Monte Carlo and numerical integration of differential equations) show that the statistical effect of a small number of reacting molecules depends on a way the molecules are distributed among the small volume nano-reactors (droplets in this study). A simple reversible association A + B = C was chosen as a model reaction, enabling to observe both thermodynamic (apparent equilibrium constant) and kinetic effects of a small number of reactant molecules. When substrates are distributed uniformly among droplets, all containing the same equal number of substrate molecules, the apparent equilibrium constant of the association is highermore » than the chemical one (observed in a macroscopic—large volume system). The average rate of the association, being initially independent of the numbers of molecules, becomes (at higher conversions) higher than that in a macroscopic system: the lower the number of substrate molecules in a droplet, the higher is the rate. This results in the correspondingly higher apparent equilibrium constant. A quite opposite behavior is observed when reactant molecules are distributed randomly among droplets: the apparent association rate and equilibrium constants are lower than those observed in large volume systems, being the lower, the lower is the average number of reacting molecules in a droplet. The random distribution of reactant molecules corresponds to ideal (equal sizes of droplets) dispersing of a reaction mixture. Our simulations have shown that when the equilibrated large volume system is dispersed, the resulting droplet system is already at equilibrium and no changes of proportions of droplets differing in reactant compositions can be observed upon prolongation of the reaction time.« less

Electrochemically stable electrolytes

DOEpatents

Angell, Charles Austen; Zhang, Sheng-Shui; Xu, Kang

1999-01-01

This invention relates generally to inorganic ionic liquids which function as electrolytes and do not crystallize at ambient temperature. More specifically, this invention is directed to quasi-salt inorganic ionic liquids which comprise the reaction product of a strong Lewis acid with an inorganic halide-donating molecule. This invention is further directed to quasi-salt inorganic ionic liquid mixtures which comprise combinations of electrolyte additives and quasi-salt inorganic ionic liquids. These quasi-salt inorganic ionic liquid mixtures are useful electrolytes.

Electrochemically stable electrolytes

DOEpatents

Angell, C.A.; Zhang, S.S.; Xu, K.

1999-01-05

This invention relates generally to inorganic ionic liquids which function as electrolytes and do not crystallize at ambient temperature. More specifically, this invention is directed to quasi-salt inorganic ionic liquids which comprise the reaction product of a strong Lewis acid with an inorganic halide-donating molecule. This invention is further directed to quasi-salt inorganic ionic liquid mixtures which comprise combinations of electrolyte additives and quasi-salt inorganic ionic liquids. These quasi-salt inorganic ionic liquid mixtures are useful electrolytes. 16 figs.

Maleimido substituted aromatic cyclotriphosphazenes

NASA Technical Reports Server (NTRS)

Kumar, D.; Fohlen, G. M.; Parker, J. A. (Inventor)

1985-01-01

4-Aminophenoxy cyclotriphosphazenes are reacted with maleic anhydride to produce maleamic acids which are converted to the maleimides. The maleimides are polymerized. By selection of starting materials (e.g., hexakis amino or trisaminophenoxy-trisphenoxy-cyclo-triphosphazenes), selection of molar proportions of reactants, use of mixtures of anhydrides and use of dianhydrides as bridging groups a variety of maleimides and polymers are produced. The polymers have high limiting oxygen indices, high char yields and other useful heat and fire resistant properties making them useful as, for example, impregnants of fabrics.

Novel duplex vapor-electrochemical method for silicon solar cells

NASA Technical Reports Server (NTRS)

Nanis, L.; Sanjurjo, A.; Sancier, K. M.; Kapur, V. K.; Bartlett, R. W.; Westphal, S.

1980-01-01

A process was developed for the economic production of high purity Si from inexpensive reactants, based on the Na reduction of SiF4 gas. The products of reaction (NaF, Si) are separated by either aqueous leaching or by direct melting of the NaF-Si product mixture. Impurities known to degrade solar cell performance are all present at sufficiently low concentrations so that melt solidification (e.g., Czochralski) will provide a silicon material suitable for solar cells.

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

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.

Lithiated imines: solvent-dependent aggregate structures and mechanisms of alkylation.

PubMed

Zuend, Stephan J; Ramirez, Antonio; Lobkovsky, Emil; Collum, David B

2006-05-03

We describe efforts to understand the structure and reactivity of lithiated cyclohexanone N-cyclohexylimine. The lithioimine affords complex solvent-dependent distributions of monomers, dimers, and trimers in a number of ethereal solvents. Careful selection of solvent provides exclusively monosolvated dimers. Rate studies on the C-alkylations reveal chronic mixtures of monomer- and dimer-based pathways. We explore the factors influencing reactants and alkylation transition structures and the marked differences between lithioimines and isostructural lithium dialkylamides with the aid of density functional theory calculations.

Aromatic cyclotriphosphazenes

NASA Technical Reports Server (NTRS)

Kamar, Devendra (Inventor); Fohlen, George M. (Inventor); Parker, John A. (Inventor)

1988-01-01

Four-Aminophenoxy cyclotriphosphazenes are reacted with maleic anhydride to produce maleamic acids which are converted to the maleimides. The maleimides are polymerized. By selection of starting materials (e.g., hexakis amino or trisaminophenoxy trisphenoxy cyclotrisphosphazenes), selection of molar porportions of reactants, use of mixtures of anhydrides and use of dianhydrides as bridging groups a variety of maleimides and polymers are produced. The polymers have high limiting oxygen indices, high char yields and other useful heat and fire resistant properties making them useful as, for example, impregnants of fabrics.

Metastable liquid lamellar structures in binary and ternary mixtures of Lennard-Jones fluids

NASA Astrophysics Data System (ADS)

Díaz-Herrera, Enrique; Ramírez-Santiago, Guillermo; Moreno Razo, José A.

2004-03-01

We have carried out extensive equilibrium MD simulations to investigate the Liquid-Vapor coexistence in partially miscible binary and ternary mixtures LJ fluids. We have studied in detail the time evolution of the density profiles and the interfacial properties in a temperature region of the phase diagram where the condensed phase is demixed. The composition of the mixtures are fixed, 50% for the binary mixture and 33.33% for the ternary mixture. The results of the simulations clearly indicate that in the range of temperatures 78 < T < 102 ^oK,--in the scale of argon-- the system evolves towards a metastable alternated liquid-liquid lamellar state in coexistence with its vapor phase. These states can be achieved if the initial configuration is fully disordered, that is, when the particles of the fluids are randomly placed on the sites of an FCC crystal or the system is completely mixed. As temperature decreases these states become very well defined and more stable in time. We find that below 90 ^oK, the alternated liquid-liquid lamellar state remains alive for 80 ns, in the scale of argon, the longest simulation we have carried out. Nonetheless, we believe that in this temperature region these states will be alive for even much longer times.

CuInS2/ZnS QD-ferroelectric liquid crystal mixtures for faster electro-optical devices and their energy storage aspects

NASA Astrophysics Data System (ADS)

Singh, Dharmendra Pratap; Vimal, Tripti; Mange, Yatin J.; Varia, Mahesh C.; Nann, Thomas; Pandey, K. K.; Manohar, Rajiv; Douali, Redouane

2018-01-01

CuInS2/ZnS core/shell quantum dots (CIS/ZnS QDs) dispersed ferroelectric liquid crystal (FLC) mixtures have been characterized for their application in electro-optical devices, energy storage, and solar cells. Physical properties of the CIS/ZnS QD-FLC (ferroelectric liquid crystal) mixtures have also been investigated with varying QD concentrations in order to optimize the critical concentration of QDs in mixtures. The presence of QDs breaks the geometrical symmetry in the FLC matrix, which results in a change in the physical properties of the mixtures. We observed the reduced values of primary and secondary order parameters (tilt angle and spontaneous polarization, respectively) for mixtures, which also depend on the concentration of QDs. The reduction of spontaneous polarization in QDs-FLC mixtures is attributed to the adverse role of flexoelectric contribution in the mixtures. The 92% faster electro-optic response and enhanced capacitance indicate the possible application of these mixtures in electro-optical devices and solar cells. Photoluminescence emission of pure FLC and QDs-FLC mixtures has been thermally tailored, which is explained by suitable models.

Flash-point prediction for binary partially miscible mixtures of flammable solvents.

PubMed

Liaw, Horng-Jang; Lu, Wen-Hung; Gerbaud, Vincent; Chen, Chan-Cheng

2008-05-30

Flash point is the most important variable used to characterize fire and explosion hazard of liquids. Herein, partially miscible mixtures are presented within the context of liquid-liquid extraction processes. This paper describes development of a model for predicting the flash point of binary partially miscible mixtures of flammable solvents. To confirm the predictive efficacy of the derived flash points, the model was verified by comparing the predicted values with the experimental data for the studied mixtures: methanol+octane; methanol+decane; acetone+decane; methanol+2,2,4-trimethylpentane; and, ethanol+tetradecane. Our results reveal that immiscibility in the two liquid phases should not be ignored in the prediction of flash point. Overall, the predictive results of this proposed model describe the experimental data well. Based on this evidence, therefore, it appears reasonable to suggest potential application for our model in assessment of fire and explosion hazards, and development of inherently safer designs for chemical processes containing binary partially miscible mixtures of flammable solvents.

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.

Low-Absorption Liquid Crystals for Infrared Beam Steering

DTIC Science & Technology

2013-10-22

Low absorption, MWIR, chlorinated liquid crystals, fluorination, FTIR, eutectic mixture, deuteration, nematic phase, birefringence, overtone...absorption compounds for LWIR and SWIR are also investigated. Key words: Low absorption, MWIR, chlorinated liquid crystals, fluorination, FTIR, eutectic ...the melting point significantly. We did careful investigation and formed a eutectic mixture consisting of five fluorinated compounds without any

Fine tuning the ionic liquid-vacuum outer atomic surface using ion mixtures.

PubMed

Villar-Garcia, Ignacio J; Fearn, Sarah; Ismail, Nur L; McIntosh, Alastair J S; Lovelock, Kevin R J

2015-03-28

Ionic liquid-vacuum outer atomic surfaces can be created that are remarkably different from the bulk composition. In this communication we demonstrate, using low-energy ion scattering (LEIS), that for ionic liquid mixtures the outer atomic surface shows significantly more atoms from anions with weaker cation-anion interactions (and vice versa).

Potential low cost, safe, high efficiency propellant for future space program

NASA Astrophysics Data System (ADS)

Zhou, D.

2005-03-01

Mixtures of nanometer or micrometer sized carbon powder suspended in hydrogen and methane/hydrogen mixtures are proposed as candidates for low cost, high efficiency propellants for future space programs. While liquid hydrogen has low weight and high heat of combustion per unit mass, because of the low mass density the heat of combustion per unit volume is low, and the liquid hydrogen storage container must be large. The proposed propellants can produce higher gross heat combustion with small volume with trade off of some weight increase. Liquid hydrogen can serve as the fluid component of the propellant in the mixtures and thus used by current rocket engine designs. For example, for the same volume a mixture of 5% methane and 95% hydrogen, can lead to an increase in the gross heat of combustion by about 10% and an increase in the Isp (specific impulse) by 21% compared to a pure liquid hydrogen propellant. At liquid hydrogen temperatures of 20.3 K, methane will be in solid state, and must be formed as fine granules (or slush) to satisfy the requirement of liquid propellant engines.

Confinement-Driven Phase Separation of Quantum Liquid Mixtures

NASA Astrophysics Data System (ADS)

Prisk, T. R.; Pantalei, C.; Kaiser, H.; Sokol, P. E.

2012-08-01

We report small-angle neutron scattering studies of liquid helium mixtures confined in Mobil Crystalline Material-41 (MCM-41), a porous silica glass with narrow cylindrical nanopores (d=3.4nm). MCM-41 is an ideal model adsorbent for fundamental studies of gas sorption in porous media because its monodisperse pores are arranged in a 2D triangular lattice. The small-angle scattering consists of a series of diffraction peaks whose intensities are determined by how the imbibed liquid fills the pores. Pure He4 adsorbed in the pores show classic, layer-by-layer film growth as a function of pore filling, leaving the long range symmetry of the system intact. In contrast, the adsorption of He3-He4 mixtures produces a structure incommensurate with the pore lattice. Neither capillary condensation nor preferential adsorption of one helium isotope to the pore walls can provide the symmetry-breaking mechanism. The scattering is consistent with the formation of randomly distributed liquid-liquid microdomains ˜2.3nm in size, providing evidence that confinement in a nanometer scale capillary can drive local phase separation in quantum liquid mixtures.

Propagation of Pressure Waves, Caused by a Thermal Shock, in Liquid Metals Containing Gas Bubbles

NASA Astrophysics Data System (ADS)

Okita, Kohei; Takagi, Shu; Matsumoto, Yoichiro

The propagation of pressure waves caused by a thermal shock in liquid mercury containing micro gas bubbles has been simulated numerically. In the present study, we clarify the influences of the introduced bubble size and void fraction on the absorption of thermal expansion of liquid mercury and attenuation of pressure waves. The mass, momentum and energy conservation equations for both bubbly mixture and gas inside each bubble are solved, in which the bubble dynamics is represented by the Keller equation. The results show that when the initial void fraction is larger than the rate of the thermal expansion of liquid mercury, the pressure rise caused by the thermal expansion decreases with decreasing the bubble radius, because of the increase of the natural frequency of bubbly mixture. On the other hand, as the bubble radius increases, the peak of pressure waves which propagate at the sound speed of mixture decreases gradually due to the dispersion effect of mixture. When the natural frequency of the mixture with large bubbles is lower than that of the thremal shock, the peak pressure at the wall increases because the pressure waves propagate through the mixture at the sound speed of liquid mercury. The comparison of the results with and without heat transfer through the gas liquid interface shows that the pressure waves are attenuated greatly by the thermal damping effect with the decrease of the void fraction which enhances the nonlinearity of bubble oscillation.

Communication: Unusual structure and transport in ionic liquid-hexane mixtures

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

Liang, Min; Khatun, Sufia; Castner, Edward W., E-mail: ecastner@rci.rutgers.edu

2015-03-28

Ionic liquids having a sufficiently amphiphilic cation can dissolve large volume fractions of alkanes, leading to mixtures with intriguing properties on molecular length scales. The trihexyl(tetradecyl)phosphonium cation paired with the bis(trifluoromethylsulfonyl)amide anion provides an ionic liquid that can dissolve large mole fractions of hexane. We present experimental results on mixtures of n-C{sub 6}D{sub 14} with this ionic liquid. High-energy X-ray scattering studies reveal a persistence of the characteristic features of ionic liquid structure even for 80% dilution with n-C{sub 6}D{sub 14}. Nuclear magnetic resonance self-diffusion results reveal decidedly non-hydrodynamic behavior where the self-diffusion of the neutral, non-polar n-C{sub 6}D{sub 14}more » is on average a factor of 21 times faster than for the cation. Exploitation of the unique structural and transport properties of these mixtures may lead to new opportunities for designer solvents for enhanced chemical reactivity and interface science.« less

Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors.

PubMed

Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

2018-04-07

A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br - in PIL-M-(Br) and TFSI - in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br - and TFSI - , respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g - ¹, 40 and 48 kW·kg - ¹, and 107 and 59.9 Wh·kg - ¹ were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively.

Communication: Unusual structure and transport in ionic liquid-hexane mixtures

DOE PAGES

Liang, Min; Khatun, Sufia; Castner, Edward W.

2015-03-28

Ionic liquids having a sufficiently amphiphilic cation can dissolve large volume fractions of alkanes, leading to mixtures with intriguing properties on molecular length scales. The trihexyl(tetradecyl)phosphonium cation paired with the bis(trifluoromethylsulfonyl)amide anion provides an ionic liquid that can dissolve large mole fractions of hexane. We present experimental results on mixtures of n-C 6D 14 with this ionic liquid. High- energy X-ray scattering studies reveal a persistence of the characteristic features of ionic liquid structure even for 80% dilution with n-C 6D 14. NMR self-diffusion results reveal decidedly non-hydrodynamic behavior where the self-diffusion of the neutral, non-polar n-C 6D 14 ismore » on average a factor of 21 times faster than for the cation. Exploitation of the unique structural and transport properties of these mixtures may lead to new opportunities for designer solvents for enhanced chemical reactivity and interface science.« less

A Review and Evaluation of the Phase Equilibria, Liquid-Phase Heats of Mixing and Excess Volumes, and Gas-Phase PVT Measurements for Nitrogen+Methane

NASA Astrophysics Data System (ADS)

Kidnay, A. J.; Miller, R. C.; Sloan, E. D.; Hiza, M. J.

1985-07-01

The available experimental data for vapor-liquid equilibria, heat of mixing, change in volume on mixing for liquid mixtures, and gas-phase PVT measurements for nitrogen+methane have been reviewed and where possible evaluated for consistency. The derived properties chosen for analysis and correlation were liquid mixture excess Gibbs free energies, and Henry's constants.

Dielectric study on mixtures of ionic liquids.

PubMed

Thoms, E; Sippel, P; Reuter, D; Weiß, M; Loidl, A; Krohns, S

2017-08-07

Ionic liquids are promising candidates for electrolytes in energy-storage systems. We demonstrate that mixing two ionic liquids allows to precisely tune their physical properties, like the dc conductivity. Moreover, these mixtures enable the gradual modification of the fragility parameter, which is believed to be a measure of the complexity of the energy landscape in supercooled liquids. The physical origin of this index is still under debate; therefore, mixing ionic liquids can provide further insights. From the chemical point of view, tuning ionic liquids via mixing is an easy and thus an economic way. For this study, we performed detailed investigations by broadband dielectric spectroscopy and differential scanning calorimetry on two mixing series of ionic liquids. One series combines an imidazole based with a pyridine based ionic liquid and the other two different anions in an imidazole based ionic liquid. The analysis of the glass-transition temperatures and the thorough evaluations of the measured dielectric permittivity and conductivity spectra reveal that the dynamics in mixtures of ionic liquids are well defined by the fractions of their parent compounds.

Organosilica Membrane with Ionic Liquid Properties for Separation of Toluene/H₂ Mixture.

PubMed

Hirota, Yuichiro; Maeda, Yohei; Yamamoto, Yusuke; Miyamoto, Manabu; Nishiyama, Norikazu

2017-08-03

In this study, we present a new concept in chemically stabilized ionic liquid membranes: an ionic liquid organosilica (ILOS) membrane, which is an organosilica membrane with ionic liquid-like properties. A silylated ionic liquid was used as a precursor for synthesis. The permselectivity, permeation mechanism, and stability of the membrane in the H₂/toluene binary system were then compared with a supported ionic liquid membrane. The membrane showed a superior separation factor of toluene/H₂ (>17,000) in a binary mixture system based on a solution-diffusion mechanism with improved durability over the supported ionic liquid membrane.

Ferroelectric BaTiO3 and LiNbO3 Nanoparticles Dispersed in Ferroelectric Liquid Crystal Mixtures: Electrooptic and Dielectric (Postprint)

DTIC Science & Technology

2016-10-14

Nematic Liquid Crystals allowing for rapidly changing moving pictures during the time frame below about 5-10 ms. Ferroelectric Liquid Crystals (FLCs...could fill this gap bearing some advantages over Nematic Liquid Crystals , mainly a fast switching time in the microsecond range, better optical...AFRL-RX-WP-JA-2017-0210 FERROELECTRIC BaTiO3 AND LiNbO3 NANOPARTICLES DISPERSED IN FERROELECTRIC LIQUID CRYSTAL MIXTURES: ELECTROOPTIC

Method for harvesting rare earth barium copper oxide single crystals

DOEpatents

Todt, V.R.; Sengupta, S.; Shi, D.

1996-04-02

A method of preparing high temperature superconductor single crystals is disclosed. The method of preparation involves preparing precursor materials of a particular composition, heating the precursor material to achieve a peritectic mixture of peritectic liquid and crystals of the high temperature superconductor, cooling the peritectic mixture to quench directly the mixture on a porous, wettable inert substrate to wick off the peritectic liquid, leaving single crystals of the high temperature superconductor on the porous substrate. Alternatively, the peritectic mixture can be cooled to a solid mass and reheated on a porous, inert substrate to melt the matrix of peritectic fluid while leaving the crystals melted, allowing the wicking away of the peritectic liquid. 2 figs.

Method for harvesting rare earth barium copper oxide single crystals

DOEpatents

Todt, Volker R.; Sengupta, Suvankar; Shi, Donglu

1996-01-01

A method of preparing high temperature superconductor single crystals. The method of preparation involves preparing precursor materials of a particular composition, heating the precursor material to achieve a peritectic mixture of peritectic liquid and crystals of the high temperature superconductor, cooling the peritectic mixture to quench directly the mixture on a porous, wettable inert substrate to wick off the peritectic liquid, leaving single crystals of the high temperature superconductor on the porous substrate. Alternatively, the peritectic mixture can be cooled to a solid mass and reheated on a porous, inert substrate to melt the matrix of peritectic fluid while leaving the crystals melted, allowing the wicking away of the peritectic liquid.

Evidence for phase separation of ethanol-water mixtures at the hydrogen terminated nanocrystalline diamond surface.

PubMed

Janssens, Stoffel D; Drijkoningen, Sien; Saitner, Marc; Boyen, Hans-Gerd; Wagner, Patrick; Larsson, Karin; Haenen, Ken

2012-07-28

Interactions between ethanol-water mixtures and a hydrophobic hydrogen terminated nanocrystalline diamond surface, are investigated by sessile drop contact angle measurements. The surface free energy of the hydrophobic surface, obtained with pure liquids, differs strongly from values obtained by ethanol-water mixtures. Here, a model which explains this difference is presented. The model suggests that, due to a higher affinity of ethanol for the hydrophobic surface, when compared to water, a phase separation occurs when a mixture of both liquids is in contact with the H-terminated diamond surface. These results are supported by a computational study giving insight in the affinity and related interaction at the liquid-solid interface.

Two-phase turbine engines. [using gas-liquid mixture accelerated in nozzles

NASA Technical Reports Server (NTRS)

Elliott, D. G.; Hays, L. G.

1976-01-01

A description is given of a two-phase turbine which utilizes a uniform mixture of gas and liquid accelerated in nozzles of the types reported by Elliott and Weinberg (1968). The mixture acts directly on an axial flow or tangential impulse turbine or is separated into gas and liquid streams which operate separately on a gas turbine and a hydraulic turbine. The basic two-phase cycles are examined, taking into account working fluids, aspects of nozzle expansion, details of turbine cycle operation, and the effect of mixture ratio variation. Attention is also given to two-phase nozzle efficiency, two-phase turbine operating characteristics and efficiencies, separator turbines, and impulse turbine experiments.

Liquid for absorption of solar heat

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

Nakamura, T.; Iwamoto, Y.; Kadotani, K.

A liquid for the absorption of solar heat, useful as an heat-absorbing medium in water heaters and heat collectors comprises: a dispersing medium selected from the group consisting of propylene glycol, mixture of propylene glycol with water, mixture of propylene glycol with water and glycerin, and mixture of glycerin with water, a dispersant selected from the group consisting of polyvinylpyrrolidone, caramel, and mixture of polyvinylpyrrolidone with caramel, and a powdered activated carbon as a black coloring material.

Thin liquid films with time-dependent chemical reactions sheared by an ambient gas flow

NASA Astrophysics Data System (ADS)

Bender, Achim; Stephan, Peter; Gambaryan-Roisman, Tatiana

2017-08-01

Chemical reactions in thin liquid films are found in many industrial applications, e.g., in combustion chambers of internal combustion engines where a fuel film can develop on pistons or cylinder walls. The reactions within the film and the turbulent outer gas flow influence film stability and lead to film breakup, which in turn can lead to deposit formation. In this work we examine the evolution and stability of a thin liquid film in the presence of a first-order chemical reaction and under the influence of a turbulent gas flow. Long-wave theory with a double perturbation analysis is used to reduce the complexity of the problem and obtain an evolution equation for the film thickness. The chemical reaction is assumed to be slow compared to film evolution and the amount of reactant in the film is limited, which means that the reaction rate decreases with time as the reactant is consumed. A linear stability analysis is performed to identify the influence of reaction parameters, material properties, and environmental conditions on the film stability limits. Results indicate that exothermic reactions have a stabilizing effect whereas endothermic reactions destabilize the film and can lead to rupture. It is shown that an initially unstable film can become stable with time as the reaction rate decreases. The shearing of the film by the external gas flow leads to the appearance of traveling waves. The shear stress magnitude has a nonmonotonic influence on film stability.

Liquid over-feeding air conditioning system and method

DOEpatents

Mei, V.C.; Chen, F.C.

1993-09-21

A refrigeration air conditioning system utilizing a liquid over-feeding operation is described. A liquid refrigerant accumulator-heat exchanger is placed in the system to provide a heat exchange relationship between hot liquid refrigerant discharged from condenser and a relatively cool mixture of liquid and vaporous refrigerant discharged from the evaporator. This heat exchange relationship substantially sub-cools the hot liquid refrigerant which undergoes little or no evaporation across the expansion device and provides a liquid over-feeding operation through the evaporator for effectively using 100 percent of evaporator for cooling purposes and for providing the aforementioned mixture of liquid and vaporous refrigerant. 1 figure.

Background Information on the He(3) Nuclear Gyroscope.

DTIC Science & Technology

1983-02-01

however, that sincew0 is not fixed by any constant of nature , its phase and frequency must be initially established by measurement when the gyro case is...sequence of longitudinal relaxation time (T1) measurements were made on a standard He3 -He4 liquid mixture (He3 concentration of 7 x 10 4) as a function of...Analysis of Experimental FPD Data on a Liquid Mixture Free precession data of a standard He 3-He4 liquid mixture (He3 concentration of 7 x 10- 4) were

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.

Controlled irrigation of a structured packing as a method for increasing the efficiency of liquid mixture separation in the distillation column

NASA Astrophysics Data System (ADS)

Pavlenko, A. N.; Zhukov, V. E.; Pecherkin, N. I.; Nazarov, A. D.; Li, X.; Li, H.; Gao, X.; Sui, H.

2017-09-01

The use of modern structured packing in the distillation columns allows much more even distribution of the liquid film over the packing surface, but it does not completely solve the problem of uniform distribution of flow parameters over the entire height of the packing. Negative stratification of vapor along the packing height caused by different densities of vapor mixture components and higher temperature in the lower part of the column leads to formation of large-scale maldistributions of temperature and mixture composition over the column cross-section even under the conditions of uniform irrigation of packing with liquid. In these experiments, the idea of compensatory action of liquid distributor on the large-scale maldistribution of mixture composition over the column cross-section was implemented. The experiments were carried out in the distillation column with the diameter of 0.9 m on 10 layers of the Mellapak 350Y packing with the total height of 2.1 m. The mixture of R-21 and R-114 was used as the working mixture. To irrigate the packing, the liquid distributorr with 126 independently controlled solenoid valves overlapping the holes with the diameter of 5 mm, specially designed by the authors, was used. Response of the column to the action of liquid distributor was observed in real time according to the indications of 3 groups of thermometers mounted in 3 different cross-sections of the column. The experiments showed that the minimal correction of the drip point pattern in the controlled liquid distributor can significantly affect the pattern of flow parameter distribution over the cross-section and height of the mass transfer surface and increase separation efficiency of the column within 20%.

Universal adsorption at the vapor-liquid interface near the consolute point

NASA Technical Reports Server (NTRS)

Schmidt, James W.

1990-01-01

The ellipticity of the vapor-liquid interface above mixtures of methylcyclohexane (C7H14) and perfluoromethylcyclohexane (C7F14) has been measured near the consolute point T(c) = 318.6 K. The data are consistent with a model of the interface that combines a short-ranged density-vs height profile in the vapor phase with a much longer-ranged composition-versus-height profile in the liquid. The value of the free parameter produced by fitting the model to the data is consistent with results from two other simple mixtures and a mixture of a polymer and solvent. This experiment combines precision ellipsometry of the vapor-liquid interface with in situ measurements of refractive indices of the liquid phases, and it precisely locates the consolute point.

Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy

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

Lam, Royce K.; Smith, Jacob W.; Saykally, Richard J., E-mail: saykally@berkeley.edu

While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure.more » The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility.« less

Acoustic composition sensor for cryogenic gas mixtures

NASA Technical Reports Server (NTRS)

Shakkottai, P.; Kwack, E. Y.; Luchik, T. S.; Back, L. H.

1991-01-01

An acoustic sensor useful for the determination of the composition of a gaseous binary mixture in cryogenic liquid spills has been characterized. One version of the instrument traps a known mixture of helium and nitrogen at ambient temperature in a tube which is interrogated by sonic pulses to determine the speed of sound and hence the composition. Experimental data shows that this sensor is quite accurate. The second version uses two unconfined microphones which sense sound pulses. Experimental data acquired during mixing when liquid nitrogen is poured into a vessel of gaseous helium is presented. Data during transient cooling of the tubular sensor containing nitrogen when the sensor is dipped into liquid nitrogen and during transient warm-up when the sensor is withdrawn are also presented. This sensor is being developed for use in the mixing of liquid cryogens with gas evolution in the simulation of liquid hydrogen/liquid oxygen explosion hazards.

Acoustic composition sensor for cryogenic gas mixtures

NASA Astrophysics Data System (ADS)

Shakkottai, P.; Kwack, E. Y.; Luchik, T. S.; Back, L. H.

An acoustic sensor useful for the determination of the composition of a gaseous binary mixture in cryogenic liquid spills has been characterized. One version of the instrument traps a known mixture of helium and nitrogen at ambient temperature in a tube which is interrogated by sonic pulses to determine the speed of sound and hence the composition. Experimental data shows that this sensor is quite accurate. The second version uses two unconfined microphones which sense sound pulses. Experimental data acquired during mixing when liquid nitrogen is poured into a vessel of gaseous helium is presented. Data during transient cooling of the tubular sensor containing nitrogen when the sensor is dipped into liquid nitrogen and during transient warm-up when the sensor is withdrawn are also presented. This sensor is being developed for use in the mixing of liquid cryogens with gas evolution in the simulation of liquid hydrogen/liquid oxygen explosion hazards.

Soft Argon-Propane Dielectric Barrier Discharge Ionization.

PubMed

Schütz, Alexander; Lara-Ortega, Felipe J; Klute, Felix David; Brandt, Sebastian; Schilling, Michael; Michels, Antje; Veza, Damir; Horvatic, Vlasta; García-Reyes, Juan F; Franzke, Joachim

2018-03-06

Dielectric barrier discharges (DBDs) have been used as soft ionization sources (DBDI) for organic mass spectrometry (DBDI-MS) for approximately ten years. Helium-based DBDI is often used because of its good ionization efficiency, low ignition voltage, and homogeneous plasma conditions. Argon needs much higher ignition voltages than helium when the same discharge geometry is used. A filamentary plasma, which is not suitable for soft ionization, may be produced instead of a homogeneous plasma. This difference results in N 2 , present in helium and argon as an impurity, being Penning-ionized by helium but not by metastable argon atoms. In this study, a mixture of argon and propane (C 3 H 8 ) was used as an ignition aid to decrease the ignition and working voltages, because propane can be Penning-ionized by argon metastables. This approach leads to homogeneous argon-based DBDI. Furthermore, operating DBDI in an open environment assumes that many uncharged analyte molecules do not interact with the reactant ions. To overcome this disadvantage, we present a novel approach, where the analyte is introduced in an enclosed system through the discharge capillary itself. This nonambient DBDI-MS arrangement is presented and characterized and could advance the novel connection of DBDI with analytical separation techniques such as gas chromatography (GC) and high-pressure liquid chromatography (HPLC) in the near future.

Supercritical Water Mixture (SCWM) Experiment in the High Temperature Insert-Reflight (HTI-R)

NASA Technical Reports Server (NTRS)

Hicks, Michael C.; Hegde, Uday G.; Garrabos, Yves; Lecoutre, Carole; Zappoli, Bernard

2013-01-01

Current research on supercritical water processes on board the International Space Station (ISS) focuses on salt precipitation and transport in a test cell designed for supercritical water. This study, known as the Supercritical Water Mixture Experiment (SCWM) serves as a precursor experiment for developing a better understanding of inorganic salt precipitation and transport during supercritical water oxidation (SCWO) processes for the eventual application of this technology for waste management and resource reclamation in microgravity conditions. During typical SCWO reactions any inorganic salts present in the reactant stream will precipitate and begin to coat reactor surfaces and control mechanisms (e.g., valves) often severely impacting the systems performance. The SCWM experiment employs a Sample Cell Unit (SCU) filled with an aqueous solution of Na2SO4 0.5-w at the critical density and uses a refurbished High Temperature Insert, which was used in an earlier ISS experiment designed to study pure water at near-critical conditions. The insert, designated as the HTI-Reflight (HTI-R) will be deployed in the DECLIC (Device for the Study of Critical Liquids and Crystallization) Facility on the International Space Station (ISS). Objectives of the study include measurement of the shift in critical temperature due to the presence of the inorganic salt, assessment of the predominant mode of precipitation (i.e., heterogeneously on SCU surfaces or homogeneously in the bulk fluid), determination of the salt morphology including size and shapes of particulate clusters, and the determination of the dominant mode of transport of salt particles in the presence of an imposed temperature gradient. Initial results from the ISS experiments will be presented and compared to findings from laboratory experiments on the ground.

Effects of equivalence ratio variation on lean, stratified methane-air laminar counterflow flames

NASA Astrophysics Data System (ADS)

Richardson, E. S.; Granet, V. E.; Eyssartier, A.; Chen, J. H.

2010-11-01

The effects of equivalence ratio variations on flame structure and propagation have been studied computationally. Equivalence ratio stratification is a key technology for advanced low emission combustors. Laminar counterflow simulations of lean methane-air combustion have been presented which show the effect of strain variations on flames stabilized in an equivalence ratio gradient, and the response of flames propagating into a mixture with a time-varying equivalence ratio. 'Back supported' lean flames, whose products are closer to stoichiometry than their reactants, display increased propagation velocities and reduced thickness compared with flames where the reactants are richer than the products. The radical concentrations in the vicinity of the flame are modified by the effect of an equivalence ratio gradient on the temperature profile and thermal dissociation. Analysis of steady flames stabilized in an equivalence ratio gradient demonstrates that the radical flux through the flame, and the modified radical concentrations in the reaction zone, contribute to the modified propagation speed and thickness of stratified flames. The modified concentrations of radical species in stratified flames mean that, in general, the reaction rate is not accurately parametrized by progress variable and equivalence ratio alone. A definition of stratified flame propagation based upon the displacement speed of a mixture fraction dependent progress variable was seen to be suitable for stratified combustion. The response times of the reaction, diffusion, and cross-dissipation components which contribute to this displacement speed have been used to explain flame response to stratification and unsteady fluid dynamic strain.

Characterizing Dissolved Gases in Cryogenic Liquid Fuels

NASA Astrophysics Data System (ADS)

Richardson, Ian A.

Pressure-Density-Temperature-Composition (PrhoT-x) measurements of cryogenic fuel mixtures are a historical challenge due to the difficulties of maintaining cryogenic temperatures and precision isolation of a mixture sample. For decades NASA has used helium to pressurize liquid hydrogen propellant tanks to maintain tank pressure and reduce boil off. This process causes helium gas to dissolve into liquid hydrogen creating a cryogenic mixture with thermodynamic properties that vary from pure liquid hydrogen. This can lead to inefficiencies in fuel storage and instabilities in fluid flow. As NASA plans for longer missions to Mars and beyond, small inefficiencies such as dissolved helium in liquid propellant become significant. Traditional NASA models are unable to account for dissolved helium due to a lack of fundamental property measurements necessary for the development of a mixture Equation Of State (EOS). The first PrhoT-x measurements of helium-hydrogen mixtures using a retrofitted single-sinker densimeter, magnetic suspension microbalance, and calibrated gas chromatograph are presented in this research. These measurements were used to develop the first multi-phase EOS for helium-hydrogen mixtures which was implemented into NASA's Generalized Fluid System Simulation Program (GFSSP) to determine the significance of mixture non-idealities. It was revealed that having dissolved helium in the propellant does not have a significant effect on the tank pressurization rate but does affect the rate at which the propellant temperature rises. PrhoT-x measurements are conducted on methane-ethane mixtures with dissolved nitrogen gas to simulate the conditions of the hydrocarbon seas of Saturn's moon Titan. Titan is the only known celestial body in the solar system besides Earth with stable liquid seas accessible on the surface. The PrhoT-x measurements are used to develop solubility models to aid in the design of the Titan Submarine. NASA is currently designing the submarine to explore the depths of Titan's methane-ethane seas to study the evolution of hydrocarbons in the universe and provide a pathfinder for future submersible designs. In addition, effervescence and freezing liquid line measurements on various liquid methane-ethane compositions with dissolved gaseous nitrogen are presented from 1.5 bar to 4.5 bar and temperatures from 92 K to 96 K to improve simulations of the conditions of the seas. These measurements will be used to validate sea property and bubble incipience models for the Titan Submarine design.

How Is the Freezing Point of a Binary Mixture of Liquids Related to the Composition? A Guided Inquiry Experiment

ERIC Educational Resources Information Center

Hunnicutt, Sally S.; Grushow, Alexander; Whitnell, Rob

2017-01-01

The principles of process-oriented guided inquiry learning (POGIL) are applied to a binary solid-liquid mixtures experiment. Over the course of two learning cycles, students predict, measure, and model the phase diagram of a mixture of fatty acids. The enthalpy of fusion of each fatty acid is determined from the results. This guided inquiry…

Measuring the Densities of Aqueous Glasses at Cryogenic Temperatures.

PubMed

Shen, Chen; Julius, Ethan F; Tyree, Timothy J; Dan, Ritwik; Moreau, David W; Thorne, Robert

2017-06-28

We demonstrate a method for determining the vitreous phase cryogenic temperature densities of aqueous mixtures, and other samples that require rapid cooling, to prepare the desired cryogenic temperature phase. Microliter to picoliter size drops are cooled by projection into a liquid nitrogen-argon (N2-Ar) mixture. The cryogenic temperature phase of the drop is evaluated using a visual assay that correlates with X-ray diffraction measurements. The density of the liquid N2-Ar mixture is adjusted by adding N2 or Ar until the drop becomes neutrally buoyant. The density of this mixture and thus of the drop is determined using a test mass and Archimedes principle. With appropriate care in drop preparation, management of gas above the liquid cryogen mixture to minimize icing, and regular mixing of the cryogenic mixture to prevent density stratification and phase separation, densities accurate to <0.5% of drops as small as 50 pL can readily be determined. Measurements on aqueous cryoprotectant mixtures provide insight into cryoprotectant action, and provide quantitative data to facilitate thermal contraction matching in biological cryopreservation.

Pressurized feed-injection spray-forming apparatus

DOEpatents

Berry, R.A.; Fincke, J.R.; McHugh, K.M.

1995-08-29

A spray apparatus and method are disclosed for injecting a heated, pressurized liquid in a first predetermined direction into a pressurized gas flow that is flowing in a second predetermined direction, to provide for atomizing and admixing the liquid with the gas to form a two-phase mixture. A valve is also disposed within the injected liquid conduit to provide for a pulsed injection of the liquid and timed deposit of the atomized gas phase. Preferred embodiments include multiple liquid feed ports and reservoirs to provide for multiphase mixtures of metals, ceramics, and polymers. 22 figs.

Pressurized feed-injection spray-forming apparatus

DOEpatents

Berry, Ray A.; Fincke, James R.; McHugh, Kevin M.

1995-01-01

A spray apparatus and method for injecting a heated, pressurized liquid in a first predetermined direction into a pressurized gas flow that is flowing in a second predetermined direction, to provide for atomizing and admixing the liquid with the gas to form a two-phase mixture. A valve is also disposed within the injected liquid conduit to provide for a pulsed injection of the liquid and timed deposit of the atomized gas phase. Preferred embodiments include multiple liquid feed ports and reservoirs to provide for multiphase mixtures of metals, ceramics, and polymers.

A quantum mechanical strategy to investigate the structure of liquids: the cases of acetonitrile, formamide, and their mixture.

PubMed

Mennucci, Benedetta; da Silva, Clarissa O

2008-06-05

A computational strategy based on quantum mechanical (QM) calculations and continuum solvation models is used to investigate the structure of liquids (either neat liquids or mixtures). The strategy is based on the comparison of calculated and experimental spectroscopic properties (IR-Raman vibrational frequencies and Raman intensities). In particular, neat formamide, neat acetonitrile, and their equimolar mixture are studied comparing isolated and solvated clusters of different nature and size. In all cases, the study seems to indicate that liquids, even when strongly associated, can be effectively modeled in terms of a shell-like system in which clusters of strongly interacting molecules (the microenvironments) are solvated by a polarizable macroenvironment represented by the rest of the molecules. Only taking into proper account both these effects can a correct picture of the liquid structure be achieved.

Reducing Dangerous Effects of Unsymmetrical Dimethyl Hydrazine as a Liquid Propellant by Addition of Hydroxyethylhydrazine, Part II, Performance with Several Oxidizers

NASA Astrophysics Data System (ADS)

Keshavarz, Mohammad Hossein; Ramadan, Alireza; Mousaviazar, Ali; Zali, Abbas; Shokrollahi, Arash

2011-07-01

This work continues the study of suitable binary liquid mixtures of unsymmetrical dimethylhydrazine (UDMH) and hydroxyethylhydrazine (HEH) to reduce the harmful effects of pure UDMH. The synthesized HEH was mixed with UDMH up to 40 wt% of HEH to study the performance and properties of binary liquid mixtures of UDMH/HEH. The existence of strong hydrogen bonding between HEH and UDMH provides low-volatile mixtures of these hydrazine derivatives. The addition of HEH significantly reduces the vapor pressure of UDMH, thus reducing the known UDMH health risk to inhalation exposure. Specific impulse was used to study performance of binary mixture UDMH/HEH with respect to pure UDMH. A binary mixture of UDMH/HEH reacts spontaneously in contact with nitrogen tetroxide, red fuming nitric acid (RFNA), and inhibited red fuming nitric acid (IRFNA).

Experimental study of isopropanol dehydrogenation over amorphous alloy raney nickel catalysts

NASA Astrophysics Data System (ADS)

Xin, Fang; Xu, Min; Li, Xun-Feng; Huai, Xiu-Lan

2013-12-01

The dehydrogenation reaction of isopropanol occurring at low temperature is of great industrial importance. It is a key procedure in isopropanol/acetone/hydrogen chemical heat pump system. An experimental investigation was performed to study the behavior of the liquid phase dehydrogenation of isopropanol over amorphous alloy Raney nickel catalysts. Un-promoted and promoted catalysts were used and their performances were compared under various catalyst amounts, acetone content in the reactant and reaction temperature ranging from 348 K to 355 K. It is found that there exists an optimum catalyst concentration which is about 0.34 g in 300 ml isopropanol. The temperature has evident effect on the reaction. The presence of activities of Fe-promoted catalyst decrease slightly compared to the un-promoted catalyst when the temperature are 348 K and 351 K. Besides, the reaction rate decreases almost linearly with the increase of acetone volume fraction in the reactant.

Fluid Mechanics Optimising Organic Synthesis

NASA Astrophysics Data System (ADS)

Leivadarou, Evgenia; Dalziel, Stuart

2015-11-01

The Vortex Fluidic Device (VFD) is a new ``green'' approach in the synthesis of organic chemicals with many industrial applications in biodiesel generation, cosmetics, protein folding and pharmaceutical production. The VFD is a rapidly rotating tube that can operate with a jet feeding drops of liquid reactants to the base of the tube. The aim of this project is to explain the fluid mechanics of the VFD that influence the rate of reactions. The reaction rate is intimately related to the intense shearing that promotes collision between reactant molecules. In the VFD, the highest shears are found at the bottom of the tube in the Rayleigh and the Ekman layer and at the walls in the Stewardson layers. As a step towards optimising the performance of the VFD we present experiments conducted in order to establish the minimum drop volume and maximum rotation rate for maximum axisymmetric spreading without fingering instability. PhD candidate, Department of Applied Mathematics and Theoretical Physics.

Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

NASA Astrophysics Data System (ADS)

Hoarfrost, Megan Lane

Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there is incredible freedom in designing the block copolymer architecture in order to optimize the mechanical and other properties of the membrane without sacrificing conductivity. The derived scaling relationships are shown to be general for many block copolymer and ionic liquid chemistries. In certain cases, the mechanism of ion conduction in the ionic liquid is affected by block copolymer nanoconfinement. The introduction of excess neutral imidazole to [Im][TFSI] leads to enhanced proton conductivity as well as a high H+ transference number due to facilitated proton hopping between imidazole molecules. We show that there is increased proton hopping when the nonstoichiometric ionic liquid is confined to lamellar block copolymer nanodomains, which we hypothesize is due to changes in the hydrogen bond structure of the ionic liquid under confinement. This, in combination with unique ion aggregation behavior, leads to a lower activation energy for macroscopic ion transport compared to that in a corresponding homopolymer/ionic liquid mixture. Through this work, we further the understanding of the relationship between membrane composition, structure, and ion transport. The findings presented herein portend the rational design of nanostructured membranes having improved mechanical properties and conductivity.

Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors

PubMed Central

Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

2018-01-01

A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br− in PIL-M-(Br) and TFSI− in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br− and TFSI−, respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g−1, 40 and 48 kW·kg−1, and 107 and 59.9 Wh·kg−1 were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively. PMID:29642456

Mixtures of the 1-ethyl-3-methylimidazolium acetate ionic liquid with different inorganic salts: insights into their interactions.

PubMed

Oliveira, Filipe S; Cabrita, Eurico J; Todorovic, Smilja; Bernardes, Carlos E S; Lopes, José N Canongia; Hodgson, Jennifer L; MacFarlane, Douglas R; Rebelo, Luís P N; Marrucho, Isabel M

2016-01-28

In this work, we explore the interactions between the ionic liquid 1-ethyl-3-methylimidazolim acetate and different inorganic salts belonging to two different cation families, those based on ammonium and others based on sodium. NMR and Raman spectroscopy are used to screen for changes in the molecular environment of the ions in the ionic liquid + inorganic salt mixtures as compared to pure ionic liquid. The ion self-diffusion coefficients are determined from NMR data, allowing the discussion of the ionicity values of the ionic liquid + inorganic salt mixtures calculated using different methods. Our data reveal that preferential interactions are established between the ionic liquid and ammonium-based salts, as opposed to sodium-based salts. Computational calculations show the formation of aggregates between the ionic liquid and the inorganic salt, which is consistent with the spectroscopic data, and indicate that the acetate anion of the ionic liquid establishes preferential interactions with the ammonium cation of the inorganic salts, leaving the imidazolium cation less engaged in the media.

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.

Lithium insertion in graphite from ternary ionic liquid-lithium salt electrolytes. I. Electrochemical characterization of the electrolytes

NASA Astrophysics Data System (ADS)

Appetecchi, Giovanni B.; Montanino, Maria; Balducci, Andrea; Lux, Simon F.; Winterb, Martin; Passerini, Stefano

In this paper we report the results of chemical-physical investigation performed on ternary room temperature ionic liquid-lithium salt mixtures as electrolytes for lithium-ion battery systems. The ternary electrolytes were made by mixing N-methyl- N-propyl pyrrolidinium bis(fluorosulfonyl) imide (PYR 13FSI) and N-butyl- N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (PYR 14TFSI) ionic liquids with lithium hexafluorophosphate (LiPF 6) or lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The mixtures were developed based on preliminary results on the cyclability of graphite electrodes in the IL-LiX binary electrolytes. The results clearly show the beneficial synergic effect of the two ionic liquids on the electrochemical properties of the mixtures.

Hazards Induced by Breach of Liquid Rocket Fuel Tanks: Conditions and Risks of Cryogenic Liquid Hydrogen-Oxygen Mixture Explosions

NASA Technical Reports Server (NTRS)

Osipov, Viatcheslav; Muratov, Cyrill; Hafiychuk, Halyna; Ponizovskya-Devine, Ekaterina; Smelyanskiy, Vadim; Mathias, Donovan; Lawrence, Scott; Werkheiser, Mary

2011-01-01

We analyze the data of purposeful rupture experiments with LOx and LH2 tanks, the Hydrogen-Oxygen Vertical Impact (HOVI) tests that were performed to clarify the ignition mechanisms, the explosive power of cryogenic H2/Ox mixtures under different conditions, and to elucidate the puzzling source of the initial formation of flames near the intertank section during the Challenger disaster. We carry out a physics-based analysis of general explosions scenarios for cryogenic gaseous H2/Ox mixtures and determine their realizability conditions, using the well-established simplified models from the detonation and deflagration theory. We study the features of aerosol H2/Ox mixture combustion and show, in particular, that aerosols intensify the deflagration flames and can induce detonation for any ignition mechanism. We propose a cavitation-induced mechanism of self-ignition of cryogenic H2/Ox mixtures that may be realized when gaseous H2 and Ox flows are mixed with a liquid Ox turbulent stream, as occurred in all HOVI tests. We present an overview of the HOVI tests to make conclusion on the risk of strong explosions in possible liquid rocket incidents and provide a semi-quantitative interpretation of the HOVI data based on aerosol combustion. We uncover the most dangerous situations and discuss the foreseeable risks which can arise in space missions and lead to tragic outcomes. Our analysis relates to only unconfined mixtures that are likely to arise as a result of liquid propellant space vehicle incidents.

Molecular simulation of fluid mixtures in bulk and at solid-liquid interfaces

NASA Astrophysics Data System (ADS)

Kern, Jesse L.

The properties of a diverse range of mixture systems at interfaces are investigated using a variety of computational techniques. Molecular simulation is used to examine the thermodynamic, structural, and transport properties of heterogeneous systems of theoretical and practical importance. The study of binary hard-sphere mixtures at a hard wall demonstrates the high accuracy of recently developed classical-density functionals. The study of aluminum--gallium solid--liquid heterogeneous interfaces predicts a significant amount of prefreezing of the liquid by adopting the structure of the solid surface. The study of ethylene-expanded methanol within model silica mesopores shows the effect of confinement and surface functionalzation on the mixture composition and transport inside of the pores. From our molecular-dynamics study of binary hard-sphere fluid mixtures at a hard wall, we obtained high-precision calculations of the wall-fluid interfacial free energies, gamma. We have considered mixtures of varying diameter ratio, alpha = 0.7,0.8,0.9; mole fraction, x 1 = 0.25,0.50,0.75; and packing fraction, eta < 0.50. Using Gibbs-Cahn Integration, gamma is calculated from the system pressure, chemical potentials, and density profiles. Recent classical density-functional theory predictions agree very well with our results. Structural, thermodynamic, and transport properties of the aluminum--gallium solid--liquid interface at 368 K are obtained for the (100), (110), and (111) orientations using molecular dynamics. Density, potential energy, stress, and diffusion profiles perpendicular to the interface are calculated. The layers of Ga that form on the Al surface are strongly adsorbed and take the in-plane structure of the underlying crystal layers for all orientations, which results in significant compressive stress on the Ga atoms. Bulk methanol--ethylene mixtures under vapor-liquid equilibrium conditions have been characterized using Monte Carlo and molecular dynamics. The simulated vapor-liquid coexistence curves for the pure-component and binary mixtures agree well with experiment, as do the mixture volumetric expansion results. Using chemical potentials obtained from the bulk simulations, the filling of a number of model silica mesopores with ethylene and methanol is simulated. We report the compositions of the confined fluid mixtures over a range of pressures and for three degrees of nominal pore hydrophobicity.

Process for the separation of components from gas mixtures

DOEpatents

Merriman, J.R.; Pashley, J.H.; Stephenson, M.J.; Dunthorn, D.I.

1973-10-01

A process for the removal, from gaseous mixtures of a desired component selected from oxygen, iodine, methyl iodide, and lower oxides of carbon, nitrogen, and sulfur is described. The gaseous mixture is contacted with a liquid fluorocarbon in an absorption zone maintained at superatmospheric pressure to preferentially absorb the desired component in the fluorocarbon. Unabsorbed constituents of the gaseous mixture are withdrawn from the absorption zone. Liquid fluorocarbon enriched in the desired component is withdrawn separately from the zone, following which the desired component is recovered from the fluorocarbon absorbent. (Official Gazette)

Photochemical synthesis of biomolecules under anoxic conditions

NASA Technical Reports Server (NTRS)

Folsome, C.; Brittain, A.; Zelko, M.

1983-01-01

The long-wavelength UV anoxic photosynthesis of uracil, various sugars (including deoxyribose and glycoaldehyde), amino acids, and other organic photoproducts is reported. The reactions were conducted in a mixture of water, calcium carbonate, hydrazine, and formaldehyde which were subjected to 24 hr or 72 hr radiation. Product yields were greatest when the hydrazine/formaldehyde ratio was one, and when the reactant concentrations were low. These data suggest that organic products can be formed in variety from those amounts of formaldehyde and hydazine precursors which are themselves formed under anoxic UV photochemical conditions.

Fire and heat resistant laminating resins based on maleimido substituted aromatic cyclotriphosphazene polymer

NASA Technical Reports Server (NTRS)

Kumar, Devendra (Inventor); Fohlen, George M. (Inventor); Parker, John A. (Inventor)

1987-01-01

4-Aminophenoxy cyclotriphosphazenes are reacted with maleic anhydride to produce maleamic acids which are converted to the maleimides. The maleimides are polymerized. By selection of starting materials (e.g., hexakis amino or trisaminophenoxy trisphenoxy cyclotriphosphazenes), selection of molar proportions of reactants, use of mixtures of anhydrides and use of dianhydrides as bridging groups a variety of maleimides and polymers are produced. The polymers have high limiting oxygen indices, high char yields and other useful heat and fire resistant properties making them useful as, for example, impregnants of fabrics.

Formation of calcium in the products of iron oxide-aluminum thermite combustion in air

NASA Astrophysics Data System (ADS)

Gromov, A. A.; Gromov, A. M.; Popenko, E. M.; Sergienko, A. V.; Sabinskaya, O. G.; Raab, B.; Teipel, U.

2016-10-01

The composition of condensed products resulting from the combustion of thermite mixtures (Al + Fe2O3) in air is studied by precise methods. It is shown that during combustion, calcium is formed and stabilized in amounts of maximal 0.55 wt %, while is missing from reactants of 99.7 wt % purity. To explain this, it is hypothesized that a low-energy nuclear reaction takes place alongside the reactions of aluminum oxidation and nitridation, resulting in the formation of calcium (Kervran-Bolotov reaction).

Notre Dame Geothermal Ionic Liquids Research: Ionic Liquids for Utilization of Geothermal Energy

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

Brennecke, Joan F.

The goal of this project was to develop ionic liquids for two geothermal energy related applications. The first goal was to design ionic liquids as high temperature heat transfer fluids. We identified appropriate compounds based on both experiments and molecular simulations. We synthesized the new ILs, and measured their thermal stability, measured storage density, viscosity, and thermal conductivity. We found that the most promising compounds for this application are aminopyridinium bis(trifluoromethylsulfonyl)imide based ILs. We also performed some measurements of thermal stability of IL mixtures and used molecular simulations to better understand the thermal conductivity of nanofluids (i.e., mixtures of ILsmore » and nanoparticles). We found that the mixtures do not follow ideal mixture theories and that the addition of nanoparticles to ILs may well have a beneficial influence on the thermal and transport properties of IL-based heat transfer fluids. The second goal was to use ionic liquids in geothermally driven absorption refrigeration systems. We performed copious thermodynamic measurements and modeling of ionic liquid/water systems, including modeling of the absorption refrigeration systems and the resulting coefficients of performance. We explored some IL/organic solvent mixtures as candidates for this application, both with experimentation and molecular simulations. We found that the COPs of all of the IL/water systems were higher than the conventional system – LiBr/H2O. Thus, IL/water systems appear very attractive for absorption refrigeration applications.« less

Method and system for low-NO.sub.x dual-fuel combustion of liquid and/or gaseous fuels

DOEpatents

Gard, Vincent; Chojnacki, Dennis A; Rabovitser, Ioseph K

2014-12-02

A method and apparatus for combustion in which a pressurized preheated liquid fuel is atomized and a portion thereof flash vaporized, creating a mixture of fuel vapor and liquid droplets. The mixture is mixed with primary combustion oxidant, producing a fuel/primary oxidant mixture which is then injected into a primary combustion chamber in which the fuel/primary oxidant mixture is partially combusted, producing a secondary gaseous fuel containing hydrogen and carbon oxides. The secondary gaseous fuel is mixed with a secondary combustion oxidant and injected into the second combustion chamber wherein complete combustion of the secondary gaseous fuel is carried out. The resulting second stage flue gas containing very low amounts of NO.sub.x is then vented from the second combustion chamber.

Catalytic combustion of hydrogen-air mixtures in stagnation flows

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

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

1993-04-01

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

The simultaneous mass and energy evaporation (SM2E) model.

PubMed

Choudhary, Rehan; Klauda, Jeffery B

2016-01-01

In this article, the Simultaneous Mass and Energy Evaporation (SM2E) model is presented. The SM2E model is based on theoretical models for mass and energy transfer. The theoretical models systematically under or over predicted at various flow conditions: laminar, transition, and turbulent. These models were harmonized with experimental measurements to eliminate systematic under or over predictions; a total of 113 measured evaporation rates were used. The SM2E model can be used to estimate evaporation rates for pure liquids as well as liquid mixtures at laminar, transition, and turbulent flow conditions. However, due to limited availability of evaporation data, the model has so far only been tested against data for pure liquids and binary mixtures. The model can take evaporative cooling into account and when the temperature of the evaporating liquid or liquid mixture is known (e.g., isothermal evaporation), the SM2E model reduces to a mass transfer-only model.

An Optically Isotropic Antiferroelectric Liquid Crystal (OI-AFLC) Display Mode Operating over a Wide Temperature Range using Ternary Bent-Core Liquid Crystal Mixtures

DOE PAGES

Bergquist, Leah; Zhang, Cuiyu; Ribeiro de Almeida, Roberta R.; ...

2017-02-07

Here, we report on the synthesis and characterization of bent-core liquid crystal (LC) compounds and the preparation of mixtures that provide an optically isotropic antiferroelectric (OI-AFLC) liquid crystal display mode over a very wide temperature interval and well below room temperature. From the collection of compounds synthesized during this study, we recognized that several ternary mixtures displayed a modulated SmC aP A phase down to below -40 °C and up to about 100 °C on both heating and cooling, as well as optical tilt angles in the transformed state of approximately 45° (optically isotropic state). The materials were fully characterizedmore » and their liquid crystal as well as electro-optical properties analyzed by polarized optical microscopy, differential scanning calorimetry, synchrotron X-ray diffraction, dielectric spectroscopy, and electro-optical tests.« less

An Optically Isotropic Antiferroelectric Liquid Crystal (OI-AFLC) Display Mode Operating over a Wide Temperature Range using Ternary Bent-Core Liquid Crystal Mixtures

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

Bergquist, Leah; Zhang, Cuiyu; Ribeiro de Almeida, Roberta R.

Here, we report on the synthesis and characterization of bent-core liquid crystal (LC) compounds and the preparation of mixtures that provide an optically isotropic antiferroelectric (OI-AFLC) liquid crystal display mode over a very wide temperature interval and well below room temperature. From the collection of compounds synthesized during this study, we recognized that several ternary mixtures displayed a modulated SmC aP A phase down to below -40 °C and up to about 100 °C on both heating and cooling, as well as optical tilt angles in the transformed state of approximately 45° (optically isotropic state). The materials were fully characterizedmore » and their liquid crystal as well as electro-optical properties analyzed by polarized optical microscopy, differential scanning calorimetry, synchrotron X-ray diffraction, dielectric spectroscopy, and electro-optical tests.« less

3D printed modular centrifugal contactors and method for separating moieties using 3D printed optimized surfaces

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

Wardle, Kent E.

The present invention provides an annular centrifugal contactor, having a housing to receive a plurality of liquids; a rotor inside the housing; an annular mixing zone, with a plurality of fluid retention reservoirs; and an adjustable stem that can be raised to restrict the flow of a liquid into the rotor or lowered to increase the flow of liquid into the rotor. The invention also provides a method for transferring moieties from a first liquid to a second liquid, the method having the steps of combining the fluids in a housing whose interior has helically shaped first channels; subjecting themore » fluids to a spinning rotor to produce a mixture, whereby the channels simultaneously conduct the mixture downwardly and upwardly; and passing the mixture through the rotor to contact second channels, whereby the channels pump the second liquid through a first aperture while the first fluid exits a second aperture.« less

Sedimentation of a two-dimensional colloidal mixture exhibiting liquid-liquid and gas-liquid phase separation: a dynamical density functional theory study.

PubMed

Malijevský, Alexandr; Archer, Andrew J

2013-10-14

We present dynamical density functional theory results for the time evolution of the density distribution of a sedimenting model two-dimensional binary mixture of colloids. The interplay between the bulk phase behaviour of the mixture, its interfacial properties at the confining walls, and the gravitational field gives rise to a rich variety of equilibrium and non-equilibrium morphologies. In the fluid state, the system exhibits both liquid-liquid and gas-liquid phase separation. As the system sediments, the phase separation significantly affects the dynamics and we explore situations where the final state is a coexistence of up to three different phases. Solving the dynamical equations in two-dimensions, we find that in certain situations the final density profiles of the two species have a symmetry that is different from that of the external potentials, which is perhaps surprising, given the statistical mechanics origin of the theory. The paper concludes with a discussion on this.

Structural and dielectric behaviors of Bi4Ti3O12 - lyotropic liquid crystalline nanocolloids

NASA Astrophysics Data System (ADS)

Shukla, Ravi K.; Raina, K. K.

2018-03-01

We investigated the structural and dielectric dynamics of nanocolloids comprising lyotropic liquid crystals and bismuth titanate (Bi4Ti3O12) spherical nanoparticles (≈16-18 nm) of varying concentration 0.05 and 0.1 wt%. The lyotropic liquid crystalline mixture was prepared by a binary mixture of cetylpyridinuium chloride and ethylene glycol mixed in 5:95 wt% ratio. Binary lyotropic mixture exhibited hexagonal lyotropic phase. Structural and textural characterizations of nanocolloids infer that the nanoparticles were homogeneously dispersed in the liquid crystalline matrix and did not perturb the hexagonal ordering of the lyotropic phase. The dielectric constant and dielectric strength were found to be increased with the rise in the Bi4Ti3O12 nanoparticles concertation in the lyotropic matrix. A significant increase of one order was observed in the ac conductivity of colloidal systems as compared to the non-doped lyotropic liquid crystal. Relaxation parameters of the non-doped lyotropic liquid crystal and colloidal systems were computed and correlated with other parameters.

Innovative aspects of protein stability in ionic liquid mixtures.

PubMed

Kumar, Awanish; Venkatesu, Pannuru

2018-06-01

Mixtures of ionic liquids (ILs) have attracted our attention because of their extraordinary performances in extraction technologies and in absorbing large amount of CO 2 gas. It has been observed that when two or more ILs are mixed in different proportions, a new solvent is obtained which is much better than that of each component of ILs from which the mixture is obtained. Within a mixture of ILs, several unidentified interactions occur among several ions which give rise to unique solvent properties to the mixture. Herein, in this review, we have highlighted the utilization of the advantageous properties of the IL mixtures in protein stability studies. This approach is exceptional and opens new directions to the use of ILs in biotechnology.

Laminar burning velocity and ignition delay time for premixed isooctane-air flames with syngas addition

NASA Astrophysics Data System (ADS)

Bhattacharya, Atmadeep; Datta, Amitava; Wensing, Michael

2017-03-01

The effects of blending syngas in different proportions to isooctane on the laminar burning velocity and ignition delay time of the fuel-air mixture have been studied in SI engine relevant conditions. The syngas is assumed to be composed of 50% H2 and 50% CO. Simulations have been carried out using a skeletal mechanism containing 143 species and 643 reaction steps. It has been found that the blending of syngas augments the laminar burning velocity of isooctane due to increase of the thermal diffusivity of the reactant mixture and alteration in the chemistry of the flame reactions. For the mixture of 30% isooctane/70% syngas, the laminar burning velocity and the ignition delay time values are very close to those corresponding to pure isooctane. Additionally, the effects of exhaust gas recirculation have been explored for the 30% isooctane/70% syngas-air flame. It is seen that the reduction in laminar burning velocity due to the dilution by the recirculated exhaust gas can be compensated by an increase in the unburnt gas temperature. The effect of the exhaust gas dilution on the ignition delay time of 30% isooctane/70% syngas-air mixture has been found to be negligible.

Low Mach number fluctuating hydrodynamics of multispecies liquid mixtures

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

Donev, Aleksandar, E-mail: donev@courant.nyu.edu; Bhattacharjee, Amit Kumar; Nonaka, Andy

We develop a low Mach number formulation of the hydrodynamic equations describing transport of mass and momentum in a multispecies mixture of incompressible miscible liquids at specified temperature and pressure, which generalizes our prior work on ideal mixtures of ideal gases [Balakrishnan et al., “Fluctuating hydrodynamics of multispecies nonreactive mixtures,” Phys. Rev. E 89 013017 (2014)] and binary liquid mixtures [Donev et al., “Low mach number fluctuating hydrodynamics of diffusively mixing fluids,” Commun. Appl. Math. Comput. Sci. 9(1), 47-105 (2014)]. In this formulation, we combine and extend a number of existing descriptions of multispecies transport available in the literature. Themore » formulation applies to non-ideal mixtures of arbitrary number of species, without the need to single out a “solvent” species, and includes contributions to the diffusive mass flux due to gradients of composition, temperature, and pressure. Momentum transport and advective mass transport are handled using a low Mach number approach that eliminates fast sound waves (pressure fluctuations) from the full compressible system of equations and leads to a quasi-incompressible formulation. Thermal fluctuations are included in our fluctuating hydrodynamics description following the principles of nonequilibrium thermodynamics. We extend the semi-implicit staggered-grid finite-volume numerical method developed in our prior work on binary liquid mixtures [Nonaka et al., “Low mach number fluctuating hydrodynamics of binary liquid mixtures,” http://arxiv.org/abs/1410.2300 (2015)] and use it to study the development of giant nonequilibrium concentration fluctuations in a ternary mixture subjected to a steady concentration gradient. We also numerically study the development of diffusion-driven gravitational instabilities in a ternary mixture and compare our numerical results to recent experimental measurements [Carballido-Landeira et al., “Mixed-mode instability of a miscible interface due to coupling between Rayleigh–Taylor and double-diffusive convective modes,” Phys. Fluids 25, 024107 (2013)] in a Hele-Shaw cell. We find that giant nonequilibrium fluctuations can trigger the instability but are eventually dominated by the deterministic growth of the unstable mode, in both quasi-two-dimensional (Hele-Shaw) and fully three-dimensional geometries used in typical shadowgraph experiments.« less

Solar driven liquid metal MHD power generator

NASA Technical Reports Server (NTRS)

Lee, J. H.; Hohl, F. (Inventor)

1983-01-01

A solar energy collector focuses solar energy onto a solar oven which is attached to a mixer which in turn is attached to the channel of a MHD generator. Gas enters the oven and a liquid metal enters the mixer. The gas/liquid metal mixture is heated by the collected solar energy and moves through the MHD generator thereby generating electrical power. The mixture is then separated and recycled.

Recovery of purified helium or hydrogen from gas mixtures

DOEpatents

Merriman, J.R.; Pashley, J.H.; Stephenson, M.J.; Dunthorn, D.I.

1974-01-15

A process is described for the removal of helium or hydrogen from gaseous mixtures also containing contaminants. The gaseous mixture is contacted with a liquid fluorocarbon in an absorption zone maintained at superatomspheric pressure to preferentially absorb the contaminants in the fluorocarbon. Unabsorbed gas enriched in hydrogen or helium is withdrawn from the absorption zone as product. Liquid fluorocarbon enriched in contaminants is withdrawn separately from the absorption zone. (10 claims)

Improvement in device performance from a mixture of a liquid crystal and photosensitive acrylic prepolymer with the photoinduced vertical alignment method

PubMed Central

Ho, Czung-Yu; Lin, Fa-Hsin; Tao, Yu-Tai; Lee, Jiunn-Yih

2011-01-01

In a multicomponent nematic liquid crystal (NLC) mixture of a liquid crystal (negative-type NLC) and a photosensitive acrylic prepolymer, photopolymerization upon UV irradiation induces the separation of the LC and photosensitive acrylic prepolymer layers, thereby leading to a vertical arrangement of LC molecules. In this study, we propose a simple vertical alignment method for LC molecules, by adding a chiral smectic A (SmA∗) liquid crystal having homeotropic texture characteristics to an NLC mixture solution. Measurements of electro-optical properties revealed that the addition of the SmA∗ LC not only strengthened the anchoring force of the copolymer alignment film surface, but also significantly enhanced the contrast ratio (∼73%), response time and grayscale switching performance of the device. PMID:27877462

Linking the structures, free volumes, and properties of ionic liquid mixtures† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc01407d

PubMed Central

Brooks, Nicholas J.; Castiglione, Franca; Doherty, Cara M.; Dolan, Andrew; Hill, Anita J.; Hunt, Patricia A.; Matthews, Richard P.; Mauri, Michele; Mele, Andrea; Simonutti, Roberto; Villar-Garcia, Ignacio J.; Weber, Cameron C.

2017-01-01

The formation of ionic liquid (IL) mixtures has been proposed as an approach to rationally fine-tune the physicochemical properties of ILs for a variety of applications. However, the effects of forming such mixtures on the resultant properties of the liquids are only beginning to be understood. Towards a more complete understanding of both the thermodynamics of mixing ILs and the effect of mixing these liquids on their structures and physicochemical properties, the spatial arrangement and free volume of IL mixtures containing the common [C4C1im]+ cation and different anions have been systematically explored using small angle X-ray scattering (SAXS), positron annihilation lifetime spectroscopy (PALS) and 129Xe NMR techniques. Anion size has the greatest effect on the spatial arrangement of the ILs and their mixtures in terms of the size of the non-polar domains and inter-ion distances. It was found that differences in coulombic attraction between oppositely charged ions arising from the distribution of charge density amongst the atoms of the anion also significantly influences these inter-ion distances. PALS and 129Xe NMR results pertaining to the free volume of these mixtures were found to strongly correlate with each other despite the vastly different timescales of these techniques. Furthermore, the excess free volumes calculated from each of these measurements were in excellent agreement with the excess volumes of mixing measured for the IL mixtures investigated. The correspondence of these techniques indicates that the static and dynamic free volume of these liquid mixtures are strongly linked. Consequently, fluxional processes such as hydrogen bonding do not significantly contribute to the free volumes of these liquids compared to the spatial arrangement of ions arising from their size, shape and coulombic attraction. Given the relationship between free volume and transport properties such as viscosity and conductivity, these results provide a link between the structures of IL mixtures, the thermodynamics of mixing and their physicochemical properties. PMID:29619199

Low energy consumption method for separating gaseous mixtures and in particular for medium purity oxygen production

DOEpatents

Jujasz, Albert J.; Burkhart, James A.; Greenberg, Ralph

1988-01-01

A method for the separation of gaseous mixtures such as air and for producing medium purity oxygen, comprising compressing the gaseous mixture in a first compressor to about 3.9-4.1 atmospheres pressure, passing said compressed gaseous mixture in heat exchange relationship with sub-ambient temperature gaseous nitrogen, dividing the cooled, pressurized gaseous mixture into first and second streams, introducing the first stream into the high pressure chamber of a double rectification column, separating the gaseous mixture in the rectification column into a liquid oxygen-enriched stream and a gaseous nitrogen stream and supplying the gaseous nitrogen stream for cooling the compressed gaseous mixture, removing the liquid oxygen-enriched stream from the low pressure chamber of the rectification column and pumping the liquid, oxygen-enriched steam to a predetermined pressure, cooling the second stream, condensing the cooled second stream and evaporating the oxygen-enriched stream in an evaporator-condenser, delivering the condensed second stream to the high pressure chamber of the rectification column, and heating the oxygen-enriched stream and blending the oxygen-enriched stream with a compressed blend-air stream to the desired oxygen concentration.

Dielectric constant of liquid alkanes and hydrocarbon mixtures

NASA Technical Reports Server (NTRS)

Sen, A. D.; Anicich, V. G.; Arakelian, T.

1992-01-01

The complex dielectric constants of n-alkanes with two to seven carbon atoms have been measured. The measurements were conducted using a slotted-line technique at 1.2 GHz and at atmospheric pressure. The temperature was varied from the melting point to the boiling point of the respective alkanes. The real part of the dielectric constant was found to decrease with increasing temperature and correlate with the change in the molar volume. An upper limit to all the loss tangents was established at 0.001. The complex dielectric constants of a few mixtures of liquid alkanes were also measured at room temperature. For a pentane-octane mixture the real part of the dielectric constant could be explained by the Clausius-Mosotti theory. For the mixtures of n-hexane-ethylacetate and n-hexane-acetone the real part of the dielectric constants could be explained by the Onsager theory extended to mixtures. The dielectric constant of the n-hexane-acetone mixture displayed deviations from the Onsager theory at the highest fractions of acetone. The dipole moments of ethylacetate and acetone were determined for dilute mixtures using the Onsager theory and were found to be in agreement with their accepted gas-phase values. The loss tangents of the mixtures exhibited a linear relationship with the volume fraction for low concentrations of the polar liquids.

On the Stability of the Detonation Wave Front in the High Explosive Liquid Mixture Tetranitromethane/Nitrobenzene

NASA Astrophysics Data System (ADS)

Fedorov, A. V.; Mikhaylov, A. L.; Men'Shikh, A. V.; Nazarov, D. V.; Finyushin, S. A.; Davydov, V. A.

2010-10-01

We performed experimental studies on the stability of the detonation wave front in mixtures of the liquids tetranitromethane (TNM) and nitrobenzene (NB). Tetranitromethane is an oxygen-rich explosive and nitrobenzene was used as a solvent or dilutant. (NB is not classed as an explosive but as an explosive would be oxygen poor and fuel rich.) The primary diagnostic was a laser velocimetry method with high temporal resolution. Data obtained were compared with the detonation parameters of the TNM/NB mixtures. In previous experimental work [1,2] it was shown that the detonation wave front in liquid explosives may be either smooth or rough. Rough detonation fronts have been reported in nitromethane, as well as nitromethane mixed with a solvent. Smooth detonation fronts have been reported in tetranitromethane. Previously, we conducted studies on the structure of the detonation wave front in liquid explosives containing tetranitromethane [3-5]. Smooth, stable fronts were recorded in pure tetranitromethane and in a 46/54 mixture of tetranitromethane and nitromethane. A pulsating, unstable detonation wave front was recorded in a 74/26 mixture of tetranitromethane and nitrobenzene. The goal of the present work is to extend our research on the structure of the detonation wave front in mixtures of tetranitromethane diluted with less energetic nitrobenzene. To this end, the following TNM/NB mixtures were studied: 95/5, 90/10, 85/15, 80/20, 74/26, and 50/50.

Continuous-flow hydrogenation of carbon dioxide to pure formic acid using an integrated scCO2 process with immobilized catalyst and base.

PubMed

Wesselbaum, Sebastian; Hintermair, Ulrich; Leitner, Walter

2012-08-20

Dual role for CO(2): Pure formic acid can be obtained continuously by hydrogenation of CO(2) in a single processing unit. An immobilized ruthenium organometallic catalyst and a nonvolatile base in an ionic liquid (IL) are combined with supercritical CO(2) as both reactant and extractive phase. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Refractive index of liquid mixtures: theory and experiment.

PubMed

Reis, João Carlos R; Lampreia, Isabel M S; Santos, Angela F S; Moita, Maria Luísa C J; Douhéret, Gérard

2010-12-03

An innovative approach is presented to interpret the refractive index of binary liquid mixtures. The concept of refractive index "before mixing" is introduced and shown to be given by the volume-fraction mixing rule of the pure-component refractive indices (Arago-Biot formula). The refractive index of thermodynamically ideal liquid mixtures is demonstrated to be given by the volume-fraction mixing rule of the pure-component squared refractive indices (Newton formula). This theoretical formulation entails a positive change of refractive index upon ideal mixing, which is interpreted in terms of dissimilar London dispersion forces centred in the dissimilar molecules making up the mixture. For real liquid mixtures, the refractive index of mixing and the excess refractive index are introduced in a thermodynamic manner. Examples of mixtures are cited for which excess refractive indices and excess molar volumes show all of the four possible sign combinations, a fact that jeopardises the finding of a general equation linking these two excess properties. Refractive indices of 69 mixtures of water with the amphiphile (R,S)-1-propoxypropan-2-ol are reported at five temperatures in the range 283-303 K. The ideal and real refractive properties of this binary system are discussed. Pear-shaped plots of excess refractive indices against excess molar volumes show that extreme positive values of excess refractive index occur at a substantially lower mole fraction of the amphiphile than extreme negative values of excess molar volume. Analysis of these plots provides insights into the mixing schemes that occur in different composition segments. A nearly linear variation is found when Balankina's ratios between excess and ideal values of refractive indices are plotted against ratios between excess and ideal values of molar volumes. It is concluded that, when coupled with volumetric properties, the new thermodynamic functions defined for the analysis of refractive indices of liquid mixtures give important complementary information on the mixing process over the whole composition range.

An analytical solubility model for nitrogen-methane-ethane ternary mixtures

NASA Astrophysics Data System (ADS)

Hartwig, Jason; Meyerhofer, Peter; Lorenz, Ralph; Lemmon, Eric

2018-01-01

Saturn's moon Titan has surface liquids of liquid hydrocarbons and a thick, cold, nitrogen atmosphere, and is a target for future exploration. Critical to the design and operation of vehicles for this environment is knowledge of the amount of dissolved nitrogen gas within the cryogenic liquid methane and ethane seas. This paper rigorously reviews experimental data on the vapor-liquid equilibrium of nitrogen/methane/ethane mixtures, noting the possibility for split liquid phases, and presents simple analytical models for conveniently predicting solubility of nitrogen in pure liquid ethane, pure liquid methane, and a mixture of liquid ethane and methane. Model coefficients are fit to three temperature ranges near the critical point, intermediate range, and near the freezing point to permit accurate predictions across the full range of thermodynamic conditions. The models are validated against the consolidated database of 2356 experimental data points, with mean absolute error between data and model less than 8% for both binary nitrogen/methane and nitrogen/ethane systems, and less than 17% for the ternary nitrogen/methane/ethane system. The model can be used to predict the mole fractions of ethane, methane, and nitrogen as a function of location within the Titan seas.

Aerosol reactor production of uniform submicron powders

NASA Technical Reports Server (NTRS)

Flagan, Richard C. (Inventor); Wu, Jin J. (Inventor)

1991-01-01

A method of producing submicron nonagglomerated particles in a single stage reactor includes introducing a reactant or mixture of reactants at one end while varying the temperature along the reactor to initiate reactions at a low rate. As homogeneously small numbers of seed particles generated in the initial section of the reactor progress through the reactor, the reaction is gradually accelerated through programmed increases in temperature along the length of the reactor to promote particle growth by chemical vapor deposition while minimizing agglomerate formation by maintaining a sufficiently low number concentration of particles in the reactor such that coagulation is inhibited within the residence time of particles in the reactor. The maximum temperature and minimum residence time is defined by a combination of temperature and residence time that is necessary to bring the reaction to completion. In one embodiment, electronic grade silane and high purity nitrogen are introduced into the reactor and temperatures of approximately 770.degree. K. to 1550.degree. K. are employed. In another embodiment silane and ammonia are employed at temperatures from 750.degree. K. to 1800.degree. K.

Aerosol reactor production of uniform submicron powders

DOEpatents

Flagan, Richard C.; Wu, Jin J.

1991-02-19

A method of producing submicron nonagglomerated particles in a single stage reactor includes introducing a reactant or mixture of reactants at one end while varying the temperature along the reactor to initiate reactions at a low rate. As homogeneously small numbers of seed particles generated in the initial section of the reactor progress through the reactor, the reaction is gradually accelerated through programmed increases in temperature along the length of the reactor to promote particle growth by chemical vapor deposition while minimizing agglomerate formation by maintaining a sufficiently low number concentration of particles in the reactor such that coagulation is inhibited within the residence time of particles in the reactor. The maximum temperature and minimum residence time is defined by a combination of temperature and residence time that is necessary to bring the reaction to completion. In one embodiment, electronic grade silane and high purity nitrogen are introduced into the reactor and temperatures of approximately 770.degree. K. to 1550.degree. K. are employed. In another embodiment silane and ammonia are employed at temperatures from 750.degree. K. to 1800.degree. K.

Photoinduced electron transfer in an imidazolium ionic liquid and in its binary mixtures with water, methanol, and 2-propanol: appearance of Marcus-type of inversion.

PubMed

Sarkar, Souravi; Mandal, Sarthak; Ghatak, Chiranjib; Rao, Vishal Govind; Ghosh, Surajit; Sarkar, Nilmoni

2012-02-02

The photoinduced electron transfer (PET) reaction has been investigated in a room temperature imidazolium ionic liquid (RTIL), 1-ethyl-3-methylimidazolium ethyl sulfate ([Emim][EtSO(4)]) and also in [Emim][EtSO(4)]-co-solvents mixtures from N,N-dimethyl aniline (DMA) to different Coumarin dyes using steady state and time-resolved fluorescence quenching measurements. We have used water and methanol and 2-propanol as the cosolvents of RTILs for the PET study. On going from neat ionic liquid to the RTIL-co-solvents mixtures the electron transfer rate has been largely enhanced. In neat RTIL as well as in [Emim][EtSO(4)]-co-solvents mixtures, a Marcus type of inversion in the PET rate have been observed.

Recovery of anhydrous hydrogen iodide

DOEpatents

O'Keefe, Dennis R.; McCorkle, Jr., Kenneth H.; de Graaf, Johannes D.

1982-01-01

Relatively dry hydrogen iodide can be recovered from a mixture of HI, I.sub.2 and H.sub.2 O. After the composition of the mixture is adjusted so that the amounts of H.sub.2 O and I.sub.2 do not exceed certain maximum limits, subjection of the mixture to superatmospheric pressure in an amount equal to about the vapor pressure of HI at the temperature in question causes distinct liquid phases to appear. One of the liquid phases contains HI and not more than about 1 weight percent water. Often the adjustment in the composition will include the step of vaporization, and the distinct layers appear following the increase in pressure of the vapor mixture. Adjustment in the composition may also include the addition of an extraction agent, such as H.sub.3 PO.sub.4, and even though the adjusted composition mixture contains a significant amount of such an agent, the creation of the distinct liquid phases is not adversely affected.

Microstructure and hydrogen bonding in water-acetonitrile mixtures.

PubMed

Mountain, Raymond D

2010-12-16

The connection of hydrogen bonding between water and acetonitrile in determining the microheterogeneity of the liquid mixture is examined using NPT molecular dynamics simulations. Mixtures for six, rigid, three-site models for acetonitrile and one water model (SPC/E) were simulated to determine the amount of water-acetonitrile hydrogen bonding. Only one of the six acetonitrile models (TraPPE-UA) was able to reproduce both the liquid density and the experimental estimates of hydrogen bonding derived from Raman scattering of the CN stretch band or from NMR quadrupole relaxation measurements. A simple modification of the acetonitrile model parameters for the models that provided poor estimates produced hydrogen-bonding results consistent with experiments for two of the models. Of these, only one of the modified models also accurately determined the density of the mixtures. The self-diffusion coefficient of liquid acetonitrile provided a final winnowing of the modified model and the successful, unmodified model. The unmodified model is provisionally recommended for simulations of water-acetonitrile mixtures.

Efficient capture of SO2 by a binary mixture of caprolactam tetrabutyl ammonium bromide ionic liquid and water.

PubMed

Duan, Erhong; Guo, Bin; Zhang, Miaomiao; Guan, Yanan; Sun, Hua; Han, Jing

2011-10-30

The solubility of SO(2) in a binary mixture of water and caprolactam tetrabutyl ammonium bromide ionic liquid (CPL-TBAB IL) was investigated. Though the ionic liquid and water were fully miscible, a phase separation occurred when SO(2) was introduced into the mixture. The SO(2) concentrated in the lower layer, and it could be released by heating the solution under reduced pressure (382.2K, 10.1 kPa). After desorption, the mixture could be reused to absorb SO(2). It was found that SO(2) acts as a switch to cause the water and CPL-TBAB IL to phase separate, and the mechanics of this phase separation process was studied by gas chromatography-mass spectrometry, fourier transform-infrared spectroscopy and Karl-Fisher titration. The absorption and desorption of SO(2) in the CPL-TBAB/water mixtures were reversible. Copyright © 2011 Elsevier B.V. All rights reserved.

Extraction and Esterification of Low-Titer Short-Chain Volatile Fatty Acids from Anaerobic Fermentation with Ionic Liquids.

PubMed

Andersen, Stephen J; Berton, Jan K E T; Naert, Pieter; Gildemyn, Sylvia; Rabaey, Korneel; Stevens, Christian V

2016-08-23

Ionic liquids can both act as a solvent and mediate esterification to valorize low-titer volatile fatty acids and generate organic solvents from renewable carbon sources including biowaste and CO2 . In this study, four phosphonium ionic liquids were tested for single-stage extraction of acetic acid from a dilute stream and esterification to ethyl acetate with added ethanol and heat. The esterification proceeded with a maximum conversion of 85.9±1.3 % after 30 min at 75 °C at a 1:1 stoichiometric ratio of reactants. Extraction and esterification can be tailored using mixed-anion ionic liquids; this is demonstrated herein using a common trihexyl(tetradecyl)phosphonium cation and a mixed chloride and bis(trifluoromethylsulfonyl)imide anion ionic liquid. As a further proof-of-concept, ethyl acetate was generated from an ionic liquid-driven esterification of an acetic acid extractant generated using CO2 as the only carbon source by microbial electrosynthesis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chromonic liquid crystalline nematic phase exhibited in binary mixture of two liquid crystals

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

Govindaiah, T. N., E-mail: tngovi.phy@gmail.com; Sreepad, H. R.; Sridhar, K. N.

2015-06-24

A binary mixture of abietic acid and orthophosphoric acid (H{sub 3}PO{sub 4}) exhibits co-existence of biphasic region of Nematic+Isotropic (N+I), lyotropic Nematic (ND) and Smectic-G (SmG) phases. The mixture exhibits N+I, N and SmG phases at different concentrations and at different temperatures. Mixtures with all concentrations of abietic acid exhibit I→N+I→N→SmG phases sequentially when the specimen is cooled from its isotropic melt. These phases have been characterized by using differential scanning calorimetric, X-ray diffraction, and optical texture studies.

Construction of Lines of Constant Density and Constant Refractive Index for Ternary Liquid Mixtures.

ERIC Educational Resources Information Center

Tasic, Aleksandar Z.; Djordjevic, Bojan D.

1983-01-01

Demonstrates construction of density constant and refractive index constant lines in triangular coordinate system on basis of systematic experimental determinations of density and refractive index for both homogeneous (single-phase) ternary liquid mixtures (of known composition) and the corresponding binary compositions. Background information,…

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.

Simple views on critical binary liquid mixtures in porous glass

NASA Astrophysics Data System (ADS)

Tremblay, L.; Socol, S. M.; Lacelle, S.

2000-01-01

A simple scenario, different from previous attempts, is proposed to resolve the problem of the slow phase separation dynamics of binary liquid mixtures confined in porous Vycor glass. We demonstrate that simply mutual diffusion, renormalized by critical composition fluctuations and geometrical hindrance of the porous glass, accounts for the slow phase separation kinetics. Capillary invasion studies of porous Vycor glass by the critical isobutyric acid-water mixture, close to the consolute solution temperature, corroborate our analysis.

Role of amphiphilic molecule on liquid crystal phases

NASA Astrophysics Data System (ADS)

Dan, Kaustabh; Roy, Madhusudan; Datta, Alokmay

2013-02-01

We have studied the effect of an amphiphilic fatty acid, Stearic Acid (StA), on the phases, wetting and polarization properties of the liquid crystalline substance N-(4-Methoxybenzylidene)-4-butylaniline (MBBA), through Differential Scanning Calorimetry and Optical Polarization Microscopy. Metastable and mesophases disappear for a MBBA:StA = 1:5 mixture. This mixture wets Si(111) and dewets Si(100) surfaces while pure MBBA dewets both. Films of this mixture also show better polarization than the pure sample.

Evaporation-triggered microdroplet nucleation and the four life phases of an evaporating Ouzo drop.

PubMed

Tan, Huanshu; Diddens, Christian; Lv, Pengyu; Kuerten, J G M; Zhang, Xuehua; Lohse, Detlef

2016-08-02

Evaporating liquid droplets are omnipresent in nature and technology, such as in inkjet printing, coating, deposition of materials, medical diagnostics, agriculture, the food industry, cosmetics, or spills of liquids. Whereas the evaporation of pure liquids, liquids with dispersed particles, or even liquid mixtures has intensively been studied over the past two decades, the evaporation of ternary mixtures of liquids with different volatilities and mutual solubilities has not yet been explored. Here we show that the evaporation of such ternary mixtures can trigger a phase transition and the nucleation of microdroplets of one of the components of the mixture. As a model system, we pick a sessile Ouzo droplet (as known from daily life-a transparent mixture of water, ethanol, and anise oil) and reveal and theoretically explain its four life phases: In phase I, the spherical cap-shaped droplet remains transparent while the more volatile ethanol is evaporating, preferentially at the rim of the drop because of the singularity there. This leads to a local ethanol concentration reduction and correspondingly to oil droplet nucleation there. This is the beginning of phase II, in which oil microdroplets quickly nucleate in the whole drop, leading to its milky color that typifies the so-called "Ouzo effect." Once all ethanol has evaporated, the drop, which now has a characteristic nonspherical cap shape, has become clear again, with a water drop sitting on an oil ring (phase III), finalizing the phase inversion. Finally, in phase IV, all water has evaporated, leaving behind a tiny spherical cap-shaped oil drop.

Evaporation-triggered microdroplet nucleation and the four life phases of an evaporating Ouzo drop

NASA Astrophysics Data System (ADS)

Tan, Huanshu; Diddens, Christian; Lv, Pengyu; Kuerten, J. G. M.; Zhang, Xuehua; Lohse, Detlef

2016-08-01

Evaporating liquid droplets are omnipresent in nature and technology, such as in inkjet printing, coating, deposition of materials, medical diagnostics, agriculture, the food industry, cosmetics, or spills of liquids. Whereas the evaporation of pure liquids, liquids with dispersed particles, or even liquid mixtures has intensively been studied over the past two decades, the evaporation of ternary mixtures of liquids with different volatilities and mutual solubilities has not yet been explored. Here we show that the evaporation of such ternary mixtures can trigger a phase transition and the nucleation of microdroplets of one of the components of the mixture. As a model system, we pick a sessile Ouzo droplet (as known from daily life—a transparent mixture of water, ethanol, and anise oil) and reveal and theoretically explain its four life phases: In phase I, the spherical cap-shaped droplet remains transparent while the more volatile ethanol is evaporating, preferentially at the rim of the drop because of the singularity there. This leads to a local ethanol concentration reduction and correspondingly to oil droplet nucleation there. This is the beginning of phase II, in which oil microdroplets quickly nucleate in the whole drop, leading to its milky color that typifies the so-called “Ouzo effect.” Once all ethanol has evaporated, the drop, which now has a characteristic nonspherical cap shape, has become clear again, with a water drop sitting on an oil ring (phase III), finalizing the phase inversion. Finally, in phase IV, all water has evaporated, leaving behind a tiny spherical cap-shaped oil drop.

Evaporation-triggered microdroplet nucleation and the four life phases of an evaporating Ouzo drop

PubMed Central

Tan, Huanshu; Diddens, Christian; Lv, Pengyu; Kuerten, J. G. M.; Zhang, Xuehua; Lohse, Detlef

2016-01-01

Evaporating liquid droplets are omnipresent in nature and technology, such as in inkjet printing, coating, deposition of materials, medical diagnostics, agriculture, the food industry, cosmetics, or spills of liquids. Whereas the evaporation of pure liquids, liquids with dispersed particles, or even liquid mixtures has intensively been studied over the past two decades, the evaporation of ternary mixtures of liquids with different volatilities and mutual solubilities has not yet been explored. Here we show that the evaporation of such ternary mixtures can trigger a phase transition and the nucleation of microdroplets of one of the components of the mixture. As a model system, we pick a sessile Ouzo droplet (as known from daily life—a transparent mixture of water, ethanol, and anise oil) and reveal and theoretically explain its four life phases: In phase I, the spherical cap-shaped droplet remains transparent while the more volatile ethanol is evaporating, preferentially at the rim of the drop because of the singularity there. This leads to a local ethanol concentration reduction and correspondingly to oil droplet nucleation there. This is the beginning of phase II, in which oil microdroplets quickly nucleate in the whole drop, leading to its milky color that typifies the so-called “Ouzo effect.” Once all ethanol has evaporated, the drop, which now has a characteristic nonspherical cap shape, has become clear again, with a water drop sitting on an oil ring (phase III), finalizing the phase inversion. Finally, in phase IV, all water has evaporated, leaving behind a tiny spherical cap-shaped oil drop. PMID:27418601

Fuel cell membrane hydration and fluid metering

DOEpatents

Jones, Daniel O.; Walsh, Michael M.

1999-01-01

A hydration system includes fuel cell fluid flow plate(s) and injection port(s). Each plate has flow channel(s) with respective inlet(s) for receiving respective portion(s) of a given stream of reactant fluid for a fuel cell. Each injection port injects a portion of liquid water directly into its respective flow channel in order to mix its respective portion of liquid water with the corresponding portion of the stream. This serves to hydrate at least corresponding part(s) of a given membrane of the corresponding fuel cell(s). The hydration system may be augmented by a metering system including flow regulator(s). Each flow regulator meters an injecting at inlet(s) of each plate of respective portions of liquid into respective portion(s) of a given stream of fluid by corresponding injection port(s).

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.

Ambient pressure fuel cell system

DOEpatents

Wilson, Mahlon S.

2000-01-01

An ambient pressure fuel cell system is provided with a fuel cell stack formed from a plurality of fuel cells having membrane/electrode assemblies (MEAs) that are hydrated with liquid water and bipolar plates with anode and cathode sides for distributing hydrogen fuel gas and water to a first side of each one of the MEAs and air with reactant oxygen gas to a second side of each one of the MEAs. A pump supplies liquid water to the fuel cells. A recirculating system may be used to return unused hydrogen fuel gas to the stack. A near-ambient pressure blower blows air through the fuel cell stack in excess of reaction stoichiometric amounts to react with the hydrogen fuel gas.

Erythorbic acid promoted formation of CdS QDs in a tube-in-tube micro-channel reactor

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

Liang, Yan; Tan, Jiawei; Wang, Jiexin

2014-12-15

Erythorbic acid assistant synthesis of CdS quantum dots (QDs) was conducted by homogeneous mixing of two continuous liquids in a high-throughput microporous tube-in-tube micro-channel reactor (MTMCR) at room temperature. The effects of the micropore size of the MTMCR, liquid flow rate, mixing time and reactant concentration on the size and size distribution of CdS QDs were investigated. It was found that the size and size distribution of CdS QDs could be tuned in the MTMCR. A combination of erythorbic acid promoted formation technique with the MTMCR may be a promising pathway for controllable mass production of QDs.

The solvated electron battery

NASA Astrophysics Data System (ADS)

Bennett, J.; Harney, D.; Mitchell, T.

A novel ambient temperture secondary battery using sodium and sulfur dissolved in liquid ammonia is being developed at ELTECH Systems corpooration. The key element of the system is the solvated electron electrode, a metallic liquid which is formed by ammonia and a number of alkali and alkaline earth metals. These solutions are excellent ionic and electronic conductors and have been shown to contain 'free' solvated electrons as the anionic species in solution. Sulfur was chosen as the cathodic reactant because of its high solubility in ammonia, and also because of the high solubiity and good conductivity of the polysulfide reaction products. Development efforts have thus far concentrated on basic electrochemical measurements and establishment of system feasibility.

Self-assembly concepts in the formation of nanostructured particles using a liquid-phase synthesis method

NASA Astrophysics Data System (ADS)

Nandiyanto, Asep Bayu Dani

2016-02-01

When synthesizing particles using a liquid-phase synthesis method, reactant components show interaction with the reaction system itself. However, current reports described successful synthesis of material with only partial information on the component-component interaction and possible self-assembly mechanism occurring during the material synthesis process. Here, self-assembly concepts in the formation of nanostructured particles are presented. Influences of self-assembly parameters (i.e., surface charge, size, and concentration of components involving the reaction) on self-organized material fabrication are described. Because understanding the interaction of the component provides significant information in regard to practical uses, this report can be relevant to further material development and fabrication.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A.; Simonetti, Dante A.; Kunkes, Edward L.

2015-12-08

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A [Verona, WI; Simonetti, Dante A [Middleton, WI; Kunkes, Edward L [Madison, WI

2011-12-13

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

Fuel cell membrane hydration and fluid metering

DOEpatents

Jones, Daniel O.; Walsh, Michael M.

2003-01-01

A hydration system includes fuel cell fluid flow plate(s) and injection port(s). Each plate has flow channel(s) with respective inlet(s) for receiving respective portion(s) of a given stream of reactant fluid for a fuel cell. Each injection port injects a portion of liquid water directly into its respective flow channel. This serves to hydrate at least corresponding part(s) of a given membrane of the corresponding fuel cell(s). The hydration system may be augmented by a metering system including flow regulator(s). Each flow regulator meters an injecting at inlet(s) of each plate of respective portions of liquid into respective portion(s) of a given stream of fluid by corresponding injection port(s).

Lipid extraction from microalgae using a single ionic liquid

DOEpatents

Salvo, Roberto Di; Reich, Alton; Dykes, Jr., H. Waite H.; Teixeira, Rodrigo

2013-05-28

A one-step process for the lysis of microalgae cell walls and separation of the cellular lipids for use in biofuel production by utilizing a hydrophilic ionic liquid, 1-butyl-3-methylimidazolium. The hydrophilic ionic liquid both lyses the microalgae cell walls and forms two immiscible layers, one of which consists of the lipid contents of the lysed cells. After mixture of the hydrophilic ionic liquid with a suspension of microalgae cells, gravity causes a hydrophobic lipid phase to move to a top phase where it is removed from the mixture and purified. The hydrophilic ionic liquid is recycled to lyse new microalgae suspensions.

Impact of water dilution and cation tail length on ionic liquid characteristics: Interplay between polar and non-polar interactions

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

Hegde, Govind A.; Bharadwaj, Vivek S.; Kinsinger, Corey L.

2016-08-14

The recalcitrance of lignocellulosic biomass poses a major challenge that hinders the economical utilization of biomass for the production of biofuel, plastics, and chemicals. Ionic liquids have become a promising solvent that addresses many issues in both the pretreatment process and the hydrolysis of the glycosidic bond for the deconstruction of cellulosic materials. However, to make the use of ionic liquids economically viable, either the cost of ionic liquids must be reduced, or a less expensive solvent (e.g., water) may be added to reduce the overall amount of ionic liquid used in addition to reducing the viscosity of the binarymore » liquid mixture. In this work, we employ atomistic molecular dynamics simulations to investigate the impact of water dilution on the overall liquid structure and properties of three imidazolium based ionic liquids. It is found that ionic liquid-water mixtures exhibit characteristics that can be grouped into two distinct regions, which are a function of the ionic liquid concentration. The trends observed in each region are found to correlate with the ordering in the local structure of the ionic liquid that arises from the dynamic interactions between the ion pairs. Simulation results suggest that there is a high level of local ordering in the molecular structure at high concentrations of ionic liquids that is driven by the aggregation of the cationic tails and the anion-water interactions. It is found that as the concentration of ionic liquids in the binary mixture is decreased, there is a point at which the competing self and cross interaction energies between the ionic liquid and water shifts away from a cation-anion dominated regime, which results in a significant change in the mixture properties. This break point, which occurs around 75% w/w ionic liquids, corresponds to the point at which water molecules percolate into the ionic liquid network disrupting the ionic liquids’ nanostructure. It is observed that as the cationic alkyl tail length increases, the changes in the binary mixtures’ properties become more pronounced.« less

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.

Gradient enhanced-fluidity liquid hydrophilic interaction chromatography of ribonucleic acid nucleosides and nucleotides: A "green" technique.

PubMed

Beilke, Michael C; Beres, Martin J; Olesik, Susan V

2016-03-04

A "green" hydrophilic interaction liquid chromatography (HILIC) technique for separating the components of mixtures with a broad range of polarities is illustrated using enhanced-fluidity liquid mobile phases. Enhanced-fluidity liquid chromatography (EFLC) involves the addition of liquid CO2 to conventional liquid mobile phases. Decreased mobile phase viscosity and increased analyte diffusivity results when a liquefied gas is dissolved in common liquid mobile phases. The impact of CO2 addition to a methanol:water (MeOH:H2O) mobile phase was studied to optimize HILIC gradient conditions. For the first time a fast separation of 16 ribonucleic acid (RNA) nucleosides/nucleotides was achieved (16min) with greater than 1.3 resolution for all analyte pairs. By using a gradient, the analysis time was reduced by over 100% compared to similar separations conducted under isocratic conditions. The optimal separation using MeOH:H2O:CO2 mobile phases was compared to MeOH:H2O and acetonitrile:water (ACN:H2O) mobile phases. Based on chromatographic performance parameters (efficiency, resolution and speed of analysis) and an assessment of the environmental impact of the mobile phase mixtures, MeOH:H2O:CO2 mixtures are preferred over ACN:H2O or MeOH:H2O mobile phases for the separation of mixtures of RNA nucleosides and nucleotides. Copyright © 2016 Elsevier B.V. All rights reserved.

Composite anode for lithium ion batteries

DOEpatents

de Guzman, Rhet C.; Ng, K.Y. Simon; Salley, Steven O.

2018-03-06

A composite anode for a lithium-ion battery is manufactured from silicon nanoparticles having diameters mostly under 10 nm; providing an oxide layer on the silicon nanoparticles; dispersing the silicon nanoparticles in a polar liquid; providing a graphene oxide suspension; mixing the polar liquid containing the dispersed silicone nanoparticles with the graphene oxide suspension to obtain a composite mixture; probe-sonicating the mixture for a predetermined time; filtering the composite mixture to obtain a solid composite; drying the composite; and reducing the composite to obtain graphene and silicon.

ETHANOL, ACETIC ACID, AND WATER ADSORPTION FROM BINARY AND TERNARY LIQUID MIXTURES ON HIGH-SILICA ZEOLITES

EPA Science Inventory

Adsorption isotherms were measured for ethanol, acetic acid, and water adsorbed on high-silica ZSM-5 zeolite powder from binary and ternary liquid mixtures at room temperature. Ethanol and water adsorption on two high-silica ZSM-5 zeolites with different aluminum contents and a h...

Constant-Pressure Combustion Charts Including Effects of Diluent Addition

NASA Technical Reports Server (NTRS)

Turner, L Richard; Bogart, Donald

1949-01-01

Charts are presented for the calculation of (a) the final temperatures and the temperature changes involved in constant-pressure combustion processes of air and in products of combustion of air and hydrocarbon fuels, and (b) the quantity of hydrocarbon fuels required in order to attain a specified combustion temperature when water, alcohol, water-alcohol mixtures, liquid ammonia, liquid carbon dioxide, liquid nitrogen, liquid oxygen, or their mixtures are added to air as diluents or refrigerants. The ideal combustion process and combustion with incomplete heat release from the primary fuel and from combustible diluents are considered. The effect of preheating the mixture of air and diluents and the effect of an initial water-vapor content in the combustion air on the required fuel quantity are also included. The charts are applicable only to processes in which the final mixture is leaner than stoichiometric and at temperatures where dissociation is unimportant. A chart is also included to permit the calculation of the stoichiometric ratio of hydrocarbon fuel to air with diluent addition. The use of the charts is illustrated by numerical examples.

Analytical Phase Equilibrium Function for Mixtures Obeying Raoult's and Henry's Laws

NASA Astrophysics Data System (ADS)

Hayes, Robert

When a mixture of two substances exists in both the liquid and gas phase at equilibrium, Raoults and Henry's laws (ideal solution and ideal dilute solution approximations) can be used to estimate the gas and liquid mole fractions at the extremes of either very little solute or solvent. By assuming that a cubic polynomial can reasonably approximate the intermediate values to these extremes as a function of mole fraction, the cubic polynomial is solved and presented. A closed form equation approximating the pressure dependence on mole fraction of the constituents is thereby obtained. As a first approximation, this is a very simple and potentially useful means to estimate gas and liquid mole fractions of equilibrium mixtures. Mixtures with an azeotrope require additional attention if this type of approach is to be utilized. This work supported in part by federal Grant NRC-HQ-84-14-G-0059.

The determination of viscosity at liquid mixtures - Comparison of approaches

NASA Astrophysics Data System (ADS)

Michal, Schmirler; Hana, Netřebská; Jan, Kolínský

2017-09-01

The research of flow field parameters for non-stationary flow of non-Newtonian fluids carried out at the Institute of Fluid Mechanics and Thermodynamics of CTU showed the need for knowledge of determination of the resulting viscosity of a mixture of several liquids. There are several sources for determining viscosity of mixtures. It is possible either to find theoretical relations in the literature or use technical tables based on experimentally measured data. This article focuses on comparing these approaches with an experiment. The experiment was performed by a Rheotest RN 4.1 rotating viscometer produced by the company RHEOTEST Medingen. The research was carried out using a solution of glycerol and water. The research has shown great differences in results in different approaches for determining the viscosity of the liquid mixtures. The result of this paper is to determine the method of viscosity calculation that is closest to the experimental data.

Flash Points of Secondary Alcohol and n-Alkane Mixtures.

PubMed

Esina, Zoya N; Miroshnikov, Alexander M; Korchuganova, Margarita R

2015-11-19

The flash point is one of the most important characteristics used to assess the ignition hazard of mixtures of flammable liquids. To determine the flash points of mixtures of secondary alcohols with n-alkanes, it is necessary to calculate the activity coefficients. In this paper, we use a model that allows us to obtain enthalpy of fusion and enthalpy of vaporization data of the pure components to calculate the liquid-solid equilibrium (LSE) and vapor-liquid equilibrium (VLE). Enthalpy of fusion and enthalpy of vaporization data of secondary alcohols in the literature are limited; thus, the prediction of these characteristics was performed using the method of thermodynamic similarity. Additionally, the empirical models provided the critical temperatures and boiling temperatures of the secondary alcohols. The modeled melting enthalpy and enthalpy of vaporization as well as the calculated LSE and VLE flash points were determined for the secondary alcohol and n-alkane mixtures.

[Effects of different excipients on properties of Tongsaimai mixture and pellet molding].

PubMed

Wang, Jin; Lv, Zhiyang; Wu, Xiaoyan; Di, Liuqing; Dong, Yu; Cai, Baochang

2011-01-01

To study preliminarily on the relationship between properties of the mixture composed of Tongsaimai extract and different excipients and pellet molding. The multivariate regression analysis was used to investigate the correlation of different mixture and pellet molding by measuring the cohesion, liquid-plastic limit of mixture, and the powder properties of pellets. The weighted coefficients of the powder properties were determined by analytic hierarchy process combined with criteria importance through intercriteria correlation. The results showed that liquid-plastic limit seemed to be a major factor, which had positive correlation with pellet molding, while cohesion had negative correlation with pellet molding in the measured range. The physical properties of the mixture has marked influence on pellet molding.

Inverse Opal Photonic Crystals as an Optofluidic Platform for Fast Analysis of Hydrocarbon Mixtures.

PubMed

Xu, Qiwei; Mahpeykar, Seyed Milad; Burgess, Ian B; Wang, Xihua

2018-06-13

Most of the reported optofluidic devices analyze liquid by measuring its refractive index. Recently, the wettability of liquid on various substrates has also been used as a key sensing parameter in optofluidic sensors. However, the above-mentioned techniques face challenges in the analysis of the relative concentration of components in an alkane hydrocarbon mixture, as both refractive indices and wettabilities of alkane hydrocarbons are very close. Here, we propose to apply volatility of liquid as the key sensing parameter, correlate it to the optical property of liquid inside inverse opal photonic crystals, and construct powerful optofluidic sensors for alkane hydrocarbon identification and analysis. We have demonstrated that via evaporation of hydrocarbons inside the periodic structure of inverse opal photonic crystals and observation of their reflection spectra, an inverse opal film could be used as a fast-response optofluidic sensor to accurately differentiate pure hydrocarbon liquids and relative concentrations of their binary and ternary mixtures in tens of seconds. In these 3D photonic crystals, pure chemicals with different volatilities would have different evaporation rates and can be easily identified via the total drying time. For multicomponent mixtures, the same strategy is applied to determine the relative concentration of each component simply by measuring drying time under different temperatures. Using this optofluidic sensing platform, we have determined the relative concentrations of ternary hydrocarbon mixtures with the difference of only one carbon between alkane hydrocarbons, which is a big step toward detailed hydrocarbon analysis for practical use.

Incorporation of ionic liquid into porous polymer monoliths to enhance the separation of small molecules in reversed-phase high-performance liquid chromatography.

PubMed

Wang, Jiafei; Bai, Ligai; Wei, Zhen; Qin, Junxiao; Ma, Yamin; Liu, Haiyan

2015-06-01

An ionic liquid was incorporated into the porous polymer monoliths to afford stationary phases with enhanced chromatographic performance for small molecules in reversed-phase high-performance liquid chromatography. The effect of the ionic liquid in the polymerization mixture on the performance of the monoliths was studied in detail. While monoliths without ionic liquid exhibited poor resolution and low efficiency, the addition of ionic liquid to the polymerization mixture provides highly increased resolution and high efficiency. The chromatographic performances of the monoliths were demonstrated by the separations of various small molecules including aromatic hydrocarbons, isomers, and homologues using a binary polar mobile phase. The present column efficiency reached 27 000 plates/m, which showed that the ionic liquid monoliths are alternative stationary phases in the separation of small molecules by high-performance liquid chromatography. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Kirkwood-Buff theory of solutions and the local composition of liquid mixtures.

PubMed

Shulgin, Ivan L; Ruckenstein, Eli

2006-06-29

The present paper is devoted to the local composition of liquid mixtures calculated in the framework of the Kirkwood-Buff theory of solutions. A new method is suggested to calculate the excess (or deficit) number of various molecules around a selected (central) molecule in binary and multicomponent liquid mixtures in terms of measurable macroscopic thermodynamic quantities, such as the derivatives of the chemical potentials with respect to concentrations, the isothermal compressibility, and the partial molar volumes. This method accounts for an inaccessible volume due to the presence of a central molecule and is applied to binary and ternary mixtures. For the ideal binary mixture it is shown that because of the difference in the volumes of the pure components there is an excess (or deficit) number of different molecules around a central molecule. The excess (or deficit) becomes zero when the components of the ideal binary mixture have the same volume. The new method is also applied to methanol + water and 2-propanol + water mixtures. In the case of the 2-propanol + water mixture, the new method, in contrast to the other ones, indicates that clusters dominated by 2-propanol disappear at high alcohol mole fractions, in agreement with experimental observations. Finally, it is shown that the application of the new procedure to the ternary mixture water/protein/cosolvent at infinite dilution of the protein led to almost the same results as the methods involving a reference state.

Viscosity minima in binary mixtures of ionic liquids + molecular solvents.

PubMed

Tariq, M; Shimizu, K; Esperança, J M S S; Canongia Lopes, J N; Rebelo, L P N

2015-05-28

The viscosity (η) of four binary mixtures (ionic liquids plus molecular solvents, ILs+MSs) was measured in the 283.15 < T/K < 363.15 temperature range. Different IL/MS combinations were selected in such a way that the corresponding η(T) functions exhibit crossover temperatures at which both pure components present identical viscosity values. Consequently, most of the obtained mixture isotherms, η(x), exhibit clear viscosity minima in the studied T-x range. The results are interpreted using auxiliary molecular dynamics (MD) simulation data in order to correlate the observed η(T,x) trends with the interactions in each mixture, including the balance between electrostatic forces and hydrogen bonding.

Detection of a new 'nematic-like' phase in liquid crystal-amphiphile mixture by differential scanning calorimetry

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

Dan, Kaustabh, E-mail: kaustabhdan@gmail.com; Roy, Madhusudan, E-mail: kaustabhdan@gmail.com; Datta, Alokmay, E-mail: kaustabhdan@gmail.com

2014-04-24

Differential Scanning Calorimetry (DSC) studies on phase transitions of the pure liquid crystalline material N-4-methoxybenzylidene-4-butylaniline (MBBA) and mixtures of MBBA and the amphiphile Stearic Acid (StA) show significant changes in the behavior of mixture from pure MBBA, as regards the nematic-isotropic (N-I) transition temperature (T{sub c}) and other thermodynamic parameters like enthalpy, specific heat and activation energy with concentration of StA. In particular, the convexity of the Arrhenius plot in pure MBBA vanishes with StA concentration pointing to the formation of a new, perhaps 'nematic-like', phase in the mixtures.

The coupling of carbon dioxide and epoxides by phenanthroline derivatives containing different Cu(II) complexes as catalyst

NASA Astrophysics Data System (ADS)

Kilic, Ahmet; Palali, Ahmet Arif; Durgun, Mustafa; Tasci, Zeynep; Ulusoy, Mahmut

2013-09-01

A series of the mononuclear Cu(II) metal complexes containing the ligand Bdppz [(9a,13a-dihydro-4,5,9,14-tetraaza-benzo[b]triphenylene-11-yl)-phenyl-methanone] (L1) and Aqphen [(12,17-dihydronaphthol[2,3-h]dipyrido[3,2-a:2‧,3‧-c]-phenazine-12,17-dione)] (L2) were synthesized and used as catalyst for the coupling of carbon dioxide (CO2) and liquid epoxide which served as both reactant and solvent. Dimethylamino pyridine (DMAP) was used as co-catalyst. The yields of epoxides to corresponding cyclic carbonates were determined by comparing the ratio of product to substrate in the 1H NMR spectrum of an aliquot of the reaction mixture. The mononuclear Cu(II) complexes of these ligands were synthesized by treating an ethanol solvent of the appropriate ligand with a different molar amount of CuCl2·2H2O. The Cu(II) complexes were characterized by FT-IR, UV-Vis, elemental analysis, melting point analysis, mass spectra, molar conductivity measurements and magnetic susceptibility techniques. The reaction of the Bdppz and Aqphen ligands in a 1:1, 1:2 or 1:3 mole ratio with CuCl2·2H2O afforded ionic Cu(II) complexes in the presence of Et3N.

In-situ synthesis of MoSi{sub 2}-Al{sub 2}O{sub 3} composite by a thermite reaction

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

Deevi, S.C.; Deevi, S.

1995-08-01

In this paper, the authors discuss the reaction mechanism involved in the thermite reaction leading to the synthesis of a composite since in an actual combustion synthesis, the reaction propagates at a velocity of 10 to 20 mm/sec. Reaction mechanism was determined by using a differential thermal analysis (DTA) and X-ray diffraction (XRD). During the combustion synthesis of MoSi{sub 2}-{alpha}Al{sub 2}O{sub 3}, reaction of MoO{sub 3}, Al and Si occurs rapidly and the reactants and products are expected to be in the liquid state at the combustion temperature. MoO{sub 3} is first reduced to MoO{sub 2}, and the reaction betweenmore » MoO{sub 2}, Al and Si leads to a composite of MoSi{sub 2}-{alpha}Al{sub 2}O{sub 3}. Differential thermal analysis reveals that the onset of exothermic reactions is preceded by melting indicating the necessity of molten Al for the synthesis of the composite. The reaction between MoO{sub 2} + 2Al +2Si can be moderated with Mo-Si mixtures such that the ratio of MoSi{sub 2} to Al{sub 2}O{sub 3} can be increased in the composite of MoSi{sub 2}-{alpha}Al{sub 2}O{sub 3}.« less

Lipase-catalyzed synthesis of xylitol monoesters: solvent engineering approach.

PubMed

Castillo, E; Pezzotti, F; Navarro, A; López-Munguía, A

2003-05-08

A solvent engineering strategy was applied to the lipase-catalyzed synthesis of xylitol-oleic acid monoesters. The different esterification degrees for this polyhydroxylated molecule were examined in different organic solvent mixtures. In this context, conditions for high selectivity towards monooleoyl xylitol synthesis were enhanced from 6 mol% in pure n-hexane to 73 mol% in 2-methyl-2-propanol/dimethylsulfoxide (DMSO) 80:20 (v/v). On the contrary, the highest production of di- and trioleoyl xylitol, corresponding to 94 mol%, was achieved in n-hexane. Changes in polarity of the reaction medium and in the molecular interactions between solvents and reactants were correlated with the activity coefficients of products. Based on experimental results and calculated thermodynamic activities, the effect of different binary mixtures of solvents on the selective production of xylitol esters is reported. From this analysis, it is concluded that in the more polar conditions (100% dimethylsulfoxide (DMSO)), the synthesis of xylitol monoesters is favored. However, these conditions are unfavorable in terms of enzyme stability. As an alternative, binary mixtures of solvents were proposed. Each mixture of solvents was characterized in terms of the quantitative polarity parameter E(T)(30) and related with the activity coefficients of xylitol esters. To our knowledge, the characterization of solvent mixtures in terms of this polarity parameter and its relationship with the selectivity of the process has not been previously reported.

CONTINUOUS GAS ANALYZER

DOEpatents

Katz, S.; Weber, C.W.

1960-02-16

A reagent gas and a sample gas are chemically combined on a continuous basis in a reaction zone maintained at a selected temperature. The reagent gas and the sample gas are introduced to the reaction zone at preselected. constant molar rates of flow. The reagent gas and the selected gas in the sample mixture combine in the reaction zone to form a product gas having a different number of moles from the sum of the moles of the reactants. The difference in the total molar rates of flow into and out of the reaction zone is measured and indicated to determine the concentration of the selected gas.

NOTE: Laboratory Studies of Catalysis of CO to Organics on Grain Analogs

NASA Astrophysics Data System (ADS)

Ferrante, R. F.; Moore, M. H.; Nuth, J. A.; Smith, T.

2000-05-01

Experiments simulating heterogeneous conversion of H 2 and CO into simple hydrocarbons in astrophysical environments have been performed, utilizing realistic cosmic grain analogs of Fe-doped silicates as Fischer-Tropsch-Type catalysts. Catalysis was studied for temperatures from 470-670 K and reactant gas mixtures of H 2/CO with a ratio of 2-100. The total gas pressure was near 0.5 bar. Maximum conversion rates of a few percentage points were achieved over a 3-h time period. Major products were methane, ethane, ethylene, carbon dioxide, and water. Products were identified by IR spectroscopy.

A high-pressure premixed flat-flame burner for chemical process studies. [of pollutant formation in hydrocarbon flames

NASA Technical Reports Server (NTRS)

Miller, I. M.

1978-01-01

A premixed flat-flame burner was designed and tested with methane-air mixtures at pressures from 1.1 to 20 atm and equivalence ratios from 0.7 to 1.1. Reactant velocity in the burner mixing chamber was used to characterize the range of stable flames at each pressure-equivalence-ratio condition. Color photographs of the flames were used to determine flame zone thickness and flame height. The results show that this burner can be used for chemical process studies in premixed high pressure methane-air flames up to 20 atm.

A molecular dynamics simulation study of dynamic process and mesoscopic structure in liquid mixture systems

NASA Astrophysics Data System (ADS)

Yang, Peng

The focus of this dissertation is the Molecular Dynamics (MD) simulation study of two different systems. In thefirst system, we study the dynamic process of graphene exfoliation, particularly graphene dispersion using ionic surfactants (Chapter 2). In the second system, we investigate the mesoscopic structure of binary solute/ionic liquid (IL) mixtures through the comparison between simulations and corresponding experiments (Chapter 3 and 4). In the graphene exfoliation study, we consider two separation mechanisms: changing the interlayer distance and sliding away the relative distance of two single-layer graphene sheets. By calculating the energy barrier as a function of separation (interlayer or sliding-away) distance and performing sodium dodecyl sulfate (SDS) structure analysis around graphene surface in SDS surfactant/water + bilayer graphene mixture systems, we find that the sliding-away mechanism is the dominant, feasible separation process. In this process, the SDS-graphene interaction gradually replaces the graphene-graphene Van der Waals (VdW) interaction, and decreases the energy barrier until almost zero at critical SDS concentration. In solute/IL study, we investigate nonpolar (CS2) and dipolar (CH 3CN) solute/IL mixture systems. MD simulation shows that at low concentrations, IL is nanosegregated into an ionic network and nonpolar domain. It is also found that CS2 molecules tend to be localized into the nonpolar domain, while CH3CN interacts with nonpolar domain as well as with the charged head groups in the ionic network because of its amphiphilicity. At high concentrations, CH3CN molecules eventually disrupt the nanostructural organization. This dissertation is organized in four chapters: (1) introduction to graphene, ionic liquids and the methodology of MD; (2) MD simulation of graphene exfoliation; (3) Nanostructural organization in acetonitrile/IL mixtures; (4) Nanostructural organization in carbon disulfide/IL mixtures; (5) Conclusions. Results of MD simulations of liquid mixture systems car-ried out in this research explain observed experiments and show the details of nanostructural organizations in small solute molecules/IL mixture. Additionally, the research successfully reveals the correct mechanism of graphene exfoliation process in liquid solution. (This will be summarized in Chapter 5.) The research presented in this dissertation enhances our understanding of the microscopic behaviors in complex liquid systems as well as the theoretical method to explore them.

Catalytic Pyrolysis of Waste Plastic Mixture

NASA Astrophysics Data System (ADS)

Sembiring, Ferdianta; Wahyu Purnomo, Chandra; Purwono, Suryo

2018-03-01

Inorganic waste especially plastics still become a major problem in many places. Low biodegradability of this materials causes the effort in recycling become very difficult. Most of the municipal solid waste (MSW) recycling facilities in developing country only use composting method to recover the organic fraction of the waste, while the inorganic fraction is still untreated. By pyrolysis, plastic waste can be treated to produce liquid fuels, flammable gas and chars. Reduction in volume and utilization of the liquid and gas as fuel are the major benefits of the process. By heat integration actually this process can become a self-sufficient system in terms of energy demand. However, the drawback of this process is usually due to the diverse type of plastic in the MSW creating low grade of liquid fuel and harmful gases. In this study, the mixture of plastics i.e. polypropylene (PP) and polyethylene terephthalate (PET) is treated using pyrolysis with catalyst in several operating temperature. PET is problematic to be treated using pyrolysis due to wax-like byproduct in liquid which may cause pipe clogging. The catalyst is the mixture of natural zeolite and bentonite which is able to handle PP and PET mixture feed to produce high grade liquid fuels in terms of calorific value and other fuel properties.

Redox chemistry at liquid/liquid interfaces

NASA Technical Reports Server (NTRS)

Volkov, A. G.; Deamer, D. W.

1997-01-01

The interface between two immiscible liquids with immobilized photosynthetic pigments can serve as the simplest model of a biological membrane convenient for the investigation of photoprocesses accompanied by spatial separation of charges. As it follows from thermodynamics, if the resolvation energies of substrates and products are very different, the interface between two immiscible liquids may act as a catalyst. Theoretical aspects of charge transfer reactions at oil/water interfaces are discussed. Conditions under which the free energy of activation of the interfacial reaction of electron transfer decreases are established. The activation energy of electron transfer depends on the charges of the reactants and dielectric permittivity of the non-aqueous phase. This can be useful when choosing a pair of immiscible solvents to decrease the activation energy of the reaction in question or to inhibit an undesired process. Experimental interfacial catalytic systems are discussed. Amphiphilic molecules such as chlorophyll or porphyrins were studied as catalysts of electron transfer reactions at the oil/water interface.

Analysis of electron transfer processes across liquid/liquid interfaces: estimation of free energy of activation using diffuse boundary model.

PubMed

Harinipriya, S; Sangaranarayanan, M V

2006-01-31

The evaluation of the free energy of activation pertaining to the electron-transfer reactions occurring at liquid/liquid interfaces is carried out employing a diffuse boundary model. The interfacial solvation numbers are estimated using a lattice gas model under the quasichemical approximation. The standard reduction potentials of the redox couples, appropriate inner potential differences, dielectric permittivities, as well as the width of the interface are included in the analysis. The methodology is applied to the reaction between [Fe(CN)6](3-/4-) and [Lu(biphthalocyanine)](3+/4+) at water/1,2-dichloroethane interface. The rate-determining step is inferred from the estimated free energy of activation for the constituent processes. The results indicate that the solvent shielding effect and the desolvation of the reactants at the interface play a central role in dictating the free energy of activation. The heterogeneous electron-transfer rate constant is evaluated from the molar reaction volume and the frequency factor.

A comparative flow visualization study of thermocapillary flow in drops in liquid-liquid systems

NASA Technical Reports Server (NTRS)

Balasubramaniam, R.; Rashidnia, N.

1991-01-01

Experiments are performed to visualize thermocapillary flow in drops in an immiscible host liquid. The host liquid used is silicone oil. Drops of three different liquids are used, viz, vegetable oil, water-methanol mixture anad pure methanol. Clear evidence of thermocapillary flow is seen in vegetable oil drops. For a mixture of water and methanol (approximately 50-50 by weight), natural convection is seen to dominate the flow outside the drop. Pure methanol drops exhibit thermocapillary flow, but dissolve in silicone oil. A small amount of water added to pure methanol significantly reduces the dissolution. Flow oscillations occur in this system for both isothermal and non-isothermal conditions.

Process for preparing a liquid fuel composition

DOEpatents

Singerman, Gary M.

1982-03-16

A process for preparing a liquid fuel composition which comprises liquefying coal, separating a mixture of phenols from said liquefied coal, converting said phenols to the corresponding mixture of anisoles, subjecting at least a portion of the remainder of said liquefied coal to hydrotreatment, subjecting at least a portion of said hydrotreated liquefied coal to reforming to obtain reformate and then combining at least a portion of said anisoles and at least a portion of said reformate to obtain said liquid fuel composition.

Calcination process for radioactive wastes

DOEpatents

Kilian, Douglas C.

1976-05-04

The present invention provides a method for minimizing the volatilization of chlorides during solidification in a fluidized-bed calciner of liquids containing sodium, nitrate and chloride ions. Zirconium and fluoride are introduced into the liquid, and one-half mole of calcium nitrate is added per mole of fluoride present in the liquid mixture. The mixture is calcined in the fluidized-bed calciner at about 500.degree.C., producing a high bulk density calcine product containing the chloride, thus tying up the chloride in the solid product and minimizing chloride volatilization.

Combustion flame-plasma hybrid reactor systems, and chemical reactant sources

DOEpatents

Kong, Peter C

2013-11-26

Combustion flame-plasma hybrid reactor systems, chemical reactant sources, and related methods are disclosed. In one embodiment, a combustion flame-plasma hybrid reactor system comprising a reaction chamber, a combustion torch positioned to direct a flame into the reaction chamber, and one or more reactant feed assemblies configured to electrically energize at least one electrically conductive solid reactant structure to form a plasma and feed each electrically conductive solid reactant structure into the plasma to form at least one product is disclosed. In an additional embodiment, a chemical reactant source for a combustion flame-plasma hybrid reactor comprising an elongated electrically conductive reactant structure consisting essentially of at least one chemical reactant is disclosed. In further embodiments, methods of forming a chemical reactant source and methods of chemically converting at least one reactant into at least one product are disclosed.

Remediation of Uranium in the Hanford Vadose Zone Using Gas-Transported Reactants: Laboratory Scale Experiments in Support of the Deep Vadose Zone Treatability Test Plan for the Hanford Central Plateau

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

Szecsody, James E.; Truex, Michael J.; Zhong, Lirong

2010-01-04

This laboratory-scale investigation is focused on decreasing mobility of uranium in subsurface contaminated sediments in the vadose zone by in situ geochemical manipulation at low water content. This geochemical manipulation of the sediment surface phases included reduction, pH change (acidic and alkaline), and additions of chemicals (phosphate, ferric iron) to form specific precipitates. Reactants were advected into 1-D columns packed with Hanford 200 area U-contaminated sediment as a reactive gas (for CO2, NH3, H2S, SO2), with a 0.1% water content mist (for NaOH, Fe(III), HCl, PO4) and with a 1% water content foam (for PO4). Uranium is present in themore » sediment in multiple phases that include (in decreasing mobility): aqueous U(VI) complexes, adsorbed U, reduced U(IV) precipitates, rind-carbonates, total carbonates, oxides, silicates, phosphates, and in vanadate minerals. Geochemical changes were evaluated in the ability to change the mixture of surface U phases to less mobile forms, as defined by a series of liquid extractions that dissolve progressively less soluble phases. Although liquid extractions provide some useful information as to the generalized uranium surface phases (and are considered operational definitions of extracted phases), positive identification (by x-ray diffraction, electron microprobe, other techniques) was also used to positively identify U phases and effects of treatment. Some of the changes in U mobility directly involve U phases, whereas other changes result in precipitate coatings on U surface phases. The long-term implication of the U surface phase changes to alter U mass mobility in the vadose zone was then investigated using simulations of 1-D infiltration and downward migration of six U phases to the water table. In terms of the short-term decrease in U mobility (in decreasing order), NH3, NaOH mist, CO2, HCl mist, and Fe(III) mist showed 20% to 35% change in U surface phases. Phosphate addition (mist or foam advected) showed inconsistent change in aqueous and adsorbed U, but significant coating (likely phosphates) on U-carbonates. The two reductive gas treatments (H2S and SO2) showed little change. For long-term decrease in U reduction, mineral phases created that had low solubility (phosphates, silicates) were desired, so NH3, phosphates (mist and foam delivered), and NaOH mist showed the greatest formation of these minerals. In addition, simulations showed the greatest decrease in U mass transport time to reach groundwater (and concentration) for these silicate/phosphate minerals. Advection of reactive gasses was the easiest to implement at the laboratory scale (and presumably field scale). Both mist and foam advection show promise and need further development, but current implementation move reactants shorter distances relative to reactive gasses. Overall, the ammonia and carbon dioxide gas had the greatest overall geochemical performance and ability to implement at field scale. Corresponding mist-delivered technologies (NaOH mist for ammonia and HCl mist for carbon dioxide) performed as well or better geochemically, but are not as easily upscaled. Phosphate delivery by mist was rated slightly higher than by foam delivery simply due to the complexity of foam injection and unknown effect of U mobility by the presence of the surfactant.« less

SEPARATION OF VAPOR-PHASE ALCOHOL/WATER MIXTURES VIA FRACTIONAL CONDENSATION USING A PILOT-SCALE DEPHLEGMATOR: ENHANCEMENT OF THE PREVAPORATION PROCESS SEPARATION FACTOR

EPA Science Inventory

In prevaporation, a liquid mixture contacts a membrane surface that preferentially permeates one of the liquid components as a vapor. Our approach to improving pervaporation performance is to replace the one-stage condenser traditionally used to condense the permeate with a frac...

Elasticity-driven partial demixing in cholesteric liquid crystal films.

PubMed

Schmidtke, Jürgen; Coles, Harry J

2009-07-01

We discuss the partial demixing of a chiral nematic mixture of a chiral and an achiral compound, induced by inhomogeneous confinement between substrates. While the effect is tiny in low molar mass mixtures, it is predicted to be noticeable in polymeric systems. The potential of the effect for improving performance of liquid crystal based photonic devices is discussed.

Blue phase liquid crystal phase transition for cyano compound chiral nematic liquid crystal mixtures with three two-ring core structures and chiral dopant concentrations

NASA Astrophysics Data System (ADS)

Shin, Jaesun; Kim, Beomjong; Jung, Wansu; Fahad, Mateen; Park, SangJin; Hong, Sung-Kyu

2017-05-01

Blue phase (BP) temperature range of a chiral nematic liquid crystal (LC) mixture is dependent upon the host nematic LC chemical structure and chiral dopant concentration. In this study, we investigated BP phase transition behaviour and helical twisting power (HTP) using three chiral dopant concentrations of cyano compound chiral nematic LC mixtures incorporating three two-ring core structures in the host nematic LCs. The effect of the host nematic LC core structure, HTP and chiral dopant concentrations were considered on BP temperature ranges, for two types of complete BPI and BPII without isotropic phase (Iso) and two types of coexistence state of BPI+Iso and BPII+Iso.

Analysis of antimycin A by reversed-phase liquid chromatography/nuclear magnetic-resonance spectrometry

USGS Publications Warehouse

Ha, Steven T.K.; Wilkins, Charles L.; Abidi, Sharon L.

1989-01-01

A mixture of closely related streptomyces fermentation products, antimycin A, Is separated, and the components are identified by using reversed-phase high-performance liquid chromatography with directly linked 400-MHz proton nuclear magnetic resonance detection. Analyses of mixtures of three amino acids, alanine, glycine, and valine, are used to determine optimal measurement conditions. Sensitivity increases of as much as a factor of 3 are achieved, at the expense of some loss in chromatographic resolution, by use of an 80-μL NMR cell, Instead of a smaller 14-μL cell. Analysis of the antimycin A mixture, using the optimal analytical high performance liquid chromatography/nuclear magnetic resonance conditions, reveals it to consist of at least 10 closely related components.

Enhancing the Capacitive Performance of Electric Double-Layer Capacitors with Ionic Liquid Mixtures

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

Lian, C.; Liu, K.; Van Aken, Katherine L.

Formulating room-temperature ionic liquid (RTIL) mixed electrolytes was recently proposed as an effective and convenient strategy to increase the capacitive performance of electrochemical capacitors. In this paper, we investigate the electrical double-layer (EDL) structure and the capacitance of two RTILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF 4), and their mixtures with onion-like carbon electrodes using experiment and classical density functional theory. The principal difference between these ionic liquids is the smaller diameter of the BF 4 – anion relative to the TFSI – anion and the EMI + cation. A volcano-shaped trend is identified for the capacitance versus themore » composition of the RTIL mixture. The mixture effect, which makes more counterions pack on and more co-ions leave from the electrode surface, leads to an increase of the counterion density within the EDL and thus a larger capacitance. Finally, these theoretical predictions are in good agreement with our experimental observations and offer guidance for designing RTIL mixtures for EDL supercapacitors.« less

Phase behaviors of binary mixtures composed of electron-rich and electron-poor triphenylene discotic liquid crystals

NASA Astrophysics Data System (ADS)

An, Lingling; Jing, Min; Xiao, Bo; Bai, Xiao-Yan; Zeng, Qing-Dao; Zhao, Ke-Qing

2016-09-01

Disk-like liquid crystals (DLCs) can self-assemble to ordered columnar mesophases and are intriguing one-dimensional organic semiconductors with high charge carrier mobility. To improve their applicable property of mesomorphic temperature ranges, we exploit the binary mixtures of electronic donor-acceptor DLC materials. The electron-rich 2,3,6,7,10,11-hexakis(alkoxy)triphenylenes (C4, C6, C8, C10, C12) and an electron-deficient tetrapentyl triphenylene-2,3,6,10-tetracarboxylate have been prepared and their binary mixtures have been investigated. The mesomorphism of the 1:1 (molar ratio) mixtures has been characterized by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), and small angel x-ray scattering (SAXS). The self-assembled monolayer structure of a discogen on a solid-liquid interface has been imaged by the high resolution scanning tunneling microscopy (STM). The match of peripheral chain length has important influence on the mesomorphism of the binary mixtures. Project supported by the National Natural Science Foundation of China (Grant Nos. 51273133 and 51443004).

Enhancing the Capacitive Performance of Electric Double-Layer Capacitors with Ionic Liquid Mixtures

DOE PAGES

Lian, C.; Liu, K.; Van Aken, Katherine L.; ...

2016-04-18

Formulating room-temperature ionic liquid (RTIL) mixed electrolytes was recently proposed as an effective and convenient strategy to increase the capacitive performance of electrochemical capacitors. In this paper, we investigate the electrical double-layer (EDL) structure and the capacitance of two RTILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF 4), and their mixtures with onion-like carbon electrodes using experiment and classical density functional theory. The principal difference between these ionic liquids is the smaller diameter of the BF 4 – anion relative to the TFSI – anion and the EMI + cation. A volcano-shaped trend is identified for the capacitance versus themore » composition of the RTIL mixture. The mixture effect, which makes more counterions pack on and more co-ions leave from the electrode surface, leads to an increase of the counterion density within the EDL and thus a larger capacitance. Finally, these theoretical predictions are in good agreement with our experimental observations and offer guidance for designing RTIL mixtures for EDL supercapacitors.« less

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.

Quantum liquids get thin

NASA Astrophysics Data System (ADS)

Ferrier-Barbut, Igor; Pfau, Tilman

2018-01-01

A liquid exists when interactions that attract its constituent particles to each other are counterbalanced by a repulsion acting at higher densities. Other characteristics of liquids are short-range correlations and the existence of surface tension (1). Ultracold atom experiments provide a privileged platform with which to observe exotic states of matter, but the densities are far too low to obtain a conventional liquid because the atoms are too far apart to create repulsive forces arising from the Pauli exclusion principle of the atoms' internal electrons. The observation of quantum liquid droplets in an ultracold mixture of two quantum fluids is now reported on page 301 of this issue by Cabrera et al. (2) and a recent preprint by Semeghini et al. (3). Unlike conventional liquids, these liquids arise from a weak attraction and repulsive many-body correlations in the mixtures.

Constructing a superhydrophobic surface on polydimethylsiloxane via spin coating and vapor-liquid sol-gel process.

PubMed

Peng, Yu-Ting; Lo, Kuo-Feng; Juang, Yi-Je

2010-04-06

In this study, a superhydrophobic surface on polydimethylsiloxane (PDMS) substrate was constructed via the proposed vapor-liquid sol-gel process in conjunction with spin coating of dodecyltrichlorosilane (DTS). Unlike the conventional sol-gel process where the reaction takes place in the liquid phase, layers of silica (SiO(2)) particles were formed through the reaction between the reactant spin-coated on the PDMS surface and vapor of the acid solution. This led to the SiO(2) particles inlaid on the PDMS surface. Followed by subsequent spin coating of DTS solution, the wrinkle-like structure was formed, and the static contact angle of the water droplet on the surface could reach 162 degrees with 2 degrees sliding angle and less than 5 degrees contact angle hysteresis. The effect of layers of SiO(2) particles, concentrations of DTS solution and surface topography on superhydrophobicity of the surface is discussed.

Dynamic bed reactor

DOEpatents

Stormo, Keith E.

1996-07-02

A dynamic bed reactor is disclosed in which a compressible open cell foam matrix is periodically compressed and expanded to move a liquid or fluid through the matrix. In preferred embodiments, the matrix contains an active material such as an enzyme, biological cell, chelating agent, oligonucleotide, adsorbent or other material that acts upon the liquid or fluid passing through the matrix. The active material may be physically immobilized in the matrix, or attached by covalent or ionic bonds. Microbeads, substantially all of which have diameters less than 50 microns, can be used to immobilize the active material in the matrix and further improve reactor efficiency. A particularly preferred matrix is made of open cell polyurethane foam, which adsorbs pollutants such as polychlorophenol or o-nitrophenol. The reactors of the present invention allow unidirectional non-laminar flow through the matrix, and promote intimate exposure of liquid reactants to active agents such as microorganisms immobilized in the matrix.

Improvement of the relaxation time and the order parameter of nematic liquid crystal using a hybrid alignment mixture of carbon nanotube and polyimide

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

Lee, Hyojin; Yang, Seungbin; Lee, Ji-Hoon, E-mail: jihoonlee@jbnu.ac.kr

2014-05-12

We examined the electrooptical properties of a nematic liquid crystal (LC) sample whose substrates were coated with a mixture of carbon nanotube (CNT) and polyimide (PI). The relaxation time of the sample coated with 1.5 wt. % CNT mixture was about 35% reduced compared to the pure polyimide sample. The elastic constant and the order parameter of the CNT-mixture sample were increased and the fast relaxation of LC could be approximated to the mean-field theory. We found the CNT-mixed polyimide formed more smooth surface than the pure PI from atomic force microscopy images, indicating the increased order parameter is related to themore » smooth surface topology of the CNT-polyimide mixture.« less

Properties of sugar-based low-melting mixtures

NASA Astrophysics Data System (ADS)

Fischer, Veronika; Kunz, Werner

2014-05-01

Physico-chemical properties of ternary sugar-based low-melting mixtures were determined. Choline chloride, urea and glucose or sorbitol, serving as sugars, were blended in various compositions. The refractive index, density, viscosity, decomposition temperatures and glass transition temperatures were measured. Further, the influence of temperature and water content was investigated. The results show that the mixtures are liquid below room temperature and the viscosity and density are dependent on the temperature and composition. Moreover, the viscosity decreases with increasing water content. These mixtures are biodegradable, low toxic, non-volatile, non-reactive with water and can be accomplished with low-cost materials. In consideration of these advantages and a melting point below room temperature, these low-melting mixtures can be a good alternative to ionic liquids as well as environmentally unfriendly and toxic solvents.

High Energy Density Solid and Liquid Hydrocarbon Fuels

DTIC Science & Technology

1989-02-01

affording a mixture of alcohols, 6a and 6b. The resulting mixture of alcohols was oxidized subsequently by using pyridinium chlorochromate (PCC) in...was added pyridinium chlorochromate (PCC, 3.00 g, 13.9 mmol), and the resulting mixture was stirred at room temperature for 1.5 h. The reaction mixture

Densities and viscosities of solutions of monoethanolamine + N-Methyldiethanolamine + water and monoethanolamine + 2-amino-2-methyl-1-propanol + water

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

Li, M.H.; Lie, Y.C.

1994-07-01

The densities and viscosities of aqueous mixtures of monoethanolamine (MEA) with N-methyldiethanolamine (MDEA) and MEA with 2-amino-2-methyl-1-propanol (AMP) have been studied at temperatures from 30 to 80 C. For density measurements, four MEA + MDEA (a total of 20 mass %) + H[sub 2]O mixtures and eight MEA + AMP (20 and 30 mass %) + H[sub 2]O mixtures were studied. For viscosity measurements, ten MEA + MDEA + H[sub 2]O mixtures and eight MEA + AMP + H[sub 2]O mixtures were measured. A Redlich-Kister equation of the excess volume was applied to represent the density of the liquid mixtures.more » The equation of Grunberg and Nissan of liquid viscosity was used to correlate the viscosity data. Both density and viscosity calculations show satisfactory results.« less

Organic fluid permeation through fluoropolymer membranes

DOEpatents

Nemser, Stuart M.; Kosaraju, Praveen; Bowser, John

2015-07-14

Separation of the components of liquid mixtures is achieved by contacting a liquid mixture with a nonporous membrane having a fluoropolymer selectively permeable layer and imposing a pressure gradient across the membrane from feed side to permeate side. Unusually high transmembrane flux is obtained when the membrane is subjected to one or more process conditions prior to separation. These include (a) leaving some residual amount of membrane casting solvent in the membrane, and (b) contacting the membrane with a component of the mixture to be separated for a duration effective to saturate the membrane with the component.

A new tunable dispersive liquid-liquid micro extraction method developed for the simultaneous preconcentration of lead and cadmium from lakes water: a multivariate study

NASA Astrophysics Data System (ADS)

Bilal, Muhammad; Kazi, Tasneem Gul; Afridi, Hassan Imran; Ali, Jamshed; Baig, Jameel Ahmed; Arain, Mohammad Balal; Khan, Mustafa

2017-08-01

A green tunable dispersive liquid-liquid micro extraction (TDLLME) technique was established for the simultaneous enrichment of lead (Pb) and cadmium (Cd) from different lakes water before analysis by flame atomic absorption spectrometry (FAAS). A solvent known as tunable polarity solvent (TPS), mixture of 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and 1-decanol, has been employed as extractant in aqueous medium. In first step this mixture can be made polar by slowly bubbling the antisolvent trigger (CO2) through the solution, which makes a monophasic solution. During this step hydrophobic complexes of the metals with 8-hydroxy quinoline (8-HQ) were extracted by TPS. Then the mixture was switched back to hydrophobic one by heating and/or bubbling nitrogen, turning the mixture into two phases again. In second phase the metals were leached out from the complexes entrapped in TPS, by treating with a solution of nitric acid and exposing the mixture to CO2, which switched the mixture into single phase. Then N2 purging and/or heating again turned the mixture into two phases. The acidic aqueous phase containing the metals was introduced to FAAS for analysis, whereas TPS was recycled for next experiment. Different parameters, affecting the efficiency the technique, were optimized by multivariate approach. The method was applied to certified reference material of water and to a real sample spiked with standards of known concentration, to confirm its validity and accuracy. LOD obtained for Pb and Cd were 0.560 and 0.056 μg L- 1 respectively. The developed method was applied successfully to the real water samples of two lakes of Sindh, Pakistan.

Method of Liquifying a gas

DOEpatents

Zollinger, William T.; Bingham, Dennis N.; McKellar, Michael G.; Wilding, Bruce M.; Klingler, Kerry M.

2006-02-14

A method of liquefying a gas is disclosed and which includes the steps of pressurizing a liquid; mixing a reactant composition with the pressurized liquid to generate a high pressure gas; supplying the high pressure gas to an expansion engine which produces a gas having a reduced pressure and temperature, and which further generates a power and/or work output; coupling the expansion engine in fluid flowing relation relative to a refrigeration assembly, and wherein the gas having the reduced temperature is provided to the refrigeration assembly; and energizing and/or actuating the refrigeration assembly, at least in part, by supplying the power and/or work output generated by the expansion engine to the refrigeration assembly, the refrigeration assembly further reducing the temperature of the gas to liquefy same.

Influence of trace elements mixture on bacterial diversity and fermentation characteristics of liquid diet fermented with probiotics under air-tight condition.

PubMed

He, Yuyong; Chen, Zhiyu; Liu, Xiaolan; Wang, Chengwei; Lu, Wei

2014-01-01

Cu2+, Zn2+, Fe2+ and I- are often supplemented to the diet of suckling and early weaning piglets, but little information is available regarding the effects of different Cu2+, Zn2+, Fe2+ and I- mixtures on bacteria growth, diversity and fermentation characteristics of fermented liquid diet for piglets. Pyrosequencing was performed to investigate the effect of Cu2+, Zn2+, Fe2+ and I- mixtures on the diversity, growth and fermentation characteristics of bacteria in the liquid diet fermented with Bacillus subtilis and Enterococcus faecalis under air-tight condition. Results showed that the mixtures of Cu2+, Zn2+, Fe2+ and I- at different concentrations promoted Bacillus growth, increased bacterial diversity and lactic acid production and lowered pH to about 5. The importance of Cu2+, Zn2+, Fe2+ and I- is different for Bacillus growth with the order Zn2+> Fe2+>Cu2+> I- in a 21-d fermentation and Cu2+>I->Fe2+>Zn2+ in a 42-d fermentation. Cu2+, Zn2+, Fe2+ and I- is recommended at a level of 150, 60, 150 and 0.6 mg/kg respectively for the production of fermented liquid diet with Bacillus subtilis. The findings improve our understanding of the influence of trace elements on liquid diet fermentation with probiotics and support the proper use of trace elements in the production of fermented liquid diet for piglets.

Ceramic-glass-metal seal by microwave heating

DOEpatents

Meek, Thomas T.; Blake, Rodger D.

1985-01-01

A method for producing a ceramic-glass-metal seal by microwaving mixes a slurry of glass sealing material and coupling agent and applies same to ceramic and metal workpieces. The slurry and workpieces are then insulated and microwaved at a power, time and frequency sufficient to cause a liquid phase reaction in the slurry. The reaction of the glass sealing material forms a chemically different seal than that which would be formed by conventional heating because it is formed by diffusion rather than by wetting of the reactants.

Ceramic-glass-metal seal by microwave heating

DOEpatents

Meek, T.T.; Blake, R.D.

1983-10-04

A method for producing a ceramic-glass-metal seal by microwaving, mixes a slurry of glass sealing material and coupling agent and applies same to ceramic and metal workpieces. The slurry and workpieces are then insulated and microwaved at a power, time and frequency sufficient to cause a liquid-phase reaction in the slurry. The reaction of the glass sealing material forms a chemically different seal than that which would be formed by conventional heating because it is formed by diffusion rather than by wetting of the reactants.

Graphene-based battery electrodes having continuous flow paths

DOEpatents

Zhang, Jiguang; Xiao, Jie; Liu, Jun; Xu, Wu; Li, Xiaolin; Wang, Deyu

2014-05-24

Some batteries can exhibit greatly improved performance by utilizing electrodes having randomly arranged graphene nanosheets forming a network of channels defining continuous flow paths through the electrode. The network of channels can provide a diffusion pathway for the liquid electrolyte and/or for reactant gases. Metal-air batteries can benefit from such electrodes. In particular Li-air batteries show extremely high capacities, wherein the network of channels allow oxygen to diffuse through the electrode and mesopores in the electrode can store discharge products.

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

Mixtures of amino-acid based ionic liquids and water.

PubMed

Chaban, Vitaly V; Fileti, Eudes Eterno

2015-09-01

New ionic liquids (ILs) involving increasing numbers of organic and inorganic ions are continuously being reported. We recently developed a new force field; in the present work, we applied that force field to investigate the structural properties of a few novel imidazolium-based ILs in aqueous mixtures via molecular dynamics (MD) simulations. Using cluster analysis, radial distribution functions, and spatial distribution functions, we argue that organic ions (imidazolium, deprotonated alanine, deprotonated methionine, deprotonated tryptophan) are well dispersed in aqueous media, irrespective of the IL content. Aqueous dispersions exhibit desirable properties for chemical engineering. The ILs exist as ion pairs in relatively dilute aqueous mixtures (10 mol%), while more concentrated mixtures feature a certain amount of larger ionic aggregates.

Distillation Separation of Hydrofluoric Acid and Nitric Acid from Acid Waste Using the Salt Effect on Vapor-Liquid Equilibrium

NASA Astrophysics Data System (ADS)

Yamamoto, Hideki; Sumoge, Iwao

2011-03-01

This study presents the distillation separation of hydrofluoric acid with use of the salt effect on the vapor-liquid equilibrium for acid aqueous solutions and acid mixtures. The vapor-liquid equilibrium of hydrofluoric acid + salt systems (fluorite, potassium nitrate, cesium nitrate) was measured using an apparatus made of perfluoro alkylvinylether. Cesium nitrate showed a salting-out effect on the vapor-liquid equilibrium of the hydrofluoric acid-water system. Fluorite and potassium nitrate showed a salting-in effect on the hydrofluoric acid-water system. Separation of hydrofluoric acid from an acid mixture containing nitric acid and hydrofluoric acid was tested by the simple distillation treatment using the salt effect of cesium nitrate (45 mass%). An acid mixture of nitric acid (5.0 mol · dm-3) and hydrofluoric acid (5.0 mol · dm-3) was prepared as a sample solution for distillation tests. The concentration of nitric acid in the first distillate decreased from 5.0 mol · dm-3 to 1.13 mol · dm-3, and the concentration of hydrofluoric acid increased to 5.41 mol · dm-3. This first distillate was further distilled without the addition of salt. The concentrations of hydrofluoric acid and nitric acid in the second distillate were 7.21 mol · dm-3 and 0.46 mol · dm-3, respectively. It was thus found that the salt effect on vapor-liquid equilibrium of acid mixtures was effective for the recycling of acids from acid mixture wastes.

Method for removing organic liquids from aqueous solutions and mixtures

DOEpatents

Hrubesh, Lawrence W.; Coronado, Paul R.; Dow, Jerome P.

2004-03-23

A method for removing organic liquids from aqueous solutions and mixtures. The method employs any porous material preferably in granular form and having small pores and a large specific surface area, that is hydrophobic so that liquid water does not readily wet its surface. In this method, organics, especially organic solvents that mix with and are more volatile than water, are separated from aqueous solution by preferentially evaporating across the liquid/solid boundary formed at the surfaces of the hydrophobic porous materials. Also, organic solvents that are immiscible with water, preferentially wet the surfaces of the hydrophobic material and are drawn within the porous materials by capillary action.

Ideal gas solubilities and solubility selectivities in a binary mixture of room-temperature ionic liquids.

PubMed

Finotello, Alexia; Bara, Jason E; Narayan, Suguna; Camper, Dean; Noble, Richard D

2008-02-28

This study focuses on the solubility behaviors of CO2, CH4, and N2 gases in binary mixtures of imidazolium-based room-temperature ionic liquids (RTILs) using 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][Tf2N]) and 1-ethyl-3-methylimidazolium tetrafluoroborate ([C2mim][BF4]) at 40 degrees C and low pressures (approximately 1 atm). The mixtures tested were 0, 25, 50, 75, 90, 95, and 100 mol % [C2mim][BF4] in [C2mim][Tf2N]. Results show that regular solution theory (RST) can be used to describe the gas solubility and selectivity behaviors in RTIL mixtures using an average mixture solubility parameter or an average measured mixture molar volume. Interestingly, the solubility selectivity, defined as the ratio of gas mole fractions in the RTIL mixture, of CO2 with N2 or CH4 in pure [C2mim][BF4] can be enhanced by adding 5 mol % [C2mim][Tf2N].

Fundamental Insights into the Dissolution and Precipitation of Cellulosic Biomass from Ionic Liquid Mixtures

NASA Astrophysics Data System (ADS)

Minnick, David L.

Lignocellulose is the most abundant biopolymer on earth making it a promising feedstock for the production of renewable chemicals and fuels. However, utilization of biomass remains a challenge as recalcitrance of cellulose and hemicellulose hinder separation and conversion of these carbohydrates. For instance, the complex inter- and intra- molecular hydrogen bonding network of cellulose renders it insoluble in nearly all aqueous and organic solvents. Alternatively, select ionic liquids (ILs) dissolve significant quantities. Through an ionic liquid mediated dissolution and precipitation process cellulose crystallinity is significantly reduced consequently enhancing subsequent chemical and biochemical reaction processes. Therefore, understanding the thermodynamics of ionic liquid - cellulose mixtures is imperative to developing an IL based biomass processing system. This dissertation illustrates solid-liquid phase equilibrium results for the dissolution and precipitation of cellulose in various IL/cosolvent, IL/antisolvent, and IL/mixed solvent systems with the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIm][DEP]). Molecular interactions between the ionic liquid, organic solvents, and cellulose are assessed by spectroscopic techniques including Kamlet-Taft solvatochromic analysis, FTIR, and NMR. Additionally, this dissertation discusses how preferential solvation of the IL cation and anion by co- and anti-solvents impact the ability of IL ions to interact with cellulose thus affecting the cellulose dissolution capacity of the various IL-solvent mixtures.

Phase behaviour, interactions, and structural studies of (amines+ionic liquids) binary mixtures.

PubMed

Jacquemin, Johan; Bendová, Magdalena; Sedláková, Zuzana; Blesic, Marijana; Holbrey, John D; Mullan, Claire L; Youngs, Tristan G A; Pison, Laure; Wagner, Zdeněk; Aim, Karel; Costa Gomes, Margarida F; Hardacre, Christopher

2012-05-14

We present a study on the phase equilibrium behaviour of binary mixtures containing two 1-alkyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide-based ionic liquids, [C(n)mim] [NTf(2)] (n=2 and 4), mixed with diethylamine or triethylamine as a function of temperature and composition using different experimental techniques. Based on this work, two systems showing an LCST and one system with a possible hourglass shape are measured. Their phase behaviours are then correlated and predicted by using Flory-Huggins equations and the UNIQUAC method implemented in Aspen. The potential of the COSMO-RS methodology to predict the phase equilibria was also tested for the binary systems studied. However, this methodology is unable to predict the trends obtained experimentally, limiting its use for systems involving amines in ionic liquids. The liquid-state structure of the binary mixture ([C(2)mim] [NTf(2)]+diethylamine) is also investigated by molecular dynamics simulation and neutron diffraction. Finally, the absorption of gaseous ethane by the ([C(2)mim][NTf(2)]+diethylamine) binary mixture is determined and compared with that observed in the pure solvents. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formulation of electroclinic, ferroelectric and antiferroelectric liquid crystal mixtures suitable for display devices

NASA Astrophysics Data System (ADS)

Debnath, Asim; Goswami, Debarghya; Mandal, Pradip Kumar

2018-04-01

Most of the liquid crystal display (LCD) devices starting from simplest wrist watches or calculators to complex laptops or flat TV sets are based on nematics. Although a tremendous improvement in the quality of display as well as reduction of manufacturing cost has taken place over the years, there are many issues which the LC industry is trying hard to address. Ferroelectric liquid crystals (FLC) are of current interest in the LCD industry since among various other advantages FLC based displays have micro-second order switching compared to milli-second order switching in nematic based displays. To meet the market demand much effort has been made to optimize the physical parameters of FLCs, such as temperature range, spontaneous polarization (PS), helical pitch (p), switching time (τ), tilt angle (θ) and rotational viscosity (γ). Multicomponent mixtures are, therefore, formulated to optimize all the required properties for practical applications since no single FLC compound can satisfy the above requirements. To the best of our knowledge electroclinic, ferroelectric and antiferroelectric liquid crystal mixtures have been formulated first time by any Indian group which have properties suitable for FLC based display devices and at par with mixtures used in the industry.

Byproduct-free mass production of compound semiconductor nanowires: zinc phosphide

NASA Astrophysics Data System (ADS)

Chen, Yixi; Polinnaya, Rakesh; Vaddiraju, Sreeram

2018-05-01

A method for the mass production of compound semiconductor nanowires that involves the direct reaction of component elements in a chemical vapor deposition chamber (CVD) is presented. This method results in nanowires, without the associated production of any other byproducts such as nanoparticles or three-dimensional (3D) bulk crystals. Furthermore, no unreacted reactants remain mixed with the nanowire product in this method. This byproduct-free nanowire production thus circumvents the need to tediously purify and collect nanowires from a mixture of products/reactants after their synthesis. Demonstration made using zinc phosphide (Zn3P2) material system as an example indicated that the direct reaction of zinc microparticles with phosphorus supplied via the vapor phase results in the production of gram quantities of nanowires. To enhance thermal transport and achieve the complete reaction of zinc microparticles, while simultaneously ensuring that the microparticles do not agglomerate into macroscale zinc particles and partly remain unreacted (owing to diffusion limitations), pellets composed of mixtures of zinc and a sacrificial salt, NH4Cl, were employed as the starting material. The sublimation by decomposition of NH4Cl in the early stages of the reaction leaves a highly porous pellet of zinc composed of only zinc microparticles, which allows for inward diffusion of phosphorus/outward diffusion of zinc and the complete conversion of zinc into Zn3P2 nanowires. NH4Cl also aids in removal of any native oxide layer present on the zinc microparticles that may prevent their reaction with phosphorus. This method may be used to mass produce many other nanowires in a byproduct-free manner, besides Zn3P2.

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.

Distributed combustion in a cyclonic burner

NASA Astrophysics Data System (ADS)

Sorrentino, Giancarlo; Sabia, Pino; de Joannon, Mara; Cavaliere, Antonio; Ragucci, Raffaele

2017-11-01

Distributed combustion regime occurs in several combustion technologies were efficient and environmentally cleaner energy conversion are primary tasks. For such technologies (MILD, LTC, etc…), working temperatures are enough low to boost the formation of several classes of pollutants, such as NOx and soot. To access this temperature range, a significant dilution as well as preheating of reactants is required. Such conditions are usually achieved by a strong recirculation of exhaust gases that simultaneously dilute and pre-heat the fresh reactants. However, the intersection of low combustion temperatures and highly diluted mixtures with intense pre-heating alters the evolution of the combustion process with respect to traditional flames, leading to significant features such as uniformity and distributed ignition. The present study numerically characterized the turbulence-chemistry and combustion regimes of propane/oxygen mixtures, highly diluted in nitrogen, at atmospheric pressure, in a cyclonic combustor under MILD Combustion operating conditions. The velocity and mixing fields were obtained using CFD with focus on mean and fluctuating quantities. The flow-field information helped differentiate between the impact of turbulence levels and dilution ones. The integral length scale along with the fluctuating velocity is critical to determine Damköhler and Karlovitz numbers. Together these numbers identify the combustion regime at which the combustor is operating. This information clearly distinguishes between conventional flames and distributed combustion. The results revealed that major controllers of the reaction regime are dilution and mixing levels; both are significantly impacted by lowering oxygen concentration through entrainment of hot reactive species from within the combustor, which is important in distributed combustion. Understanding the controlling factors of distributed regime is critical for the development and deployment of these novel combustion technologies for near zero emissions from high intensity combustors and energy savings using fossil and biofuels for sustainable energy conversion.

Brillouin-scattering study of liquid-glass transitions in ternary mixtures of water, trehalose, and an ionic liquid

NASA Astrophysics Data System (ADS)

Takayama, Haruki; Shibata, Tomohiko; Ishii, Takahiro; Kojima, Seiji

2013-04-01

Ternary mixtures of water, sugar, and ionic liquid have been studied as new candidates for bioprotectants. To clarify the elastic properties and relaxation dynamics of the supercooled liquid and glassy states at low temperatures, the liquid-glass transitions were investigated by using a micro-Brillouin-scattering technique. The refractive index was measured accurately as a function of content and temperature to determine the sound velocity and the attenuation from Brillouin frequency shift and peak width. The relaxation times of structural relaxations related to liquidglass transitions were determined as functions of temperature. The Meyer-Neldel rule was found to hold for the activation energy and the prefactor of the Arrhenius law for the relaxation time.

Resolving Discrepancies in the Measurements of the Interfacial Tension for the CO2 + H2O Mixture by Computer Simulation.

PubMed

Müller, Erich A; Mejía, Andrés

2014-04-03

Literature values regarding the pressure dependence of the interfacial tension of the system of carbon dioxide (CO2) + water (H2O) show an unexplained divergence and scatter at the transition between low-pressure gas-liquid equilibrium and the high-pressure liquid-liquid equilibrium. We employ the Statistical Associating Fluid Theory (SAFT) and canonical molecular dynamics simulations based on the corresponding coarse grained force field to map out the phase diagram of the mixture and the interfacial tension for this system. We showcase how at ambient temperatures a triple point (gas-liquid-liquid) is expected and detail the implications that the appearance of the third phase has on the interfacial tensions of the system.

Effects of variation in chain length on ternary polymer electrolyte - Ionic liquid mixture - A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Raju, S. G.; Hariharan, Krishnan S.; Park, Da-Hye; Kang, HyoRang; Kolake, Subramanya Mayya

2015-10-01

Molecular dynamics (MD) simulations of ternary polymer electrolyte - ionic liquid mixtures are conducted using an all-atom model. N-alkyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([CnMPy][TFSI], n = 1, 3, 6, 9) and polyethylene oxide (PEO) are used. Microscopic structure, energetics and dynamics of ionic liquid (IL) in these ternary mixtures are studied. Properties of these four pure IL are also calculated and compared to that in ternary mixtures. Interaction between pyrrolidinium cation and TFSI is stronger and there is larger propensity of ion-pair formation in ternary mixtures. Unlike the case in imidazolium IL, near neighbor structural correlation between TFSI reduces with increase in chain length on cation in both pure IL and ternary mixtures. Using spatial density maps, regions where PEO and TFSI interact with pyrrolidinium cation are identified. Oxygens of PEO are above and below the pyrrolidinium ring and away from the bulky alkyl groups whereas TFSI is present close to nitrogen atom of CnMPy. In pure IL, diffusion coefficient (D) of C3MPy is larger than of TFSI but D of C9MPy and C6MPy are larger than that of TFSI. The reasons for alkyl chain dependent phenomena are explored.

Mechanism for Increasing the Pressure in an Oil Well by a Combustible Oxidizing Liquid Mixture

NASA Astrophysics Data System (ADS)

Melik-Gaikazov, G. V.

2014-09-01

A method of estimating the pressure pulse arising in a deep oil well as a result of the thermal explosion of a combustible oxidizing liquid mixture in it is presented. It was established that less than 10% of this mixture is expended for the formation of a pressure pulse in this well. The conditions under which a tubing string positioned in such a well experiences a plastic bending and its walls are crumpled were determined. The maximum admissible difference between the pressures at the walls of this tube were calculated, and axial compression loads were related to critical forces of different orders. It is shown that, when the indicated tube is submerged in the liquid in the well, its resistance to a short-time axial compression load increases.

Investigation on the structure of liquid N-methylformamide-dimethylsulfoxide mixtures

NASA Astrophysics Data System (ADS)

Cordeiro, João M. M.; Soper, Alan K.

2011-03-01

The structures of liquid mixtures of N-methylformamide (NMF) and dimethyl sulfoxide (DMSO) at two concentrations (80% and 50% NMF) are investigated using a combination of neutron diffraction augmented with isotopic substitution and empirical potential structure refinement simulations. The results indicate that the NMF and DMSO molecules are hydrogen-bonded to one another with a preference for NMF-DMSO hydrogen bonding, compared to the NMF-NMF ones. The liquid is orientationally structured as a consequence of these hydrogen bonds between molecules. NMF-DMSO dimers are very stable species in the bulk of the mixture. The structure of the dimers is such that the angle between the molecular dipole moments is around 60°. The NMF molecules are well solvated in DMSO with potential implications for peptides solvation in this solvent.

Ionic liquids for separation of olefin-paraffin mixtures

DOEpatents

Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

2013-09-17

The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

Ionic liquids for separation of olefin-paraffin mixtures

DOEpatents

Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

2014-07-15

The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

Numerical modeling and analytical modeling of cryogenic carbon capture in a de-sublimating heat exchanger

NASA Astrophysics Data System (ADS)

Yu, Zhitao; Miller, Franklin; Pfotenhauer, John M.

2017-12-01

Both a numerical and analytical model of the heat and mass transfer processes in a CO2, N2 mixture gas de-sublimating cross-flow finned duct heat exchanger system is developed to predict the heat transferred from a mixture gas to liquid nitrogen and the de-sublimating rate of CO2 in the mixture gas. The mixture gas outlet temperature, liquid nitrogen outlet temperature, CO2 mole fraction, temperature distribution and de-sublimating rate of CO2 through the whole heat exchanger was computed using both the numerical and analytic model. The numerical model is built using EES [1] (engineering equation solver). According to the simulation, a cross-flow finned duct heat exchanger can be designed and fabricated to validate the models. The performance of the heat exchanger is evaluated as functions of dimensionless variables, such as the ratio of the mass flow rate of liquid nitrogen to the mass flow rate of inlet flue gas.

Protic ionic liquids based on the dimeric and oligomeric anions: [(AcO)xH(x-1)]-.

PubMed

Johansson, K M; Izgorodina, E I; Forsyth, M; MacFarlane, D R; Seddon, K R

2008-05-28

We describe a fluidity and conductivity study as a function of composition in N-methylpyrrolidine-acetic acid mixtures. The simple 1 : 1 acid-base mixture appears to form an ionic liquid, but its degree of ionicity is quite low and such liquids are better thought of as poorly dissociated mixtures of acid and base. The composition consisting of 3 moles acetic acid and 1 mole N-methylpyrrolidine is shown to form the highest ionicity mixture in this binary due to the presence of oligomeric anionic species [(AcO)(x)H(x-1)](-) stabilised by hydrogen bonds. These oligomeric species, being weaker bases than the acetate anion, shift the proton transfer equilibrium towards formation of ionic species, thus generating a higher degree of ionicity than is present at the 1 : 1 composition. A Walden plot analysis, thermogravimetric behaviour and proton NMR data, as well as ab initio calculations of the oligomeric species, all support this conclusion.

[Evaluation of chromatographic performance of polymerized ionic liquid stationary phase for capillary gas chromatography].

PubMed

Chen, Xiaoyan; Lu, Kai; Qi, Meiling; Fu, Ruonong

2009-11-01

The selectivity and thermal stability of ionic liquids as the stationary phases for capillary gas chromatography (CGC) have attracted much attention of researchers in recent years. In this study, 1-vinyl-3-benzyl imidazolium-bis(trifluoromethane-sulphonyl)imidate (VBIm-NTf2) was synthesized and polymerized (PVBIm-NTf2) in a CGC column. In comparison with VBIm-NTf2, PVBIm-NTf2 exhibits much better thermal stability and chromatographic selectivity, and achieves satisfactory resolution for Grob test mixture, alcohols mixture, esters mixture and aromatics mixture with narrow and symmetric peak shapes. The satisfactory resolution and selectivity of the polymerized column still remain after conditioned at 250 degrees C for 6 h. Additionally, the Abraham solvation parameters of PVBIm-NTf2 were determined and the interactions between the stationary phase and solutes were elucidated. The present work demonstrates that the polymerization is an effective way to improve the selectivity and thermal stability of common ionic liquids as CGC stationary phases.

Absorption degree analysis on biogas separation with ionic liquid systems.

PubMed

Zhang, Xin; Zhang, Suojiang; Bao, Di; Huang, Ying; Zhang, Xiangping

2015-01-01

For biogas upgrading, present work mainly focuses on either thermodynamics or mass transfer properties. A systematical study on these two aspects is important for developing a new biogas separation process. In this work, a new criterion "absorption degree", which combines both thermodynamics and mass transfer properties, was proposed for the first time to comprehensively evaluate the absorption performance. Henry's law constants of CO2 and CH4 in ionic liquids-polyethylene glycol dimethyl ethers mixtures were investigated. The liquid-side mass transfer coefficients (kL) were determined. The results indicate that IL-NHD mixtures exhibit not only a high CO2/CH4 selectivity, but also a fast kL for CO2 absorption. The [bmim][NO3]+NHD mixtures present a high absorption degree value for CO2 but a low value for CH4. For presenting a highest relative absorption degree value, the 50wt% [bmim][NO3]+50wt% NHD mixture is recommended for biogas upgrading. Copyright © 2014 Elsevier Ltd. All rights reserved.

An Introduction to the Understanding of Solubility.

ERIC Educational Resources Information Center

Letcher, Trevor M.; Battino, Rubin

2001-01-01

Explores different solubility processes and related issues, including the second law of thermodynamics and ideal mixtures, real liquids, intermolecular forces, and solids in liquids or gases in liquids. (Contains 22 references.) (ASK)

Adsorption on hydrophobic porous glass near the liquid/liquid coexistence curve of a binary liquid mixture

NASA Astrophysics Data System (ADS)

Grüll, H.; Woermann, D.

1997-01-01

A differential refractometric method is used to study the temperature and composition dependence of the adsorptive properties of porous glass in 2-butoxyethanol (abbreviated C4E1)/water mixtures. The surface of the adsorbent carries hydrophobic -SiO-C8H17 as well as hydrophilic -SiOH groups. The experiments are carried out close to the liquid/liquid coexistence curve in the vicinity of the lower critical point of the system. Depending on the temperature and composition of the mixtures either C4E1 or water is preferentially adsorbed. There exists a line along which the net adsorption vanishes. For compositions x>xc (x, mole fraction of C4E1; xc, critical composition) the amount of substance of adsorbed water ñ ws(Tp) per unit gram of adsorbent at temperature Tp increases with increasing values of the temperature difference (Tp-Tc) in the range 0 K<(Tp-Tc)<4 K. Tp is the temperature of phase separation of the bulk mixture in the presence of the adsorbent. Beginning at temperatures (Tp-Tc)>4 K the adsorbed amount of substance ñ ws(Tp) decreases. At (Tp-Tc)>8 K it reaches a value which is smaller by a factor of about 10 compared with its maximum value. This phenomenon is reminiscent of a wetting transition.

Adsorption of hydrophobin/β-casein mixtures at the solid-liquid interface.

PubMed

Tucker, I M; Petkov, J T; Penfold, J; Thomas, R K; Cox, A R; Hedges, N

2016-09-15

The adsorption behaviour of mixtures of the proteins β-casein and hydrophobin at the hydrophilic solid-liquid surface have been studied by neutron reflectivity. The results of measurements from sequential adsorption and co-adsorption from solution are contrasted. The adsorption properties of protein mixtures are important for a wide range of applications. Because of competing factors the adsorption behaviour of protein mixtures at interfaces is often difficult to predict. This is particularly true for mixtures containing hydrophobin as hydrophobin possesses some unusual surface properties. At β-casein concentrations ⩾0.1wt% β-casein largely displaces a pre-adsorbed layer of hydrophobin at the interface, similar to that observed in hydrophobin-surfactant mixtures. In the composition and concentration range studied here for the co-adsorption of β-casein-hydrophobin mixtures the adsorption is dominated by the β-casein adsorption. The results provide an important insight into how the competitive adsorption in protein mixtures of hydrophobin and β-casein can impact upon the modification of solid surface properties and the potential for a wide range of colloid stabilisation applications. Copyright © 2016 Elsevier Inc. All rights reserved.

Deep-release of Epon 828 epoxy from the shock-driven reaction product phase

NASA Astrophysics Data System (ADS)

Lang, John; Fredenburg, Anthony; Coe, Joshua; Dattelbaum, Dana

2017-06-01

A challenge in improving equations-of-state (EOS) for polymers and their product phase is the lack of off-Hugoniot data. Here, we describe a novel experimental approach for obtaining release pathways along isentropes from the shocked products. A series of gas-gun experiments was conducted to obtain release isentropes of the products for 70/30 wt% Epon 828 epoxy resin/Jeffamine T-403 curing agent. Thin epoxy flyers backed by a low-density syntactic foam were impacted into LiF windows at up to 6.3 mm/ μs, creating stresses in excess of those required for reaction ( 25 GPa). Following a sustained shock input, a rarefaction fan from the back of the thin flyer reduced the pressure in the epoxy products along a release isentrope. Optical velocimetry (PDV) was used to measure the particle velocity at the epoxy/LiF interface. Numerical simulations using several different EOS describing the reactant-to-product transformation were conducted, and the results were compared with measured wave profiles. The best agreement with experiment was obtained using separate tabular EOS for the polymer ``reactant'' (e.g. epoxy) and product mixture, suggesting the transition to the products is irreversible.

Combined goal gasifier and fuel cell system and method

DOEpatents

Gmeindl, Frank D.; Geisbrecht, Rodney A.

1990-01-01

A molten carbonate fuel cell is combined with a catalytic coal or coal char gasifier for providing the reactant gases comprising hydrogen, carbon monoxide and carbon dioxide used in the operation of the fuel cell. These reactant gases are stripped of sulfur compounds and particulate material and are then separated in discrete gas streams for conveyance to appropriate electrodes in the fuel cell. The gasifier is arranged to receive the reaction products generated at the anode of the fuel cell by the electricity-producing electrochemical reaction therein. These reaction products from the anode are formed primarily of high temperature steam and carbon dioxide to provide the steam, the atmosphere and the heat necessary to endothermically pyrolyze the coal or char in the presence of a catalyst. The reaction products generated at the cathode are substantially formed of carbon dioxide which is used to heat air being admixed with the carbon dioxide stream from the gasifier for providing the oxygen required for the reaction in the fuel cell and for driving an expansion device for energy recovery. A portion of this carbon dioxide from the cathode may be recycled into the fuel cell with the air-carbon dioxide mixture.

Temperature modulation and quadrature detection for selective titration of two-state exchanging reactants.

PubMed

Zrelli, K; Barilero, T; Cavatore, E; Berthoumieux, H; Le Saux, T; Croquette, V; Lemarchand, A; Gosse, C; Jullien, L

2011-04-01

Biological samples exhibit huge molecular diversity over large concentration ranges. Titrating a given compound in such mixtures is often difficult, and innovative strategies emphasizing selectivity are thus demanded. To overcome limitations inherent to thermodynamics, we here present a generic technique where discrimination relies on the dynamics of interaction between the target of interest and a probe introduced in excess. Considering an ensemble of two-state exchanging reactants submitted to temperature modulation, we first demonstrate that the amplitude of the out-of-phase concentration oscillations is maximum for every compound involved in a reaction whose equilibrium constant is equal to unity and whose relaxation time is equal to the inverse of the excitation angular frequency. Taking advantage of this feature, we next devise a highly specific detection protocol and validate it using a microfabricated resistive heater and an epifluorescence microscope, as well as labeled oligonucleotides to model species displaying various dynamic properties. As expected, quantification of a sought for strand is obtained even if interfering reagents are present in similar amounts. Moreover, our approach does not require any separation and is compatible with imaging. It could then benefit some of the numerous binding assays performed every day in life sciences.

Ionic Liquids as templating agents in formation of uranium-containing nanomaterials

DOEpatents

Visser, Ann E; Bridges, Nicholas J

2014-06-10

A method for forming nanoparticles containing uranium oxide is described. The method includes combining a uranium-containing feedstock with an ionic liquid to form a mixture and holding the mixture at an elevated temperature for a period of time to form the product nanoparticles. The method can be carried out at low temperatures, for instance less than about 300.degree. C.

Chemical Kinetics Interpretation of Hypergolicity of Ionic Liquid-Based Systems

DTIC Science & Technology

2009-04-01

acid (WFNA) mixtures 6 4. Thermochemistry of imidazoles, triazoles and tetrazoles 8 5. Thermochemistry of compounds formed...reactivity of gaseous mixtures formed above ionic liquids (ILs) when mixed with white fuming nitric acid (WFNA). After a general introduction on the...replacement for NTO is also of interest but probably less crucial. For instance, NTO could be replaced by nitric acid (or by any other suitable

Apparatus and method for phosphate-accelerated bioremediation

DOEpatents

Looney, Brian B.; Pfiffner, Susan M.; Phelps, Tommy J.; Lombard, Kenneth H.; Hazen, Terry C.; Borthen, James W.

1998-01-01

An apparatus and method for supplying a vapor-phase nutrient to contaminated soil for in situ bioremediation. The apparatus includes a housing adapted for containing a quantity of the liquid nutrient, a conduit in communication with the interior of the housing, means for causing a gas to flow through the conduit, and means for contacting the gas with the liquid so that a portion thereof evaporates and mixes with the gas. The mixture of gas and nutrient vapor is delivered to the contaminated site via a system of injection and extraction wells configured to the site and provides for the use of a passive delivery system. The mixture has a partial pressure of vaporized nutrient that is no greater than the vapor pressure of the liquid. If desired, the nutrient and/or the gas may be heated to increase the vapor pressure and the nutrient concentration of the mixture. Preferably, the nutrient is a volatile, substantially nontoxic and nonflammable organic phosphate that is a liquid at environmental temperatures, such as triethyl phosphate or tributyl phosphate.

Apparatus and method for phosphate-accelerated bioremediation

DOEpatents

Looney, B.B.; Phelps, T.J.; Hazen, T.C.; Pfiffner, S.M.; Lombard, K.H.; Borthen, J.W.

1994-01-01

An apparatus and method for supplying a vapor-phase nutrient to contaminated soil for in situ bioremediation. The apparatus includes a housing adapted for containing a quantity of the liquid nutrient, a conduit in fluid communication with the interior of the housing, means for causing a gas to flow through the conduit, and means for contacting the gas with the liquid so that a portion thereof evaporates and mixes with the gas. The mixture of gas and nutrient vapor is delivered to the contaminated site via a system of injection and extraction wells configured to the site. The mixture has a partial pressure of vaporized nutrient that is no greater than the vapor pressure of the liquid. If desired, the nutrient and/or the gas may be heated to increase the vapor pressure and the nutrient concentration of the mixture. Preferably, the nutrient is a volatile, substantially nontoxic and nonflammable organic phosphate that is a liquid at environmental temperatures, such as triethyl phosphate or tributyl phosphate.

Method for phosphate-accelerated bioremediation

DOEpatents

Looney, Brian B.; Lombard, Kenneth H.; Hazen, Terry C.; Pfiffner, Susan M.; Phelps, Tommy J.; Borthen, James W.

1996-01-01

An apparatus and method for supplying a vapor-phase nutrient to contaminated soil for in situ bioremediation. The apparatus includes a housing adapted for containing a quantity of the liquid nutrient, a conduit in fluid communication with the interior of the housing, means for causing a gas to flow through the conduit, and means for contacting the gas with the liquid so that a portion thereof evaporates and mixes with the gas. The mixture of gas and nutrient vapor is delivered to the contaminated site via a system of injection and extraction wells configured to the site. The mixture has a partial pressure of vaporized nutrient that is no greater than the vapor pressure of the liquid. If desired, the nutrient and/or the gas may be heated to increase the vapor pressure and the nutrient concentration of the mixture. Preferably, the nutrient is a volatile, substantially nontoxic and nonflammable organic phosphate that is a liquid at environmental temperatures, such as triethyl phosphate or tributyl phosphate.

Refractive index, molar refraction and comparative refractive index study of propylene carbonate binary liquid mixtures.

PubMed

Wankhede, Dnyaneshwar Shamrao

2012-06-01

Refractive indices (n) have been experimentally determined for the binary liquid-liquid mixtures of Propylene carbonate (PC) (1) with benzene, ethylbenzene, o-xylene and p-xylene (2) at 298.15, 303.15 and 308.15 K over the entire mole fraction range. The experimental values of n are utilised to calculate deviation in refractive index (Δn), molar refraction (R) and deviation in molar refraction (ΔR). A comparative study of Arago-Biot (A-B), Newton (NW), Eyring and John (E-J) equations for determining refractive index of a liquid has been carried out to test their validity for all the binary mixtures over the entire composition range at 298.15 K. Comparison of various mixing relations is represented in terms of average deviation (AVD). The Δn and ΔR values have been fitted to Redlich-Kister equation at 298.15 K and standard deviations have been calculated. The results are discussed in terms of intermolecular interactions present amongst the components.

Study of liquid?liquid demixing from drug solution

NASA Astrophysics Data System (ADS)

Lafferrère, Laurent; Hoff, Christian; Veesler, Stéphane

2004-09-01

In pharmaceutical industry, a deep understanding of the phase diagram is required in design of crystallization processes. We have investigated the phase diagram of a pharmaceutical compound (C 35H 41Cl 2N 3O 2) in a mixture of ethanol/water. This phase diagram exhibits a solid-solid (polymorphism) and a liquid-liquid-phase separation (LLPS) as a function of temperature and drug substance concentration. This study focuses on the LLPS which is metastable with respect to the crystallization of the two polymorphs FI and FII of C 35H 41Cl 2N 3O 2 in an ethanol/water mixture. The LLPS is metastable towards the solubility curve on the whole solvent-solute concentrations and temperature range studied. The LLPS occurred within the metastable zone for crystallization. In our experiments the liquid-liquid-phase transition prevented the drug from crystallizing, while it changed the medium and the conditions of crystallization, which consequently affected the process. The coexistence curves for the liquid phases, also named TL-L boundary, and the spinodal line were measured for a ternary mixture of water-drug-ethanol at atmospheric pressure over a temperature range of 10-50°C. This temperature range corresponds to that used in the crystallization process. Static Light Scattering, HPLC measurements and Karl-Fischer titration were applied to investigate the drug-phase diagram. The isoplethe section of the phase diagram exhibits four regions: one homogeneous (one liquid) and three two-phases (two regions with one liquid+one solid and one region with two liquids), the two solids phases being two polymorphs.

Turbidity of a Binary Fluid Mixture: Determining Eta

NASA Technical Reports Server (NTRS)

Jacobs, Donald T.

1996-01-01

A ground based (1-g) experiment is in progress that will measure the turbidity of a density-matched, binary fluid mixture extremely close to its liquid-liquid critical point. By covering the range of reduced temperatures t equivalent to (T-T(sub c)) / T(sub c) from 10(exp -8) to 10(exp -2), the turbidity measurements will allow the critical exponent eta to be determined. No experiment has precisely determined a value of the critical exponent eta, yet its value is significant to theorists in critical phenomena. Relatively simple critical phenomena, as in the liquid-liquid system studied here, serve as model systems for more complex systems near a critical point.

Do group 1 metal salts form deep eutectic solvents?

PubMed

Abbott, A P; D'Agostino, C; Davis, S J; Gladden, L F; Mantle, M D

2016-09-14

Mixtures of metal salts such as ZnCl 2 , AlCl 3 and CrCl 3 ·6H 2 O form eutectic mixtures with complexing agents, such as urea. The aim of this research was to see if alkali metal salts also formed eutectics in the same way. It is shown that only a limited number of sodium salts form homogeneous liquids at ambient temperatures and then only with glycerol. None of these mixtures showed eutectic behaviour but the liquids showed the physical properties similar to the group of mixtures classified as deep eutectic solvents. This study focussed on four sodium salts: NaBr, NaOAc, NaOAc·3H 2 O and Na 2 B 4 O 7 ·10H 2 O. The ionic conductivity and viscosity of these salts with glycerol were studied, and it was found that unlike previous studies of quaternary ammonium salts with glycerol, where the salt decreased the viscosity, most of the sodium salts increased the viscosity. This suggests that sodium salts have a structure making effect on glycerol. This phenomenon is probably due to the high charge density of Na + , which coordinates to the glycerol. 1 H and 23 Na NMR diffusion and relaxation methods have been used to understand the molecular dynamics in the glycerol-salt mixtures, and probe the effect of water on some of these systems. The results reveal a complex dynamic behaviour of the different species within these liquids. Generally, the translational dynamics of the 1 H species, probed by means of PFG NMR diffusion coefficients, is in line with the viscosity of these liquids. However, 1 H and 23 Na T 1 relaxation measurements suggest that the Na-containing species also play a crucial role in the structure of the liquids.

Molecular dynamics study of polysaccharides in binary solvent mixtures of an ionic liquid and water.

PubMed

Liu, Hanbin; Sale, Kenneth L; Simmons, Blake A; Singh, Seema

2011-09-01

Some ionic liquids (ILs) have great promise as effective solvents for biomass pretreatment, and there are several that have been reported that can dissolve large amounts of cellulose. The solubilized cellulose can then be recovered by addition of antisolvents, such as water or ethanol, and this regeneration process plays an important role in the subsequent enzymatic saccharification reactions and in the recovery of the ionic liquid. To date, little is known about the fundamental intermolecular interactions that drive the dissolution and subsequent regeneration of cellulose in complex mixtures of ionic liquids, water, and cellulose. To investigate these interactions, in this work, molecular dynamics (MD) simulations were carried out to study binary and ternary mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) with water and a cellulose oligomer. Simulations of a cellulose oligomer dissolved in three concentrations of binary mixtures of [C2mim][OAc] and water were used to represent the ternary system in the dissolution phase (high [C2mim][OAc] concentration) and present during the initial phase of the regeneration step (intermediate and low [C2mim][OAc] concentrations). The MD analysis of the structure and dynamics that exist in these binary and ternary mixtures provides information on the key intermolecular interactions between cellulose and [C2mim][OAc] that lead to dissolution of cellulose and the key intermolecular interactions in the intermediate states of cellulose precipitation as a function of water content in the cellulose/IL/water system. The analysis of this intermediate state provides new insight into the molecular driving forces present in this ternary system. © 2011 American Chemical Society

Superconducting cable cooling system by helium gas and a mixture of gas and liquid helium

DOEpatents

Dean, John W.

1977-01-01

Thermally contacting, oppositely streaming cryogenic fluid streams in the same enclosure in a closed cycle that changes from a cool high pressure helium gas to a cooler reduced pressure helium fluid comprised of a mixture of gas and boiling liquid so as to be near the same temperature but at different pressures respectively in go and return legs that are in thermal contact with each other and in thermal contact with a longitudinally extending superconducting transmission line enclosed in the same cable enclosure that insulates the line from the ambient at a temperature T.sub.1. By first circulating the fluid in a go leg from a refrigerator at one end of the line as a high pressure helium gas near the normal boiling temperature of helium; then circulating the gas through an expander at the other end of the line where the gas becomes a mixture of reduced pressure gas and boiling liquid at its boiling temperature; then by circulating the mixture in a return leg that is separated from but in thermal contact with the gas in the go leg and in the same enclosure therewith; and finally returning the resulting low pressure gas to the refrigerator for compression into a high pressure gas at T.sub.2 is a closed cycle, where T.sub.1 >T.sub.2, the temperature distribution is such that the line temperature is nearly constant along its length from the refrigerator to the expander due to the boiling of the liquid in the mixture. A heat exchanger between the go and return lines removes the gas from the liquid in the return leg while cooling the go leg.

Ionic liquids as solvents for Čerenkov counting and the effect of a wavelength shifter.

PubMed

Mirenda, M; Rodrigues, D; Ferreyra, C; Arenillas, P; Sarmiento, G P; Krimer, N; Japas, M L

2018-04-01

We study the wavelength shift of the Čerenkov light - generated in the ionic liquid (BMIMCl) - caused by the addition of the highly fluorescent ionic liquid (BMIMHPTS). 18 F and 32 P efficiencies increases up to 124% and 14%, respectively, compared with the values obtained with pure BMIMCl. With this improvement, ionic liquid mixtures become a good alternative - when using the TDCR-Cherenkov technique - to standardize radionuclides having electron emissions energies close to the threshold energy in water (∼ 260keV). As an advantage compared with other solvents, the Ionic liquid mixture can be reused, in the case of short-lived radionuclides, by simply removing all water content in a vacuum oven. Copyright © 2017 Elsevier Ltd. All rights reserved.

Low temperature oxidation of benzene and toluene in mixture with n-decane

PubMed Central

Herbinet, Olivier; Husson, Benoit; Ferrari, Maude; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique

2013-01-01

The oxidation of two blends, benzene/n-decane and toluene/n-decane, was studied in a jet-stirred reactor with gas chromatography analysis (temperatures from 500 to 1100 K, atmospheric pressure, stoichiometric mixtures). The studied hydrocarbon mixtures contained 75% of aromatics in order to highlight the chemistry of the low-temperature oxidation of these two aromatic compounds which have a very low reactivity compared to large alkanes. The difference of behavior between the two aromatic reactants is highly pronounced concerning the formation of derived aromatic products below 800 K. In the case of benzene, only phenol could be quantified. In the case of toluene, significant amounts of benzaldehyde, benzene, and cresols were also formed, as well as several heavy aromatic products such as bibenzyl, phenylbenzylether, methylphenylbenzylether, and ethylphenylphenol. A comparison with results obtained with neat n-decane showed that the reactivity of the alkane is inhibited by the presence of benzene and, to a larger extent, toluene. An improved model for the oxidation of toluene was developed based on recent theoretical studies of the elementary steps involved in the low-temperature chemistry of this molecule. Simulations using this model were successfully compared with the obtained experimental results. PMID:23762017

Sequestration of non-pure carbon dioxide streams in iron oxyhydroxide-containing saline repositories

USGS Publications Warehouse

Garcia, S.; Rosenbauer, Robert J.; Palandri, James L.; Maroto-Valer, M. Mercedes

2012-01-01

Iron oxyhydroxide, goethite (α-FeOOH), was evaluated as a potential formation mineral reactant for trapping CO2 in a mineral phase such as siderite (FeCO3), when a mixture of CO2-SO 2 flue gas is injected into a saline aquifer. Two thermodynamic simulations were conducted, equilibrating a CO2-SO2 fluid mixture with a NaCl-brine and Fe-rich rocks at 150 °C and 300 bar. The modeling studies evaluated mineral and fluid composition at equilibrium and the influence of pH buffering in the system. Results show siderite precipitates both in the buffered and unbuffered system; however, the presence of an alkaline pH buffer enhances the stability of the carbonate. Based on the model, an experiment was designed to compare with thermodynamic predictions. A CO2-SO2 gas mixture was reacted in 150 ml of NaCl-NaOH brine containing 10 g of goethite at 150 °C and 300 bar for 24 days. Mineralogical and brine chemistry confirmed siderite as the predominant reaction product in the system. Seventy-six mg of CO2 are sequestered in siderite per 10 g of goethite.

Discriminant analysis of fused positive and negative ion mobility spectra using multivariate self-modeling mixture analysis and neural networks.

PubMed

Chen, Ping; Harrington, Peter B

2008-02-01

A new method coupling multivariate self-modeling mixture analysis and pattern recognition has been developed to identify toxic industrial chemicals using fused positive and negative ion mobility spectra (dual scan spectra). A Smiths lightweight chemical detector (LCD), which can measure positive and negative ion mobility spectra simultaneously, was used to acquire the data. Simple-to-use interactive self-modeling mixture analysis (SIMPLISMA) was used to separate the analytical peaks in the ion mobility spectra from the background reactant ion peaks (RIP). The SIMPLSIMA analytical components of the positive and negative ion peaks were combined together in a butterfly representation (i.e., negative spectra are reported with negative drift times and reflected with respect to the ordinate and juxtaposed with the positive ion mobility spectra). Temperature constrained cascade-correlation neural network (TCCCN) models were built to classify the toxic industrial chemicals. Seven common toxic industrial chemicals were used in this project to evaluate the performance of the algorithm. Ten bootstrapped Latin partitions demonstrated that the classification of neural networks using the SIMPLISMA components was statistically better than neural network models trained with fused ion mobility spectra (IMS).

Ambient cure polyimide foams prepared from aromatic polyisocyanates, aromatic polycarboxylic compounds, furfuryl alcohol, and a strong inorganic acid

NASA Technical Reports Server (NTRS)

Sawko, Paul M. (Inventor); Riccitiello, Salvatore R. (Inventor); Hamermesh, Charles L. (Inventor)

1980-01-01

Flame and temperature resistant polyimide foams are prepared by the reaction of an aromatic dianhydride, e.g., pyromellitic dianhydride, with an aromatic polyisocyanate, e.g., polymethylene polyphenylisocyanate (PAPI) in the presence of an inorganic acid and a lower molecular weight alcohol, e.g., dilute sulfuric acid or phosphoric acid and furfuryl alcohol. The exothermic reaction between the acid and the alcohol provides the heat necessary for the other reactants to polymerize without the application of any external heat. Such mixtures, therefore, are ideally suited for in situ foam formation, especially where the application of heat is not practical or possible.

Palladium-Mediated Catalysis Leads to Intramolecular Narcissistic Self-Sorting on a Cavitand Platform.

PubMed

Nagymihály, Zoltán; Caturello, Naidel A M S; Takátsy, Anikó; Aragay, Gemma; Kollár, László; Albuquerque, Rodrigo Q; Csók, Zsolt

2017-01-06

Palladium-catalyzed aminocarbonylation reactions have been used to directly convert a tetraiodocavitand intermediate into the corresponding carboxamides and 2-ketocarboxamides. When complex mixtures of the amine reactants are employed in competition experiments using polar solvents, such as DMF, no "mixed" products possessing structurally different amide fragments are detected either by 1 H or 13 C NMR. Only highly symmetrical cavitands are sorted out of a large number of potentially feasible products, which represents a rare example of intramolecular, narcissistic self-sorting. Our experimental results along with thermodynamic energy analysis suggest that the observed self-sorting is a symmetry-driven, kinetically controlled process.

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.

Ionic Liquids Database- (ILThermo)

National Institute of Standards and Technology Data Gateway

SRD 147 NIST Ionic Liquids Database- (ILThermo) (Web, free access)   IUPAC Ionic Liquids Database, ILThermo, is a free web research tool that allows users worldwide to access an up-to-date data collection from the publications on experimental investigations of thermodynamic, and transport properties of ionic liquids as well as binary and ternary mixtures containing ionic liquids.

Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities

DOEpatents

Dumesic, James A [Verona, WI; Ruiz, Juan Carlos Serrano [Madison, WI; West, Ryan M [Madison, WI

2012-04-03

Described is a method to make liquid chemicals, such as functional intermediates, solvents, and liquid fuels from biomass-derived cellulose. The method is cascading; the product stream from an upstream reaction can be used as the feedstock in the next downstream reaction. The method includes the steps of deconstructing cellulose to yield a product mixture comprising levulinic acid and formic acid, converting the levulinic acid to .gamma.-valerolactone, and converting the .gamma.-valerolactone to pentanoic acid. Alternatively, the .gamma.-valerolactone can be converted to a mixture of n-butenes. The pentanoic acid so formed can be further reacted to yield a host of valuable products. For example, the pentanoic acid can be decarboxylated yield 1-butene or ketonized to yield 5-nonanone. The 5-nonanone can be hydrodeoxygenated to yield nonane, or 5-nonanone can be reduced to yield 5-nonanol. The 5-nonanol can be dehydrated to yield nonene, which can be dimerized to yield a mixture of C.sub.9 and C.sub.18 olefins, which can be hydrogenated to yield a mixture of alkanes. Alternatively, the nonene may be isomerized to yield a mixture of branched olefins, which can be hydrogenated to yield a mixture of branched alkanes. The mixture of n-butenes formed from .gamma.-valerolactone can also be subjected to isomerization and oligomerization to yield olefins in the gasoline, jet and Diesel fuel ranges.

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.

A Study on Optimal Sizing of Pipeline Transporting Equi-sized Particulate Solid-Liquid Mixture

NASA Astrophysics Data System (ADS)

Asim, Taimoor; Mishra, Rakesh; Pradhan, Suman; Ubbi, Kuldip

2012-05-01

Pipelines transporting solid-liquid mixtures are of practical interest to the oil and pipe industry throughout the world. Such pipelines are known as slurry pipelines where the solid medium of the flow is commonly known as slurry. The optimal designing of such pipelines is of commercial interests for their widespread acceptance. A methodology has been evolved for the optimal sizing of a pipeline transporting solid-liquid mixture. Least cost principle has been used in sizing such pipelines, which involves the determination of pipe diameter corresponding to the minimum cost for given solid throughput. The detailed analysis with regard to transportation of slurry having solids of uniformly graded particles size has been included. The proposed methodology can be used for designing a pipeline for transporting any solid material for different solid throughput.

Lattice model for water-solute mixtures.

PubMed

Furlan, A P; Almarza, N G; Barbosa, M C

2016-10-14

A lattice model for the study of mixtures of associating liquids is proposed. Solvent and solute are modeled by adapting the associating lattice gas (ALG) model. The nature of interaction of solute/solvent is controlled by tuning the energy interactions between the patches of ALG model. We have studied three set of parameters, resulting in, hydrophilic, inert, and hydrophobic interactions. Extensive Monte Carlo simulations were carried out, and the behavior of pure components and the excess properties of the mixtures have been studied. The pure components, water (solvent) and solute, have quite similar phase diagrams, presenting gas, low density liquid, and high density liquid phases. In the case of solute, the regions of coexistence are substantially reduced when compared with both the water and the standard ALG models. A numerical procedure has been developed in order to attain series of results at constant pressure from simulations of the lattice gas model in the grand canonical ensemble. The excess properties of the mixtures, volume and enthalpy as the function of the solute fraction, have been studied for different interaction parameters of the model. Our model is able to reproduce qualitatively well the excess volume and enthalpy for different aqueous solutions. For the hydrophilic case, we show that the model is able to reproduce the excess volume and enthalpy of mixtures of small alcohols and amines. The inert case reproduces the behavior of large alcohols such as propanol, butanol, and pentanol. For the last case (hydrophobic), the excess properties reproduce the behavior of ionic liquids in aqueous solution.

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

Nguyen, Luan; Tao, Franklin, E-mail: franklin.tao.2011@gmail.com; Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ studymore » of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.« less

Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis.

PubMed

Nguyen, Luan; Tao, Franklin Feng

2016-06-01

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

Assessment and prediction of joint algal toxicity of binary mixtures of graphene and ionic liquids.

PubMed

Wang, Zhuang; Zhang, Fan; Wang, Se; Peijnenburg, Willie J G M

2017-10-01

Graphene and ionic liquids (ILs) released into the environment will interact with each other. So far however, the risks associated with the concurrent exposure of biota to graphene and ILs in the environment have received little attention. The research reported here focused on observing and predicting the joint toxicity effects in the green alga Scenedesmus obliquus exposed to binary mixtures of intrinsic graphene (iG)/graphene oxide (GO) and five ILs of varying anionic and cationic types. The isolated ILs in the binary mixtures were the main contributors to toxicity. The binary GO-IL mixtures resulted in more severe joint toxicity than the binary iG-IL mixtures, irrespective of mixture ratios. The mechanism of the joint toxicity may be associated with the adsorption capability of the graphenes for the ILs, the dispersion stability of the graphenes in aquatic media, and modulation of the binary mixtures-induced oxidative stress. A toxic unit assessment showed that the graphene and IL toxicities were additive at low concentration of the mixtures but antagonistic at high concentration of the mixtures. Predictions made using the concentration addition and independent action models were close to the observed joint toxicities regardless of mixture types and mixture ratios. These findings provide new insights that are of use in the risk assessment of mixtures of engineered nanoparticles and other environmentally relevant contaminants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nano-particle dynamics during capillary suction.

PubMed

Kuijpers, C J; Huinink, H P; Tomozeiu, N; Erich, S J F; Adan, O C G

2018-07-01

Due to the increased use of nanoparticles in everyday applications, there is a need for theoretical descriptions of particle transport and attachment in porous media. It should be possible to develop a one dimensional model to describe nanoparticle retention during capillary transport of liquid mixtures in porous media. Water-glycerol-nanoparticle mixtures were prepared and the penetration process in porous Al 2 O 3 samples of varying pore size is measured using NMR imaging. The liquid and particle front can be measured by utilizing T 2 relaxation effects from the paramagnetic nanoparticles. A good agreement between experimental data and the predicted particle retention by the developed theory is found. Using the model, the binding constant for Fe 2 O 3 nanoparticles on sintered Al 2 O 3 samples and the maximum surface coverage are determined. Furthermore, we show that the penetrating liquid front follows a square root of time behavior as predicted by Darcy's law. However, scaling with the liquid parameters is no longer sufficient to map different liquid mixtures onto a single master curve. The Darcy model should be extended to address the two formed domains (with and without particles) and their interaction, to give an accurate prediction for the penetrating liquid front. Copyright © 2018 Elsevier Inc. All rights reserved.

Hydrothermal pretreatment of several lignocellulosic mixtures containing wheat straw and two hardwood residues available in Southern Europe.

PubMed

Silva-Fernandes, Talita; Duarte, Luís Chorão; Carvalheiro, Florbela; Loureiro-Dias, Maria Conceição; Fonseca, César; Gírio, Francisco

2015-05-01

This work studied the processing of biomass mixtures containing three lignocellulosic materials largely available in Southern Europe, eucalyptus residues (ER), wheat straw (WS) and olive tree pruning (OP). The mixtures were chemically characterized, and their pretreatment, by autohydrolysis, evaluated within a severity factor (logR0) ranging from 1.73 up to 4.24. A simple modeling strategy was used to optimize the autohydrolysis conditions based on the chemical characterization of the liquid fraction. The solid fraction was characterized to quantify the polysaccharide and lignin content. The pretreatment conditions for maximal saccharides recovery in the liquid fraction were at a severity range (logR0) of 3.65-3.72, independently of the mixture tested, which suggests that autohydrolysis can effectively process mixtures of lignocellulosic materials for further biochemical conversion processes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Exergie /4th revised and enlarged edition/

NASA Astrophysics Data System (ADS)

Baloh, T.; Wittwer, E.

The theoretical concept of exergy is explained and its practical applications are discussed. Equilibrium and thermal equilibrium are reviewed as background, and exergy is considered as a reference point for solid-liquid, liquid-liquid, and liquid-gas systems. Exergetic calculations and their graphic depictions are covered. The concepts of enthalpy and entropy are reviewed in detail, including their applications to gas mixtures, solutions, and isolated substances. The exergy of gas mixtures, solutions, and isolated substances is discussed, including moist air, liquid water in water vapor, dry air, and saturation-limited solutions. Mollier exergy-enthalpy-entropy diagrams are presented for two-component systems, and exergy losses for throttling, isobaric mixing, and heat transfer are addressed. The relationship of exergy to various processes is covered, including chemical processes, combustion, and nuclear reactions. The optimization of evaporation plants through exergy is discussed. Calculative examples are presented for energy production and heating, industrial chemical processes, separation of liquid air, nuclear reactors, and others.

Phase equilibrium measurements on nine binary mixtures

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

Wilding, W.V.; Giles, N.F.; Wilson, L.C.

1996-11-01

Phase equilibrium measurements have been performed on nine binary mixtures. The PTx method was used to obtain vapor-liquid equilibrium data for the following systems at two temperatures each: (aminoethyl)piperazine + diethylenetriamine; 2-butoxyethyl acetate + 2-butoxyethanol; 2-methyl-2-propanol + 2-methylbutane; 2-methyl-2-propanol + 2-methyl-2-butene; methacrylonitrile + methanol; 1-chloro-1,1-difluoroethane + hydrogen chloride; 2-(hexyloxy)ethanol + ethylene glycol; butane + ammonia; propionaldehyde + butane. Equilibrium vapor and liquid phase compositions were derived form the PTx data using the Soave equation of state to represent the vapor phase and the Wilson or the NRTL activity coefficient model to represent the liquid phase. A large immiscibility region existsmore » in the butane + ammonia system at 0 C. Therefore, separate vapor-liquid-liquid equilibrium measurements were performed on this system to more precisely determine the miscibility limits and the composition of the vapor phase in equilibrium with the two liquid phases.« less

Density and refractive index data of binary and ternary mixtures of imidazolium-based ionic liquids, n-hexane and organic compounds involved in the kinetic resolution of rac-2-pentanol.

PubMed

Montalbán, Mercedes G; Collado-González, Mar; Lozano-Pérez, A Abel; Baños, F Guillermo Díaz; Víllora, Gloria

2018-08-01

This data article is related to the subject of the research article "Extraction of Organic Compounds Involved in the Kinetic Resolution of rac-2-Pentanol from n-Hexane by Imidazolium-based Ionic Liquids: Liquid-Liquid Equilibrium" (Montalbán et al., 2018) [1]. It contains experimental data of density and refractive index of binary and ternary mixtures of imidazolium-based ionic liquids, n -hexane and organic compounds involved in the kinetic resolution of rac -2-pentanol ( rac -2-pentanol, vinyl butyrate, rac -2-pentyl butyrate or butyric acid) measured at 303.15 K and 1 atm. These data are presented as calibration curves which help to determine the composition of the ionic liquid-rich phase knowing its density or refractive index.

Catalytic bioreactors and methods of using same

DOEpatents

Worden, Robert Mark; Liu, Yangmu Chloe

2017-07-25

Various embodiments provide a bioreactor for producing a bioproduct comprising one or more catalytically active zones located in a housing and adapted to keep two incompatible gaseous reactants separated when in a gas phase, wherein each of the one or more catalytically active zones may comprise a catalytic component retainer and a catalytic component retained within and/or thereon. Each of the catalytically active zones may additionally or alternatively comprise a liquid medium located on either side of the catalytic component retainer. Catalytic component may include a microbial cell culture located within and/or on the catalytic component retainer, a suspended catalytic component suspended in the liquid medium, or a combination thereof. Methods of using various embodiments of the bioreactor to produce a bioproduct, such as isobutanol, are also provided.

Tunable integration of absorption-membrane-adsorption for efficiently separating low boiling gas mixtures near normal temperature

PubMed Central

Liu, Huang; Pan, Yong; Liu, Bei; Sun, Changyu; Guo, Ping; Gao, Xueteng; Yang, Lanying; Ma, Qinglan; Chen, Guangjin

2016-01-01

Separation of low boiling gas mixtures is widely concerned in process industries. Now their separations heavily rely upon energy-intensive cryogenic processes. Here, we report a pseudo-absorption process for separating low boiling gas mixtures near normal temperature. In this process, absorption-membrane-adsorption is integrated by suspending suitable porous ZIF material in suitable solvent and forming selectively permeable liquid membrane around ZIF particles. Green solvents like water and glycol were used to form ZIF-8 slurry and tune the permeability of liquid membrane surrounding ZIF-8 particles. We found glycol molecules form tighter membrane while water molecules form looser membrane because of the hydrophobicity of ZIF-8. When using mixing solvents composed of glycol and water, the permeability of liquid membrane becomes tunable. It is shown that ZIF-8/water slurry always manifests remarkable higher separation selectivity than solid ZIF-8 and it could be tuned to further enhance the capture of light hydrocarbons by adding suitable quantity of glycol to water. Because of its lower viscosity and higher sorption/desorption rate, tunable ZIF-8/water-glycol slurry could be readily used as liquid absorbent to separate different kinds of low boiling gas mixtures by applying a multistage separation process in one traditional absorption tower, especially for the capture of light hydrocarbons. PMID:26892255

Solvent effects on the polar network of ionic liquid solutions

NASA Astrophysics Data System (ADS)

Bernardes, Carlos E. S.; Shimizu, Karina; Canongia Lopes, José N.

2015-05-01

Molecular dynamics simulations were used to probe mixtures of ionic liquids (ILs) with common molecular solvents. Four types of systems were considered: (i) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide plus benzene, hexafluorobenzene or 1,2-difluorobenzene mixtures; (ii) choline-based ILs plus ether mixtures (iii) choline-based ILs plus n-alkanol mixtures; and (iv) 1-butyl-3-methylimidazolium nitrate and 1-ethyl-3-methylimidazolium ethyl sulfate aqueous mixtures. The results produced a wealth of structural and aggregation information that highlight the resilience of the polar network of the ILs (formed by clusters of alternating ions and counter-ions) to the addition of different types of molecular solvent. The analysis of the MD data also shows that the intricate balance between different types of interaction (electrostatic, van der Waals, H-bond-like) between the different species present in the mixtures has a profound effect on the morphology of the mixtures at a mesoscopic scale. In the case of the IL aqueous solutions, the present results suggest an alternative interpretation for very recently published x-ray and neutron diffraction data on similar systems.

Characterisation of aerosol combustible mixtures generated using condensation process

NASA Astrophysics Data System (ADS)

Saat, Aminuddin; Dutta, Nilabza; Wahid, Mazlan A.

2012-06-01

An accidental release of a liquid flammable substance might be formed as an aerosol (droplet and vapour mixture). This phenomenon might be due to high pressure sprays, pressurised liquid leaks and through condensation when hot vapour is rapidly cooled. Such phenomena require a fundamental investigation of mixture characterisation prior to any subsequent process such as evaporation and combustion. This paper describes characterisation study of droplet and vapour mixtures generated in a fan stirred vessel using condensation technique. Aerosol of isooctane mixtures were generated by expansion from initially a premixed gaseous fuel-air mixture. The distribution of droplets within the mixture was characterised using laser diagnostics. Nearly monosized droplet clouds were generated and the droplet diameter was defined as a function of expansion time. The effect of changes in pressure, temperature, fuel-air fraction and expansion ratio on droplet diameter was evaluated. It is shown that aerosol generation by expansion was influenced by the initial pressure and temperature, equivalence ratio and expansion rates. All these parameters affected the onset of condensation which in turn affected the variation in droplet diameter.

Method for Predicting Hypergolic Mixture Flammability Limits

DTIC Science & Technology

2017-02-01

liquid phase, in the gas phase, at the liquid / liquid interface and at the gas / liquid interface during hypergolic ignition and the interactions...of what happens in the liquid phase, in the gas phase, at the liquid / liquid interface and at the gas / liquid interface during hypergolic ignition...and the interactions of all these phases. The ignition happens in the gas -phase but products formed here and there (in the liquid phase or at

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

Martínez-Ruiz, F. J.; Blas, F. J., E-mail: felipe@uhu.es; Moreno-Ventas Bravo, A. I.

We determine the interfacial properties of a symmetrical binary mixture of equal-sized spherical Lennard-Jones molecules, σ{sub 11} = σ{sub 22}, with the same dispersive energy between like species, ϵ{sub 11} = ϵ{sub 22}, but different dispersive energies between unlike species low enough to induce phase separation. We use the extensions of the improved version of the inhomogeneous long-range corrections of Janecek [J. Phys. Chem. B 110, 6264 (2006)], presented recently by MacDowell and Blas [J. Chem. Phys. 131, 074705 (2009)] and Martínez-Ruiz et al. [J. Chem. Phys. 141, 184701 (2014)], to deal with the interaction energy and microscopic components ofmore » the pressure tensor. We perform Monte Carlo simulations in the canonical ensemble to obtain the interfacial properties of the symmetrical mixture with different cut-off distances r{sub c} and in combination with the inhomogeneous long-range corrections. The pressure tensor is obtained using the mechanical (virial) and thermodynamic route. The liquid-liquid interfacial tension is also evaluated using three different procedures, the Irving-Kirkwood method, the difference between the macroscopic components of the pressure tensor, and the test-area methodology. This allows to check the validity of the recent extensions presented to deal with the contributions due to long-range corrections for intermolecular energy and pressure tensor in the case of binary mixtures that exhibit liquid-liquid immiscibility. In addition to the pressure tensor and the surface tension, we also obtain density profiles and coexistence densities and compositions as functions of pressure, at a given temperature. According to our results, the main effect of increasing the cut-off distance r{sub c} is to sharpen the liquid-liquid interface and to increase the width of the biphasic coexistence region. Particularly interesting is the presence of a relative minimum in the total density profiles of the symmetrical mixture. This minimum is related with a desorption of the molecules at the interface, a direct consequence of a combination of the weak dispersive interactions between unlike species of the symmetrical binary mixture, and the presence of an interfacial region separating the two immiscible liquid phases in coexistence.« less

On the validity of Stokes-Einstein and Stokes-Einstein-Debye relations in ionic liquids and ionic-liquid mixtures.

PubMed

Köddermann, Thorsten; Ludwig, Ralf; Paschek, Dietmar

2008-09-15

Stokes-Einstein (SE) and Stokes-Einstein-Debye (SED) relations in the neat ionic liquid (IL) [C(2)mim][NTf(2)] and IL/chloroform mixtures are studied by means of molecular dynamics (MD) simulations. For this purpose, we simulate the translational diffusion coefficients of the cations and anions, the rotational correlation times of the C(2)--H bond in the cation C(2)mim(+), and the viscosities of the whole system. We find that the SE and SED relations are not valid for the pure ionic liquid, nor for IL/chloroform mixtures down to the miscibility gap (at 50 wt % IL). The deviations from both relations could be related to dynamical heterogeneities described by the non-Gaussian parameter alpha(t). If alpha(t) is close to zero, at a concentration of 1 wt % IL in chloroform, both relations become valid. Then, the effective radii and volumes calculated from the SE and SED equations can be related to the structures found in the MD simulations, such as aggregates of ion pairs. Overall, similarities are observed between the dynamical properties of supercooled water and those of ionic liquids.

Method of preparing electrodes with porous current collector structures and solid reactants for secondary electrochemical cells

DOEpatents

Gay, Eddie C.; Martino, Fredric J.

1976-01-01

Particulate electrode reactants, for instance transition metal sulfides for the positive electrodes and lithium alloys for the negative electrodes, are vibratorily compacted into porous, electrically conductive structures. Structures of high porosity support sufficient reactant material to provide high cell capacity per unit weight while serving as an electrical current collector to improve the utilization of reactant materials. Pore sizes of the structure and particle sizes of the reactant material are selected to permit uniform vibratory loading of the substrate without settling of the reactant material during cycling.

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.

One-pot aldol condensation and hydrodeoxygenation of biomass-derived carbonyl compounds for biodiesel synthesis.

PubMed

Faba, Laura; Díaz, Eva; Ordóñez, Salvador

2014-10-01

Integrating reaction steps is of key interest in the development of processes for transforming lignocellulosic materials into drop-in fuels. We propose a procedure for performing the aldol condensation (reaction between furfural and acetone is taken as model reaction) and the total hydrodeoxygenation of the resulting condensation adducts in one step, yielding n-alkanes. Different combinations of catalysts (bifunctional catalysts or mechanical mixtures), reaction conditions, and solvents (aqueous and organic) have been tested for performing these reactions in an isothermal batch reactor. The results suggest that the use of bifunctional catalysts and aqueous phase lead to an effective integration of both reactions. Therefore, selectivities to n-alkanes higher than 50% were obtained using this catalyst at typical hydrogenation conditions (T=493 K, P=4.5 MPa, 24 h reaction time). The use of organic solvent, carbonaceous supports, or mechanical mixtures of monofunctional catalysts leads to poorer results owing to side effects; mainly, hydrogenation of reactants and adsorption processes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Porous Titanium Parts Fabricated by Sintering of TiH2 and Ti Powder Mixtures

NASA Astrophysics Data System (ADS)

Peng, Qin; Yang, Bin; Friedrich, Bernd

2018-01-01

A new simple powder metallurgy process by sintering TiH2 powders was used to manufacture porous Ti components. The effects of the processing parameters (pressure of cold isostatic pressing and sintering temperature) and the TiH2/Ti ratio in the powder mixtures on the impurities, the linear shrinkage and the pore properties (including overall and open porosities) were comprehensively determined. The addition of TiH2 as a reactant has been found beneficial for the synthesis of porous Ti components. The formation mechanisms of pores were demonstrated based on the dehydrogenation process of TiH2 during sintering, resulting in highest reactivity due to the "in statu nascendi" generation of the metal. In addition, the hardness and corrosion resistance of all the sintered samples were evaluated, related to the overall and open porosities. As a result, an optimal composition of Ti-40 wt.% TiH2 was defined, as its maximum open porosity was about 23%.

Diffuse interfacelets in transcritical flows of propellants into high-pressure combustors

NASA Astrophysics Data System (ADS)

Urzay, Javier; Jofre, Lluis

2017-11-01

Rocket engines and new generations of high-power jet engines and diesel engines oftentimes involve the injection of one or more reactants at subcritical temperatures into combustor environments at high pressures, and more particularly, at pressures higher than those corresponding to the critical points of the individual components of the mixture, which typically range from 13 to 50 bars for most propellants. This class of trajectories in the thermodynamic space has been traditionally referred to as transcritical. Under particular conditions often found in hydrocarbon-fueled chemical propulsion systems, and despite the prevailing high pressures, the flow in the combustor may contain regions close to the injector where a diffuse interface is formed in between the fuel and oxidizer streams that is sustained by surface-tension forces as a result of the elevation of the critical pressure of the mixture. This talk describes progress towards modeling these effects in the conservation equations. Funded by the US Department of Energy.

Auto-ignition of methane-air mixtures flowing along an array of thin catalytic plates

NASA Astrophysics Data System (ADS)

Treviño, C.

2010-12-01

In this paper, the heterogeneous ignition of a methane-air mixture flowing along an infinite array of catalytic parallel plates has been studied by inclusion of gas expansion effects and the finite heat conduction on the plates. The system of equations considers the full compressible Navier-Stokes equations coupled with the energy equations of the plates. The gas expansion effects which arise from temperature changes have been considered. The heterogeneous kinetics considers the adsorption and desorption reactions for both reactants. The limits of large and small longitudinal thermal conductance of the plate material are analyzed and the critical conditions for ignition are obtained in closed form. The governing equations are solved numerically using finite differences. The results show that ignition is more easily produced as the longitudinal wall thermal conductance increases, and the effects of the gas expansion on the catalytic ignition process are rather small due to the large value of the activation energy of the desorption reaction of adsorbed oxygen atoms.

Cryogenic on-orbit liquid depot storage acquisition and transfer (COLD-SAT) experiment subsystem instrumentation and wire harness design report

NASA Technical Reports Server (NTRS)

Edwards, Lawrence G.

1994-01-01

Subcritical cryogens such as liquid hydrogen (LH2) and liquid oxygen (LO2) are required for space based transportation propellant, reactant, and life support systems. Future long-duration space missions will require on-orbit systems capable of long-term cryogen storage and efficient fluid transfer capabilities. COLD-SAT, which stands for cryogenic orbiting liquid depot-storage acquisition and transfer, is a free-flying liquid hydrogen management flight experiment. Experiments to determine optimum methods of fluid storage and transfer will be performed on the COLD-SAT mission. The success of the mission is directly related to the type and accuracy of measurements made. The instrumentation and measurement techniques used are therefore critical to the success of the mission. This paper presents the results of the COLD-SAT experiment subsystem instrumentation and wire harness design effort. Candidate transducers capable of fulfilling the COLD-SAT experiment measurement requirements are identified. Signal conditioning techniques, data acquisition requirements, and measurement uncertainty analysis are presented. Electrical harnessing materials and wiring techniques for the instrumentation designed to minimize heat conduction to the cryogenic tanks and provide optimum measurement accuracy are listed.

49 CFR 178.338-11 - Discharge control devices.

Code of Federal Regulations, 2010 CFR

2010-10-01

... devices. (a) Excess-flow valves are not required. (b) Each liquid filling and liquid discharge line must... tank that is used to transport argon, carbon dioxide, helium, krypton, neon, nitrogen, xenon, or mixtures thereof, each liquid filling and liquid discharge line must be provided with an on-vehicle...

Liquid methane gelled with methanol and water reduces rate of nitrogen absorption

NASA Technical Reports Server (NTRS)

Vanderwall, E. M.

1972-01-01

Dilution of gelant vapor with inert carrier gas accomplishes gelation. Mixture is injected through heated tube and orifice into liquid methane for immediate condensation within bulk of liquid. Direct dispersion of particles in liquid avoids condensation on walls of vessel and eliminates additional mixing.

Exploration of dielectric relaxations of a room temperature anti-ferroelectric liquid crystal mixture

NASA Astrophysics Data System (ADS)

Dwivedi, Aanchal; Verma, Rohit; Dhar, R.; Dabrowski, R.

2018-05-01

Dielectric characterization of a technologically important room temperature anti-ferroelectric liquid crystal (AFLC) mixture has been carried out as a function of temperature and frequency. The mixture has a phase sequence of I-SmA*-SmC*-SmCA* -SmIA* -Cr. Electrical study for the planar anchoring of the molecules demonstrates seven relaxation mechanisms in various mesophases of the mixture. Dielectric spectrum of paraelectric SmA* phase exhibits a relaxation mechanism due to the tilt fluctuation of the molecules. In ferroelectric SmC* phase, Goldstone mode has been observed due to the fluctuation in azimuthal angle. In antiferroelectric SmCA*and hexatic SmIA* phases two relaxation mechanisms are observed due to bond orientation order & anti-phase fluctuation and rotation around the short axes respectively.

Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities

DOEpatents

Dumesic, James A.; Ruiz, Juan Carlos Serrano; West, Ryan M.

2015-06-30

Described is a method to make liquid chemicals. The method includes deconstructing cellulose to yield a product mixture comprising levulinic acid and formic acid, converting the levulinic acid to .gamma.-valerolactone, and converting the .gamma.-valerolactone to pentanoic acid. Alternatively, the .gamma.-valerolactone can be converted to a mixture of n-butenes. The pentanoic acid can be decarboxylated yield 1-butene or ketonized to yield 5-nonanone. The 5-nonanone can be hydrodeoxygenated to yield nonane, or 5-nonanone can be reduced to yield 5-nonanol. The 5-nonanol can be dehydrated to yield nonene, which can be dimerized to yield a mixture of C.sub.9 and C.sub.18 olefins, which can be hydrogenated to yield a mixture of alkanes.

Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities

DOEpatents

Dumesic, James A [Verona, WI; Ruiz, Juan Carlos Serrano [Madison, WI; West, Ryan M [Madison, WI

2014-01-07

Described is a method to make liquid chemicals. The method includes deconstructing cellulose to yield a product mixture comprising levulinic acid and formic acid, converting the levulinic acid to .gamma.-valerolactone, and converting the .gamma.-valerolactone to pentanoic acid. Alternatively, the .gamma.-valerolactone can be conveted to a mixture of n-butenes. The pentanoic acid can be decarboxylated yield 1-butene or ketonized to yield 5-nonanone. The 5-nonanone can be hydrodeoxygenated to yield nonane, or 5-nonanone can be reduced to yield 5-nonanol. The 5-nonanol can be dehydrated to yield nonene, which can be dimerized to yield a mixture of C.sub.9 and C.sub.18 olefins, which can be hydrogenated to yield a mixture of alkanes.

Relationship between composition of mixture charged and that in circulation in an auto refrigerant cascade and a J-T refrigerator operating in liquid refrigerant supply mode

NASA Astrophysics Data System (ADS)

Sreenivas, Bura; Nayak, H. Gurudath; Venkatarathnam, G.

2017-01-01

The composition of the refrigerant mixture in circulation during steady state operation of J-T and allied refrigerators is not the same as that charged due to liquid hold up in the heat exchangers and phase separators, as well as the differential solubility of different refrigerant components in the compressor lubricating oil. The performance of refrigerators/liquefiers operating on mixed refrigerant cycles is dependent on the mixture composition. It is therefore important to charge the right mixture that results in an optimum composition in circulation during steady state operation. The relationship between the charged and circulating composition has been experimentally studied in a J-T refrigerator operating in the liquid refrigerant supply (LRS) mode and an auto refrigerant cascade refrigerator (with a phase separator) operating in the gas refrigerant supply (GRS) mode. The results of the study are presented in this work. The results show that the method presented earlier for J-T refrigerators operating in GRS mode is also applicable in the case of refrigerators studied in this work.

Process for stabilization of coal liquid fractions

DOEpatents

Davies, Geoffrey; El-Toukhy, Ahmed

1987-01-01

Coal liquid fractions to be used as fuels are stabilized against gum formation and viscosity increases during storage, permitting the fuel to be burned as is, without further expensive treatments to remove gums or gum-forming materials. Stabilization is accomplished by addition of cyclohexanol or other simple inexpensive secondary and tertiary alcohols, secondary and tertiary amines, and ketones to such coal liquids at levels of 5-25% by weight with respect to the coal liquid being treated. Cyclohexanol is a particularly effective and cost-efficient stabilizer. Other stabilizers are isopropanol, diphenylmethanol, tertiary butanol, dipropylamine, triethylamine, diphenylamine, ethylmethylketone, cyclohexanone, methylphenylketone, and benzophenone. Experimental data indicate that stabilization is achieved by breaking hydrogen bonds between phenols in the coal liquid, thereby preventing or retarding oxidative coupling. In addition, it has been found that coal liquid fractions stabilized according to the invention can be mixed with petroleum-derived liquid fuels to produce mixtures in which gum deposition is prevented or reduced relative to similar mixtures not containing stabilizer.

Phase separations in mixtures of a liquid crystal and a nanocolloidal particle.

PubMed

Matsuyama, Akihiko

2009-11-28

We present a mean field theory to describe phase separations in mixtures of a liquid crystal and a nanocolloidal particle. By taking into account a nematic, a smectic A ordering of the liquid crystal, and a crystalline ordering of the nanoparticle, we calculate the phase diagrams on the temperature-concentration plane. We predict various phase separations, such as a smectic A-crystal phase separation and a smectic A-isotropic-crystal triple point, etc., depending on the interactions between the liquid crystal and the colloidal surface. Inside binodal curves, we find new unstable and metastable regions, which are important in the phase ordering dynamics. We also find a crystalline ordering of the nanoparticles dispersed in a smectic A phase and a nematic phase. The cooperative phenomena between liquid-crystalline ordering and crystalline ordering induce a variety of phase diagrams.

Anomalous Quasiparticle Reflection from the Surface of a ^{3}He-^{4}He Dilute Solution.

PubMed

Ikegami, Hiroki; Kim, Kitak; Sato, Daisuke; Kono, Kimitoshi; Choi, Hyoungsoon; Monarkha, Yuriy P

2017-11-10

A free surface of a dilute ^{3}He-^{4}He liquid mixture is a unique system where two Fermi liquids with distinct dimensions coexist: a three-dimensional (3D) ^{3}He Fermi liquid in the bulk and a two-dimensional (2D) ^{3}He Fermi liquid at the surface. To investigate a novel effect generated by the interaction between the two Fermi liquids, the mobility of a Wigner crystal of electrons formed on the free surface of the mixture is studied. An anomalous enhancement of the mobility, compared with the case where the 3D and 2D systems do not interact with each other, is observed. The enhancement is explained by the nontrivial reflection of 3D quasiparticles from the surface covered with the 2D ^{3}He system.

Ceramic-glass-ceramic seal by microwave heating

DOEpatents

Meek, T.T.; Blake, R.D.

1983-10-04

A method for producing a ceramic-glass-ceramic seal by microwaving, mixes a slurry of glass sealing material and coupling agent and applies same to ceramic workpieces. The slurry and workpieces are placed together, insulated and then microwaved at a power, time and frequency sufficient to cause a liquid phase reaction in the slurry. The reaction of the glass sealing material forms a chemically different seal than that which would be formed by conventional heating because it is formed by a diffusion rather than by wetting of the reactants.

Ceramic-glass-ceramic seal by microwave heating

DOEpatents

Meek, Thomas T.; Blake, Rodger D.

1985-01-01

A method for producing a ceramic-glass-ceramic seal by microwaving, mixes a slurry of glass sealing material and coupling agent and applies same to ceramic workpieces. The slurry and workpieces are placed together, insulated and then microwaved at a power, time and frequency sufficient to cause a liquid phase reaction in the slurry. The reaction of the glass sealing material forms a chemically different seal than that which would be formed by conventional heating because it is formed by a diffusion rather than by wetting of the reactants.

Process and apparatus for adding and removing particles from pressurized reactors

DOEpatents

Milligan, John D.

1983-01-01

A method for adding and removing fine particles from a pressurized reactor is provided, which comprises connecting the reactor to a container, sealing the container from the reactor, filling the container with particles and a liquid material compatible with the reactants, pressurizing the container to substantially the reactor pressure, removing the seal between the reactor and the container, permitting particles to fall into or out of the reactor, and resealing the container from the reactor. An apparatus for adding and removing particles is also disclosed.

Production of aromatics from di- and polyoxygenates

DOEpatents

Beck, Taylor; Blank, Brian; Jones, Casey; Woods, Elizabeth; Cortright, Randy

2016-08-02

Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Ni.sub.nSn.sub.m alloy and a crystalline alumina support.

Production of aromatics from di- and polyoxygenates

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

Beck, Taylor; Blank, Brian; Jones, Casey

Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Ni.sub.nSn.sub.m alloy and a crystalline aluminamore » support.« less

Production of aromatics from di- and polyoxygenates

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

Beck, Taylor; Blank, Brian; Jones, Casey

Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Group VIII metal and a crystallinemore » alumina support.« less

Synergic effects in the extraction of paracetamol from aqueous NaCl solution by the binary mixtures of diethyl ether and low molecular weight primary alcohols

NASA Astrophysics Data System (ADS)

Nikolić, G. M.; Živković, J. V.; Atanasković, D. S.; Nikolić, M. G.

2013-12-01

Liquid-liquid extraction of paracetamol from aqueous NaCl solutions was performed with diethyl ether, 1-propanol, 1-butanol, isobutanol, 1-pentanol, and binary mixtures diethyl ether/1-propanol, diethyl ether/1-butanol, and diethyl ether/isobutanol. Among the pure solvents investigated in this study best extraction efficacy was obtained with 1-butanol. Synergic effects in the extraction with binary mixtures was investigated and compared with some other systems used for the extraction of poorly extractable compounds. Results obtained in this study may be of both fundamental and practical importance.

Quantum liquid droplets in a mixture of Bose-Einstein condensates

NASA Astrophysics Data System (ADS)

Cabrera, C. R.; Tanzi, L.; Sanz, J.; Naylor, B.; Thomas, P.; Cheiney, P.; Tarruell, L.

2018-01-01

Quantum droplets are small clusters of atoms self-bound by the balance of attractive and repulsive forces. Here, we report on the observation of droplets solely stabilized by contact interactions in a mixture of two Bose-Einstein condensates. We demonstrate that they are several orders of magnitude more dilute than liquid helium by directly measuring their size and density via in situ imaging. We show that the droplets are stablized against collapse by quantum fluctuations and that they require a minimum atom number to be stable. Below that number, quantum pressure drives a liquid-to-gas transition that we map out as a function of interaction strength. These ultradilute isotropic liquids remain weakly interacting and constitute an ideal platform to benchmark quantum many-body theories.

Molecular dynamics simulation for the test of calibrated OPLS-AA force field for binary liquid mixture of tri-iso-amyl phosphate and n-dodecane.

PubMed

Das, Arya; Ali, Sk Musharaf

2018-02-21

Tri-isoamyl phosphate (TiAP) has been proposed to be an alternative for tri-butyl phosphate (TBP) in the Plutonium Uranium Extraction (PUREX) process. Recently, we have successfully calibrated and tested all-atom optimized potentials for liquid simulations using Mulliken partial charges for pure TiAP, TBP, and dodecane by performing molecular dynamics (MD) simulation. It is of immense importance to extend this potential for the various molecular properties of TiAP and TiAP/n-dodecane binary mixtures using MD simulation. Earlier, efforts were devoted to find out a suitable force field which can explain both structural and dynamical properties by empirical parameterization. Therefore, the present MD study reports the structural, dynamical, and thermodynamical properties with different mole fractions of TiAP-dodecane mixtures at the entire range of mole fraction of 0-1 employing our calibrated Mulliken embedded optimized potentials for liquid simulation (OPLS) force field. The calculated electric dipole moment of TiAP was seen to be almost unaffected by the TiAP concentration in the dodecane diluent. The calculated liquid densities of the TiAP-dodecane mixture are in good agreement with the experimental data. The mixture densities at different temperatures are also studied which was found to be reduced with temperature as expected. The plot of diffusivities for TiAP and dodecane against mole fraction in the binary mixture intersects at a composition in the range of 25%-30% of TiAP in dodecane, which is very much closer to the TBP/n-dodecane composition used in the PUREX process. The excess volume of mixing was found to be positive for the entire range of mole fraction and the excess enthalpy of mixing was shown to be endothermic for the TBP/n-dodecane mixture as well as TiAP/n-dodecane mixture as reported experimentally. The spatial pair correlation functions are evaluated between TiAP-TiAP and TiAP-dodecane molecules. Further, shear viscosity has been computed by performing the non-equilibrium molecular dynamics employing the periodic perturbation method. The calculated shear viscosity of the binary mixture is found to be in excellent agreement with the experimental values. The use of the newly calibrated OPLS force field embedding Mulliken charges is shown to be equally reliable in predicting the structural and dynamical properties for the mixture without incorporating any arbitrary scaling in the force field or Lennard-Jones parameters. Further, the present MD simulation results demonstrate that the Stokes-Einstein relation breaks down at the molecular level. The present methodology might be adopted to evaluate the liquid state properties of an aqueous-organic biphasic system, which is of great significance in the interfacial science and technology.