Investigation of Embedded Si/C System Exposed to a Hybrid Reaction of Centrifugal-Assisted Thermite Method

PubMed Central

Mahmoodian, Reza; Yahya, Rosiyah; Dabbagh, Ali; Hamdi, Mohd; Hassan, Mohsen A.

2015-01-01

A novel method is proposed to study the behavior and phase formation of a Si+C compacted pellet under centrifugal acceleration in a hybrid reaction. Si+C as elemental mixture in the form of a pellet is embedded in a centrifugal tube. The pellet assembly and tube are exposed to the sudden thermal energy of a thermite reaction resulted in a hybrid reaction. The hybrid reaction of thermite and Si+C produced unique phases. X-ray diffraction pattern (XRD) as well as microstructural and elemental analyses are then investigated. XRD pattern showed formation of materials with possible electronic and magnetic properties. The cooling rate and the molten particle viscosity mathematical model of the process are meant to assist in understanding the physical and chemical phenomena took place during and after reaction. The results analysis revealed that up to 85% of materials converted into secondary products as ceramics-matrix composite. PMID:26641651

Investigation of Embedded Si/C System Exposed to a Hybrid Reaction of Centrifugal-Assisted Thermite Method.

PubMed

Mahmoodian, Reza; Yahya, Rosiyah; Dabbagh, Ali; Hamdi, Mohd; Hassan, Mohsen A

2015-01-01

A novel method is proposed to study the behavior and phase formation of a Si+C compacted pellet under centrifugal acceleration in a hybrid reaction. Si+C as elemental mixture in the form of a pellet is embedded in a centrifugal tube. The pellet assembly and tube are exposed to the sudden thermal energy of a thermite reaction resulted in a hybrid reaction. The hybrid reaction of thermite and Si+C produced unique phases. X-ray diffraction pattern (XRD) as well as microstructural and elemental analyses are then investigated. XRD pattern showed formation of materials with possible electronic and magnetic properties. The cooling rate and the molten particle viscosity mathematical model of the process are meant to assist in understanding the physical and chemical phenomena took place during and after reaction. The results analysis revealed that up to 85% of materials converted into secondary products as ceramics-matrix composite.

Optimization of o-phtaldialdehyde/2-mercaptoethanol postcolumn reaction for the hydrophilic interaction liquid chromatography determination of memantine utilizing a silica hydride stationary phase.

PubMed

Douša, Michal; Pivoňková, Veronika; Sýkora, David

2016-08-01

A rapid procedure for the determination of memantine based on hydrophilic interaction chromatography with fluorescence detection was developed. Fluorescence detection after postcolumn derivatization with o-phtaldialdehyde/2-mercaptoethanol was performed at excitation and emission wavelengths of 345 and 450 nm, respectively. The postcolumn reaction conditions such as reaction temperature, derivatization reagent flow rate, and reagents concentration were studied due to steric hindrance of amino group of memantine. The derivatization reaction was applied for the hydrophilic interaction liquid chromatography method which was based on Cogent Silica-C stationary phase with a mobile phase consisting of a mixture of 10 mmol/L citric acid and 10 mmol/L o-phosphoric acid (pH 6.0) with acetonitrile using an isocratic composition of 2:8 v/v. The benefit of the reported approach consists in a simple sample pretreatment and a quick and sensitive hydrophilic interaction chromatography method. The developed method was validated in terms of linearity, accuracy, precision, and selectivity according to the International Conference on Harmonisation guidelines. The developed method was successfully applied for the analysis of commercial memantine tablets. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Visualizing non-equilibrium lithiation of spinel oxide via in situ transmission electron microscopy

PubMed Central

He, Kai; Zhang, Sen; Li, Jing; Yu, Xiqian; Meng, Qingping; Zhu, Yizhou; Hu, Enyuan; Sun, Ke; Yun, Hongseok; Yang, Xiao-Qing; Zhu, Yimei; Gan, Hong; Mo, Yifei; Stach, Eric A.; Murray, Christopher B.; Su, Dong

2016-01-01

Spinel transition metal oxides are important electrode materials for lithium-ion batteries, whose lithiation undergoes a two-step reaction, whereby intercalation and conversion occur in a sequential manner. These two reactions are known to have distinct reaction dynamics, but it is unclear how their kinetics affects the overall electrochemical response. Here we explore the lithiation of nanosized magnetite by employing a strain-sensitive, bright-field scanning transmission electron microscopy approach. This method allows direct, real-time, high-resolution visualization of how lithiation proceeds along specific reaction pathways. We find that the initial intercalation process follows a two-phase reaction sequence, whereas further lithiation leads to the coexistence of three distinct phases within single nanoparticles, which has not been previously reported to the best of our knowledge. We use phase-field theory to model and describe these non-equilibrium reaction pathways, and to directly correlate the observed phase evolution with the battery's discharge performance. PMID:27157119

Solid catalyzed isoparaffin alkylation at supercritical fluid and near-supercritical fluid conditions

DOEpatents

Ginosar, Daniel M.; Fox, Robert V.; Kong, Peter C.

2000-01-01

This invention relates to an improved method for the alkylation reaction of isoparaffins with olefins over solid catalysts including contacting a mixture of an isoparaffin, an olefin and a phase-modifying material with a solid acid catalyst member under alkylation conversion conditions at either supercritical fluid, or near-supercritical fluid conditions, at a temperature and a pressure relative to the critical temperature(T.sub.c) and the critical pressure(P.sub.c) of the reaction mixture. The phase-modifying phase-modifying material is employed to promote the reaction's achievement of either a supercritical fluid state or a near-supercritical state while simultaneously allowing for decreased reaction temperature and longer catalyst life.

Unimolecular Reaction Pathways of a γ-Ketohydroperoxide from Combined Application of Automated Reaction Discovery Methods

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

Grambow, Colin A.; Jamal, Adeel; Li, Yi -Pei

Ketohydroperoxides are important in liquid-phase autoxidation and in gas-phase partial oxidation and pre-ignition chemistry, but because of their low concentration, instability, and various analytical chemistry limitations, it has been challenging to experimentally determine their reactivity, and only a few pathways are known. In the present work, 75 elementary-step unimolecular reactions of the simplest γ-ketohydroperoxide, 3-hydroperoxypropanal, were discovered by a combination of density functional theory with several automated transition-state search algorithms: the Berny algorithm coupled with the freezing string method, single- and double-ended growing string methods, the heuristic KinBot algorithm, and the single-component artificial force induced reaction method (SC-AFIR). The presentmore » joint approach significantly outperforms previous manual and automated transition-state searches – 68 of the reactions of γ-ketohydroperoxide discovered here were previously unknown and completely unexpected. All of the methods found the lowest-energy transition state, which corresponds to the first step of the Korcek mechanism, but each algorithm except for SC-AFIR detected several reactions not found by any of the other methods. We show that the low-barrier chemical reactions involve promising new chemistry that may be relevant in atmospheric and combustion systems. Our study highlights the complexity of chemical space exploration and the advantage of combined application of several approaches. Altogether, the present work demonstrates both the power and the weaknesses of existing fully automated approaches for reaction discovery which suggest possible directions for further method development and assessment in order to enable reliable discovery of all important reactions of any specified reactant(s).« less

Unimolecular Reaction Pathways of a γ-Ketohydroperoxide from Combined Application of Automated Reaction Discovery Methods

DOE PAGES

Grambow, Colin A.; Jamal, Adeel; Li, Yi -Pei; ...

2017-12-22

Ketohydroperoxides are important in liquid-phase autoxidation and in gas-phase partial oxidation and pre-ignition chemistry, but because of their low concentration, instability, and various analytical chemistry limitations, it has been challenging to experimentally determine their reactivity, and only a few pathways are known. In the present work, 75 elementary-step unimolecular reactions of the simplest γ-ketohydroperoxide, 3-hydroperoxypropanal, were discovered by a combination of density functional theory with several automated transition-state search algorithms: the Berny algorithm coupled with the freezing string method, single- and double-ended growing string methods, the heuristic KinBot algorithm, and the single-component artificial force induced reaction method (SC-AFIR). The presentmore » joint approach significantly outperforms previous manual and automated transition-state searches – 68 of the reactions of γ-ketohydroperoxide discovered here were previously unknown and completely unexpected. All of the methods found the lowest-energy transition state, which corresponds to the first step of the Korcek mechanism, but each algorithm except for SC-AFIR detected several reactions not found by any of the other methods. We show that the low-barrier chemical reactions involve promising new chemistry that may be relevant in atmospheric and combustion systems. Our study highlights the complexity of chemical space exploration and the advantage of combined application of several approaches. Altogether, the present work demonstrates both the power and the weaknesses of existing fully automated approaches for reaction discovery which suggest possible directions for further method development and assessment in order to enable reliable discovery of all important reactions of any specified reactant(s).« less

Exploring reaction pathways in the hydrothermal growth of phase-pure bismuth ferrites

NASA Astrophysics Data System (ADS)

Goldman, Abby R.; Fredricks, Jeremy L.; Estroff, Lara A.

2017-06-01

Phase-pure bismuth ferrites (BiFeO3 and Bi2Fe4O9) are grown using hydrothermal synthesis. In addition to varying the KOH, bismuth, and iron salt concentrations to tune which crystalline phases are formed, we identified that a 48 h, pre-furnace, room temperature reaction is critical for the formation of phase-pure BiFeO3. To understand the reaction pathways leading to the different bismuth ferrite phases, we investigate the changes in composition of the intermediate products as a function of reagent concentrations and room temperature reaction times. During the syntheses that included a room temperature reaction, Bi25FeO40 is formed in the intermediate products, and BiFeO3 is the majority phase of the final products. The BiFeO3 crystals grown using this method are clusters of faceted subunits. These results indicate that forming Bi25FeO40 is a productive route to the formation of BiFeO3. Bi2Fe4O9 is formed via an alternate reaction pathway that proceeded via an amorphous precursor. This improved understanding of how hydrothermal synthesis can be used to control the phase-purity and morphology of bismuth ferrites opens doors to explore the multiferroic properties of BiFeO3 with complex morphologies.

Extended lattice Boltzmann scheme for droplet combustion.

PubMed

Ashna, Mostafa; Rahimian, Mohammad Hassan; Fakhari, Abbas

2017-05-01

The available lattice Boltzmann (LB) models for combustion or phase change are focused on either single-phase flow combustion or two-phase flow with evaporation assuming a constant density for both liquid and gas phases. To pave the way towards simulation of spray combustion, we propose a two-phase LB method for modeling combustion of liquid fuel droplets. We develop an LB scheme to model phase change and combustion by taking into account the density variation in the gas phase and accounting for the chemical reaction based on the Cahn-Hilliard free-energy approach. Evaporation of liquid fuel is modeled by adding a source term, which is due to the divergence of the velocity field being nontrivial, in the continuity equation. The low-Mach-number approximation in the governing Navier-Stokes and energy equations is used to incorporate source terms due to heat release from chemical reactions, density variation, and nonluminous radiative heat loss. Additionally, the conservation equation for chemical species is formulated by including a source term due to chemical reaction. To validate the model, we consider the combustion of n-heptane and n-butanol droplets in stagnant air using overall single-step reactions. The diameter history and flame standoff ratio obtained from the proposed LB method are found to be in good agreement with available numerical and experimental data. The present LB scheme is believed to be a promising approach for modeling spray combustion.

Directional Solidification and Liquidus Projection of the Sn-Co-Cu System

NASA Astrophysics Data System (ADS)

Chen, Sinn-Wen; Chang, Jui-Shen; Pan, Kevin; Hsu, Chia-Ming; Hsu, Che-Wei

2013-04-01

This study investigates the Sn-Co-Cu ternary system, which is of interest to the electronics industry. Ternary Sn-Co-Cu alloys were prepared, their as-solidified microstructures were examined, and their primary solidification phases were determined. The primary solidification phases observed were Cu, Co, Co3Sn2, CoSn, CoSn2, Cu6Sn5, Co3Sn2, γ, and β phases. Although there are ternary compounds reported in this ternary system, no ternary compound was found as the primary solidification phase. The directional solidification technique was applied when difficulties were encountered using the conventional quenching method to distinguish the primary solidification phases, such as Cu6Sn5, Cu3Sn, and γ phases. Of all the primary solidification phases, the Co3Sn2 and Co phases have the largest compositional regimes in which alloys display them as the primary solidification phases. There are four class II reactions and four class III reactions. The reactions with the highest and lowest reaction temperatures are both class III reactions, and are L + CoSn2 + Cu6Sn5 = CoSn3 at 621.5 K (348.3 °C) and L + Co3Sn2 + CoSn = Cu6Sn5 at 1157.8 K (884.6 °C), respectively.

Synthesis and Purification of Iodoaziridines Involving Quantitative Selection of the Optimal Stationary Phase for Chromatography

PubMed Central

Boultwood, Tom; Affron, Dominic P.; Bull, James A.

2014-01-01

The highly diastereoselective preparation of cis-N-Ts-iodoaziridines through reaction of diiodomethyllithium with N-Ts aldimines is described. Diiodomethyllithium is prepared by the deprotonation of diiodomethane with LiHMDS, in a THF/diethyl ether mixture, at -78 °Cin the dark. These conditions are essential for the stability of the LiCHI2 reagent generated. The subsequent dropwise addition of N-Ts aldimines to the preformed diiodomethyllithium solution affords an amino-diiodide intermediate, which is not isolated. Rapid warming of the reaction mixture to 0 °C promotes cyclization to afford iodoaziridines with exclusive cis-diastereoselectivity. The addition and cyclization stages of the reaction are mediated in one reaction flask by careful temperature control. Due to the sensitivity of the iodoaziridines to purification, assessment of suitable methods of purification is required. A protocol to assess the stability of sensitive compounds to stationary phases for column chromatography is described. This method is suitable to apply to new iodoaziridines, or other potentially sensitive novel compounds. Consequently this method may find application in range of synthetic projects. The procedure involves firstly the assessment of the reaction yield, prior to purification, by 1H NMR spectroscopy with comparison to an internal standard. Portions of impure product mixture are then exposed to slurries of various stationary phases appropriate for chromatography, in a solvent system suitable as the eluent in flash chromatography. After stirring for 30 min to mimic chromatography, followed by filtering, the samples are analyzed by 1H NMR spectroscopy. Calculated yields for each stationary phase are then compared to that initially obtained from the crude reaction mixture. The results obtained provide a quantitative assessment of the stability of the compound to the different stationary phases; hence the optimal can be selected. The choice of basic alumina, modified to activity IV, as a suitable stationary phase has allowed isolation of certain iodoaziridines in excellent yield and purity. PMID:24893769

Quinazoline derivatives: synthesis and bioactivities

PubMed Central

2013-01-01

Owing to the significant biological activities, quinazoline derivatives have drawn more and more attention in the synthesis and bioactivities research. This review summarizes the recent advances in the synthesis and biological activities investigations of quinazoline derivatives. According to the main method the authors adopted in their research design, those synthetic methods were divided into five main classifications, including Aza-reaction, Microwave-assisted reaction, Metal-mediated reaction, Ultrasound-promoted reaction and Phase-transfer catalysis reaction. The biological activities of the synthesized quinazoline derivatives also are discussed. PMID:23731671

Textured catalysts, methods of making textured catalysts, and methods of catalyzing reactions conducted in hydrothermal conditions

DOEpatents

Werpy, Todd [West Richland, WA; Wang, Yong [Richland, WA

2003-12-30

A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

Synthesis of alloys with controlled phase structure

DOEpatents

Guthrie, Stephen Everett; Thomas, George John; Bauer, Walter; Yang, Nancy Yuan Chi

1999-04-20

A method for preparing controlled phase alloys useful for engineering and hydrogen storage applications. This novel method avoids melting the constituents by employing vapor transport, in a hydrogen atmosphere, of an active metal constituent, having a high vapor pressure at temperatures .apprxeq.300 C. and its subsequent condensation on and reaction with the other constituent (substrate) of an alloy thereby forming a controlled phase alloy and preferably a single phase alloy. It is preferred that the substrate material be a metal powder such that diffusion of the active metal constituent, preferably magnesium, and reaction therewith can be completed within a reasonable time and at temperatures .apprxeq.300 C. thereby avoiding undesirable effects such as sintering, local compositional inhomogeneities, segregation, and formation of unwanted second phases such as intermetallic compounds.

Synthesis of alloys with controlled phase structure

DOEpatents

Guthrie, S.E.; Thomas, G.J.; Bauer, W.; Yang, N.Y.C.

1999-04-20

A method is described for preparing controlled phase alloys useful for engineering and hydrogen storage applications. This novel method avoids melting the constituents by employing vapor transport, in a hydrogen atmosphere, of an active metal constituent, having a high vapor pressure at temperatures {approx_equal}300 C and its subsequent condensation on and reaction with the other constituent (substrate) of an alloy thereby forming a controlled phase alloy and preferably a single phase alloy. It is preferred that the substrate material be a metal powder such that diffusion of the active metal constituent, preferably magnesium, and reaction therewith can be completed within a reasonable time and at temperatures {approx_equal}300 C thereby avoiding undesirable effects such as sintering, local compositional inhomogeneities, segregation, and formation of unwanted second phases such as intermetallic compounds. 4 figs.

Exploring chemical reaction mechanisms through harmonic Fourier beads path optimization.

PubMed

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

2013-10-28

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

The Hydroxyl Radical Reaction Rate Constant and Products of Dimethyl Succinate

DTIC Science & Technology

2008-03-01

phase reaction of OH + DMS, 10 liters of chamber content were flowed over 2,4- dinitrophenylhydrazine (DNPH) impregnated cartridges. Hydrazones formed... dinitrophenylhydrazine (DNPH) derivatization (method described in experimental methods), and GC/MS/MS (where samples were directly introduced into the mass

Boron-carbide-aluminum and boron-carbide-reactive metal cermets

DOEpatents

Halverson, Danny C.; Pyzik, Aleksander J.; Aksay, Ilhan A.

1986-01-01

Hard, tough, lightweight boron-carbide-reactive metal composites, particularly boron-carbide-aluminum composites, are produced. These composites have compositions with a plurality of phases. A method is provided, including the steps of wetting and reacting the starting materials, by which the microstructures in the resulting composites can be controllably selected. Starting compositions, reaction temperatures, reaction times, and reaction atmospheres are parameters for controlling the process and resulting compositions. The ceramic phases are homogeneously distributed in the metal phases and adhesive forces at ceramic-metal interfaces are maximized. An initial consolidation step is used to achieve fully dense composites. Microstructures of boron-carbide-aluminum cermets have been produced with modulus of rupture exceeding 110 ksi and fracture toughness exceeding 12 ksi.sqroot.in. These composites and methods can be used to form a variety of structural elements.

Boron-carbide-aluminum and boron-carbide-reactive metal cermets. [B/sub 4/C-Al

DOEpatents

Halverson, D.C.; Pyzik, A.J.; Aksay, I.A.

1985-05-06

Hard, tough, lighweight boron-carbide-reactive metal composites, particularly boron-carbide-aluminum composites, are produced. These composites have compositions with a plurality of phases. A method is provided, including the steps of wetting and reacting the starting materials, by which the microstructures in the resulting composites can be controllably selected. Starting compositions, reaction temperatures, reaction times, and reaction atmospheres are parameters for controlling the process and resulting compositions. The ceramic phases are homogeneously distributed in the metal phases and adhesive forces at ceramic-metal interfaces are maximized. An initial consolidated step is used to achieve fully dense composites. Microstructures of boron-carbide-aluminum cermets have been produced with modules of rupture exceeding 110 ksi and fracture toughness exceeding 12 ksi..sqrt..in. These composites and methods can be used to form a variety of structural elements.

Perspective on Diabatic Models of Chemical Reactivity as Illustrated by the Gas-Phase SN2 Reaction of Acetate Ion with 1,2-Dichloroethane

PubMed Central

Valero, Rosendo; Song, Lingchun; Gao, Jiali; Truhlar, Donald G.

2009-01-01

Diabatic models are widely employed for studying chemical reactivity in condensed phases and enzymes, but there has been little discussion of the pros and cons of various diabatic representations for this purpose. Here we discuss and contrast six different schemes for computing diabatic potentials for a charge rearrangement reaction. They include (i) the variational diabatic configurations (VDC) constructed by variationally optimizing individual valence bond structures and (ii) the consistent diabatic configurations (CDC) obtained by variationally optimizing the ground-state adiabatic energy, both in the nonorthogonal molecular orbital valence bond (MOVB) method, along with the orthogonalized (iii) VDC-MOVB and (iv) CDC-MOVB models. In addition, we consider (v) the fourfold way (based on diabatic molecular orbitals and configuration uniformity), and (vi) empirical valence bond (EVB) theory. To make the considerations concrete, we calculate diabatic electronic states and diabatic potential energies along the reaction path that connects the reactant and the product ion-molecule complexes of the gas-phase bimolecular nucleophilic substitution (SN2) reaction of 1,2-dichloethane (DCE) with acetate ion, which is a model reaction corresponding to the reaction catalyzed by haloalkane dehalogenase. We utilize ab initio block-localized molecular orbital theory to construct the MOVB diabatic states and ab initio multi-configuration quasidegenerate perturbation theory to construct the fourfold-way diabatic states; the latter are calculated at reaction path geometries obtained with the M06-2X density functional. The EVB diabatic states are computed with parameters taken from the literature. The MOVB and fourfold-way adiabatic and diabatic potential energy profiles along the reaction path are in qualitative but not quantitative agreement with each other. In order to validate that these wave-function-based diabatic states are qualitatively correct, we show that the reaction energy and barrier for the adiabatic ground state, obtained with these methods, agree reasonably well with the results of high-level calculations using the composite G3SX and G3SX(MP3) methods and the BMC-CCSD multi-coefficient correlation method. However, a comparison of the EVB gas-phase adiabatic ground-state reaction path with those obtained from MOVB and with the fourfold way reveals that the EVB reaction path geometries show a systematic shift towards the products region, and that the EVB lowest-energy path has a much lower barrier. The free energies of solvation and activation energy in water reported from dynamical calculations based on EVB also imply a low activation barrier in the gas phase. In addition, calculations of the free energy of solvation using the recently proposed SM8 continuum solvation model with CM4M partial atomic charges lead to an activation barrier in reasonable agreement with experiment only when the geometries and the gas-phase barrier are those obtained from electronic structure calculations, i.e., methods i–v. These comparisons show the danger of basing the diabatic states on molecular mechanics without the explicit calculation of electronic wave functions. Furthermore, comparison of schemes i–v with one another shows that significantly different quantitative results can be obtained by using different methods for extracting diabatic states from wave function calculations, and it is important for each user to justify the choice of diabatization method in the context of its intended use. PMID:20047005

High-performance liquid chromatography analysis methods developed for quantifying enzymatic esterification of flavonoids in ionic liquids.

PubMed

Lue, Bena-Marie; Guo, Zheng; Xu, Xuebing

2008-07-11

Methods using reversed-phase high-performance liquid chromatography (RP-HPLC) with ELSD were investigated to quantify enzymatic reactions of flavonoids with fatty acids in the presence of diverse room temperature ionic liquids (RTILs). A buffered salt (preferably triethylamine-acetate) was found essential for separation of flavonoids from strongly polar RTILs, whereby RTILs were generally visible as two major peaks identified based on an ion-pairing/exchanging hypothesis. C8 and C12 stationary phases were optimal while mobile phase pH (3-7) had only a minor influence on separation. The method developed was successfully applied for primary screening of RTILs (>20), with in depth evaluation of substrates in 10 RTILs, for their evaluation as reaction media.

Fluorometric method for the determination of gas-phase hydrogen peroxide

NASA Technical Reports Server (NTRS)

Kok, Gregory L.; Lazrus, Allan L.

1986-01-01

The fluorometric gas-phase hydrogen peroxide procedure is based on the technique used by Lazrus et. al. for the determination of H2O2 in the liquid phase. The analytical method utilizes the reaction of H2O2 with horseradish peroxidase and p-hydroxphenylacetic acid (POPHA) to form the fluorescent dimer of POPHA. The analytical reaction responds stoichiometrically to both H2O2 and some organic hydroperoxides. To discriminate H2O2 from organic hydroperoxides, catalase is used to preferentially destroy H2O2. Using a dual-channel flow system the H2O2 concentration is determined by difference.

Comparison of TiO2 photocatalysis, electrochemically assisted Fenton reaction and direct electrochemistry for simulation of phase I metabolism reactions of drugs.

PubMed

Ruokolainen, Miina; Gul, Turan; Permentier, Hjalmar; Sikanen, Tiina; Kostiainen, Risto; Kotiaho, Tapio

2016-02-15

The feasibility of titanium dioxide (TiO2) photocatalysis, electrochemically assisted Fenton reaction (EC-Fenton) and direct electrochemical oxidation (EC) for simulation of phase I metabolism of drugs was studied by comparing the reaction products of buspirone, promazine, testosterone and 7-ethoxycoumarin with phase I metabolites of the same compounds produced in vitro by human liver microsomes (HLM). Reaction products were analysed by UHPLC-MS. TiO2 photocatalysis simulated the in vitro phase I metabolism in HLM more comprehensively than did EC-Fenton or EC. Even though TiO2 photocatalysis, EC-Fenton and EC do not allow comprehensive prediction of phase I metabolism, all three methods produce several important metabolites without the need for demanding purification steps to remove the biological matrix. Importantly, TiO2 photocatalysis produces aliphatic and aromatic hydroxylation products where direct EC fails. Furthermore, TiO2 photocatalysis is an extremely rapid, simple and inexpensive way to generate oxidation products in a clean matrix and the reaction can be simply initiated and quenched by switching the UV lamp on/off. Copyright © 2015 Elsevier B.V. All rights reserved.

Production of aligned microfibers and nanofibers and derived functional monoliths

DOEpatents

Hu, Michael Z [Knoxville, TN; DePaoli, David W [Knoxville, TN; Kuritz, Tanya [Kingston, TN; Omatete, Ogbemi [New Port Richey, FL

2007-08-14

The present invention comprises a method for producing microfibers and nanofibers and further fabricating derived solid monolithic materials having aligned uniform micro- or nanofibrils. A method for producing fibers ranging in diameter from micrometer-sized to nanometer-sized comprises the steps of producing an electric field and preparing a solid precipitative reaction media wherein the media comprises at least one chemical reactive precursor and a solvent having low electrical conductivity and wherein a solid precipitation reaction process for nucleation and growth of a solid phase occurs within the media. Then, subjecting the media to the electric field to induce in-situ growth of microfibers or nanofibers during the reaction process within the media causing precipitative growth of solid phase particles wherein the reaction conditions and reaction kinetics control the size, morphology and composition of the fibers. The fibers can then be wet pressed while under electric field into a solid monolith slab, dried and consolidated.

Chapter 5: Modulation Excitation Spectroscopy with Phase-Sensitive Detection for Surface Analysis

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

Shulda, Sarah; Richards, Ryan M.

Advancements in in situ spectroscopic techniques have led to significant progress being made in elucidating heterogeneous reaction mechanisms. The potential of these progressive methods is often limited only by the complexity of the system and noise in the data. Short-lived intermediates can be challenging, if not impossible, to identify with conventional spectra analysis means. Often equally difficult is separating signals that arise from active and inactive species. Modulation excitation spectroscopy combined with phase-sensitive detection analysis is a powerful tool for removing noise from the data while simultaneously revealing the underlying kinetics of the reaction. A stimulus is applied at amore » constant frequency to the reaction system, for example, a reactant cycled with an inert phase. Through mathematical manipulation of the data, any signal contributing to the overall spectra but not oscillating with the same frequency as the stimulus will be dampened or removed. With phase-sensitive detection, signals oscillating with the stimulus frequency but with various lag times are amplified providing valuable kinetic information. In this chapter, some examples are provided from the literature that have successfully used modulation excitation spectroscopy with phase-sensitive detection to uncover previously unobserved reaction intermediates and kinetics. Examples from a broad range of spectroscopic methods are included to provide perspective to the reader.« less

Determination of osthol and its metabolites in a phase I reaction system and the Caco-2 cell model by HPLC-UV and LC-MS/MS

PubMed Central

Yuan, Zhenting; Xu, Haiyan; Wang, Ke; Zhao, Zhonghua; Hu, Ming

2012-01-01

A straightforward and sensitive reversed-phase high-performance liquid chromatography (HPLC) assay was developed and validated for the analysis of osthol and its phase I metabolites (internal standard: umbelliferone). The method was validated for the determination of osthol with respect to selectivity, precision, linearity, limit of detection, recovery, and stability. The linear response range was 0.47 ~ 60 μM, and the average recoveries ranged from 98 to 101%. The inter-day and intra-day relative standard deviations were both less than 5%. Using this method, we showed that more than 80% of osthol was metabolized in 20 min in a phase I metabolic reaction system. Transport experiments in the Caco-2 cell culture model indicated that osthol was easily absorbed with high absorptive permeability (>10×10-6 cm/sec). The permeability did not display concentration-dependence or vectorial-dependence and is mildly temperature sensitive (activation energy less than 10 Kcal/mole), indicating passive mechanism of transport. When analyzed by LC-MS/MS, five metabolites were detected in a phase I reaction system and in the receiver side of a modified Caco-2 cell model, which was supplemented with the phase I reaction system. The major metabolites appeared to be desmethyl-osthol and multiple isomers of dehydro-osthol. In conclusion, a likely cause of poor osthol bioavailability is rapid phase I metabolism via the cytochrome P-450 pathways. PMID:19304430

7Li(d,p)8Li transfer reaction in the NCSM/RGM approach

NASA Astrophysics Data System (ADS)

Raimondi, F.; Hupin, G.; Navrátil, P.; Quaglioni, S.

2018-03-01

Recently, we applied an ab initio method, the no-core shell model combined with the resonating group method, to the transfer reactions with light p-shell nuclei as targets and deuteron as the projectile. In particular, we studied the elastic scattering of deuterium on 7Li and the 7Li(d,p)8Li transfer reaction starting from a realistic two-nucleon interaction. In this contribution, we review of our main results on the 7Li(d,p)8Li transfer reaction, and we extend the study of the relevant reaction channels, by showing the dominant resonant phase shifts of the scattering matrix. We assess also the impact of the polarization effects of the deuteron below the breakup on the positive-parity resonant states in the reaction. For this purpose, we perform an analysis of the convergence trend of the phase and eigenphase shifts, with respect to the number of deuteron pseudostates included in the model space.

The electrum-tarnish method for the determination of the fugacity of sulfur in laboratory sulfide systems

USGS Publications Warehouse

Barton, P.B.; Toulmin, P.

1964-01-01

A new method for the determination of the fugacity of sulfur in laboratory systems consists of visual observation of the development and decomposition of a sulfide tarnish phase on silver-gold alloy (electrum) of precisely known composition. The alloy system is calibrated against pure sulfur. The method has the following advantages: simple apparatus; ability to cover a large range of fugacity of S2; ability to cover a large temperature range by permitting runs of long duration; ability to tolerate other components in the gas phase; and ease of recovery of the quenched charges for determinations of phases and compositions. Results obtained by the electrum-tarnish method are in satisfactory agreement with those obtained by other workers for the fs2 vs. T curves for the assemblage Ni(1-x)S + NiS2. The electrum-tarnish method shows promise for investigating many other reactions. Univariant reactions studied by this method can be represented as lines forming a genetic grid in terms of the environmental parameters fs2 and T, The slopes of such lines can yield valuable thermodynamic data for the phases involved, but activity coefficients must be known for phases of variable composition. ?? 1964.

Rapid gas hydrate formation process

DOEpatents

Brown, Thomas D.; Taylor, Charles E.; Unione, Alfred J.

2013-01-15

The disclosure provides a method and apparatus for forming gas hydrates from a two-phase mixture of water and a hydrate forming gas. The two-phase mixture is created in a mixing zone which may be wholly included within the body of a spray nozzle. The two-phase mixture is subsequently sprayed into a reaction zone, where the reaction zone is under pressure and temperature conditions suitable for formation of the gas hydrate. The reaction zone pressure is less than the mixing zone pressure so that expansion of the hydrate-forming gas in the mixture provides a degree of cooling by the Joule-Thompson effect and provides more intimate mixing between the water and the hydrate-forming gas. The result of the process is the formation of gas hydrates continuously and with a greatly reduced induction time. An apparatus for conduct of the method is further provided.

Investigation of Thermochemistry Associated with the Carbon–Carbon Coupling Reactions of Furan and Furfural Using ab Initio Methods

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

Liu, Cong; Assary, Rajeev S.; Curtiss, Larry A.

2014-06-26

Upgrading of furan and small oxygenates obtained from the decomposition of cellulosic materials via formation of carbon-carbon bonds is critical to effective conversion of biomass to liquid transportation fuels. Simulation-driven molecular level understanding of carbon-carbon bond formation is required to design efficient catalysts and processes. Accurate quantum chemical methods are utilized here to predict the reaction energetics for conversion of furan (C4H4O) to C5-C8 ethers and the transformation of furfural (C5H6O2) to C13-C26 alkanes. Furan, can be coupled with various C1 to C4 lower molecular weight carbohydrates obtained from the pyrolysis via Diels-Alder type reactions in the gas phase tomore » produce C5-C8 cyclic ethers. The computed reaction barriers for these reactions (~25 kcal/mol) are lower than the cellulose activation or decomposition reactions (~50 kcal/mol). Cycloaddition of C5-C8 cyclo-ethers with furans can also occur in the gas phase, and the computed activation energy is similar to that of the first Diels-Alder reaction. Furfural, obtained from biomass, can be coupled with aldehydes or ketones with α-hydrogen atoms to form longer chain aldol products and these aldol products can undergo vapor phase hydrocycloaddition (activation barrier of ~20 kcal/mol) to form the precursors of C26 cyclic hydrocarbons. These thermochemical studies provide the basis for further vapor phase catalytic studies required for upgrading of furans/furfurals to longer chain hydrocarbons.« less

An experimental design method leading to chemical Turing patterns.

PubMed

Horváth, Judit; Szalai, István; De Kepper, Patrick

2009-05-08

Chemical reaction-diffusion patterns often serve as prototypes for pattern formation in living systems, but only two isothermal single-phase reaction systems have produced sustained stationary reaction-diffusion patterns so far. We designed an experimental method to search for additional systems on the basis of three steps: (i) generate spatial bistability by operating autoactivated reactions in open spatial reactors; (ii) use an independent negative-feedback species to produce spatiotemporal oscillations; and (iii) induce a space-scale separation of the activatory and inhibitory processes with a low-mobility complexing agent. We successfully applied this method to a hydrogen-ion autoactivated reaction, the thiourea-iodate-sulfite (TuIS) reaction, and noticeably produced stationary hexagonal arrays of spots and parallel stripes of pH patterns attributed to a Turing bifurcation. This method could be extended to biochemical reactions.

MAX phase – Alumina composites via elemental and exchange reactions in the Ti{sub n+1}AC{sub n} systems (A=Al, Si, Ga, Ge, In and Sn)

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

Cuskelly, Dylan, E-mail: dylan.cuskelly@uon.edu.au; Richards, Erin; Kisi, Erich, E-mail: Erich.Kisi@newcastle.edu.au

2016-05-15

Extension of the aluminothermal exchange reaction synthesis of M{sub n+1}AX{sub n} phases to systems where the element ‘A’ is not the reducing agent was investigated in systems TiO{sub 2}–A–Al–C for A=Al, Si, Ga, Ge, In and Sn as well as Cr{sub 2}O{sub 3}–Ga–Al–C. MAX phase-Al{sub 2}O{sub 3} composites were made in all systems except those with A=Ga or In. The effectiveness of conversion to MAX phases was generally in the range 63–96% without optimisation of starting ratios. Optimisation in the Ti–Si–C system gave a MAX phase component with >98% Ti{sub 3}SiC{sub 2}. - Graphical abstract: A range of Ti{sub n+1}AX{submore » n} phases with different A elements were synthesised directly from the M oxide via exchange reactions. The process has now been shown to be general in all the systems marked in green in the table. - Highlights: • Ti{sub n+1}AC{sub n} phases were produced via a single step exchange reaction. • 3 MAX phase systems were successful via this method for the first time. • Cr{sub 2}GeC was also able to be produced via an exchange reaction. • The interconversion reaction in MAX phases is more general than previously thought.« less

Apparatus and method for constant flow oxidizing of organic materials

DOEpatents

Surma, Jeffrey E.; Nelson, Norvell; Steward, G. Anthony; Bryan, Garry H.

1999-01-01

The invention is a method and apparatus using high cerium concentration in the anolyte of an electrochemical cell to oxidize organic materials. The method and apparatus further use an ultrasonic mixer to enhance the oxidation rate of the organic material in the electrochemical cell. A reaction vessel provides an advantage of independent reaction temperature control and electrochemical cell temperature control. A separate or independent reaction vessel may be used without an ultrasonic mixer to oxidize gaseous phase organic materials.

Gas-Phase Reactions of Dimethyl Disulfide with Aliphatic Carbanions - A Mass Spectrometry and Computational Study

NASA Astrophysics Data System (ADS)

Franczuk, Barbara; Danikiewicz, Witold

2018-03-01

Ion-molecule reactions of Me2S2 with a wide range of aliphatic carbanions differing by structure and proton affinity values have been studied in the gas phase using mass spectrometry techniques and DFT calculations. The analysis of the spectra shows a variety of product ions formed via different reaction mechanisms, depending on the structure and proton affinity of the carbanion. Product ions of thiophilic reaction ( m/z 47), SN2 ( m/z 79), and E2 elimination - addition sequence of reactions ( m/z 93) can be observed. Primary products of thiophilic reaction can undergo subsequent SN2 and proton transfer reactions. Gibbs free energy profiles calculated for experimentally observed reactions using PBE0/6-311+G(2d,p) method show good agreement with experimental results. [Figure not available: see fulltext.

Thermochemical Studies of Epoxides and Related Compounds

PubMed Central

Morgan, Kathleen M.; Ellis, Jamie A.; Lee, Joseph; Fulton, Ashley; Wilson, Shavonda L.; Dupart, Patrick S.; Dastoori, Rosanna

2013-01-01

Gas phase heats of formation for the our butene oxide isomers are reported. They were obtained by measuring the condensed-phase heat of reduction to the corresponding alcohol using reaction calorimetry. Heats of vaporization were determined, and allow gas-phase heats of formation to be obtained. The experimental measurements are compared to calculations obtained using a variety of computational methods. Overall, the G3 and CBS-APNO methods agree quite well with the experimental data. The influence of alkyl substituents on epoxide stability is discussed. Comparisons to alkenes, cyclopropanes, aziridines, thiiranes and phosphiranes are also made. Isodesmic-type reactions were used to determine strain energies of the epoxides and related compounds with various substituents. PMID:23551240

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

NASA Technical Reports Server (NTRS)

Dateo, Christopher E.; Walch, Stephen P.

2002-01-01

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

On The Validity of the Assumed PDF Method for Modeling Binary Mixing/Reaction of Evaporated Vapor in GAS/Liquid-Droplet Turbulent Shear Flow

NASA Technical Reports Server (NTRS)

Miller, R. S.; Bellan, J.

1997-01-01

An Investigation of the statistical description of binary mixing and/or reaction between a carrier gas and an evaporated vapor species in two-phase gas-liquid turbulent flows is perfomed through both theroetical analysis and comparisons with results from direct numerical simulations (DNS) of a two-phase mixing layer.

A Versatile Low Temperature Synthetic Route to Zintl Phase Precursors: Na4Si4, Na4Ge4 and K4Ge4 as Examples

PubMed Central

Ma, Xuchu; Xu, Fen; Atkins, Tonya; Goforth, Andrea M.; Neiner, Doinita; Navrotsky, Alexandra; Kauzlarich, Susan M.

2010-01-01

Na4Si4 and Na4Ge4 are ideal chemical precursors for inorganic clathrate structures, clusters, and nanocrystals. The monoclinic Zintl phases, Na4Si4 and Na4Ge4, contain isolated homo-tetrahedranide [Si4]4− and [Ge4]4− clusters surrounded by alkali metal cations. In this study, a simple scalable route has been applied to prepare Zintl phases of composition Na4Si4 and Na4Ge4 using the reaction between NaH and Si or Ge at low temperature (420 °C for Na4Si4 and 270 °C for Na4Ge4). The method was also applied to K4Ge4, using KH and Ge as raw materials, to show the versatility of this approach. The influence of specific reaction conditions on the purity of these Zintl phases has been studied by controlling five factors: the method of reagent mixing (manual or ball milled), the stoichiometry between raw materials, the reaction temperature, the heating time and the gas flow rate. Moderate ball-milling and excess NaH or KH facilitate the formation of pure Na4Si4, Na4Ge4 or K4Ge4 at 420 °C (Na4Si4) or 270 °C (both M4Ge4 compounds, M = Na, K). TG/DSC analysis of the reaction of NaH and Ge indicates that ball milling reduces the temperature for reaction and confirms the formation temperature. This method provides large quantities of high quality Na4Si4 and Na4Ge4 without the need for specialized laboratory equipment, such as Schlenk lines, niobium/tantalum containers, or an arc welder, thereby expanding the accessibility and chemical utility of these phases by making them more convenient to prepare. This new synthetic method may also be extended to lithium-containing Zintl phases (LiH is commercially available) as well as to alkali metal-tetrel Zintl compounds of other compositions, e.g. K4Ge9. PMID:19921060

Top-Down and Bottom-Up Approaches in Engineering 1 T Phase Molybdenum Disulfide (MoS2 ): Towards Highly Catalytically Active Materials.

PubMed

Chua, Chun Kiang; Loo, Adeline Huiling; Pumera, Martin

2016-09-26

The metallic 1 T phase of MoS2 has been widely identified to be responsible for the improved performances of MoS2 in applications including hydrogen evolution reactions and electrochemical supercapacitors. To this aim, various synthetic methods have been reported to obtain 1 T phase-rich MoS2 . Here, the aim is to evaluate the efficiencies of the bottom-up (hydrothermal reaction) and top-down (chemical exfoliation) approaches in producing 1 T phase MoS2 . It is established in this study that the 1 T phase MoS2 produced through the bottom-up approach contains a high proportion of 1 T phase and demonstrates excellent electrochemical and electrical properties. Its performance in the hydrogen evolution reaction and electrochemical supercapacitors also surpassed that of 1 T phase MoS2 produced through a top-down approach. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of citrus limonoid glucosides by high performance liquid chromatography coupled to post-column reaction with Ehrlich’s Reagent

USDA-ARS?s Scientific Manuscript database

A method for the identification and quantification of citrus limonoid glucosides in juices based upon high performance liquid chromatography (HPLC) separation coupled to post-column reaction with Ehrlichs’s reagent has been developed. This method utilizes a phenyl stationary phase and an isocratic ...

Acridine orange staining reaction as an index of physiological activity in Escherichia coli

NASA Technical Reports Server (NTRS)

McFeters, G. A.; Singh, A.; Byun, S.; Callis, P. R.; Williams, S.

1991-01-01

The assumption that the acridine orange (AO) color reaction may be used as an index of physiological activity was investigated in laboratory grown Escherichia coli. Spectrofluorometric observations of purified nucleic acids, ribosomes and the microscopic color of bacteriophage-infected cells stained with AO confirmed the theory that single-stranded nucleic acids emit orange to red fluorescence while those that are double-stranded fluoresce green in vivo. Bacteria growing actively in a rich medium could be distinguished from cells in stationary phase by the AO reaction. Cells from log phase appeared red, whereas those in stationary phase were green. However, this differentiation was not seen when the bacteria were grown in a minimal medium or when a variation of the staining method was used. Also, shifting bacteria in stationary phase to starvation conditions rapidly changed their AO staining reaction. Boiling and exposure to lethal concentrations of azide and formalin resulted in stationary-phase cells that appeared red after staining but bacteria killed with chlorine remained green. These findings indicate that the AO staining reaction may be suggestive of physiological activity under defined conditions. However, variables in staining and fixation procedures as well as uncertainties associated with mixed bacterial populations in environmental samples may produce results that are not consistent with the classical interpretation of this reaction. The importance of validating the putative physiological implications of this staining reaction is stressed.

Wang-Landau Reaction Ensemble Method: Simulation of Weak Polyelectrolytes and General Acid-Base Reactions.

PubMed

Landsgesell, Jonas; Holm, Christian; Smiatek, Jens

2017-02-14

We present a novel method for the study of weak polyelectrolytes and general acid-base reactions in molecular dynamics and Monte Carlo simulations. The approach combines the advantages of the reaction ensemble and the Wang-Landau sampling method. Deprotonation and protonation reactions are simulated explicitly with the help of the reaction ensemble method, while the accurate sampling of the corresponding phase space is achieved by the Wang-Landau approach. The combination of both techniques provides a sufficient statistical accuracy such that meaningful estimates for the density of states and the partition sum can be obtained. With regard to these estimates, several thermodynamic observables like the heat capacity or reaction free energies can be calculated. We demonstrate that the computation times for the calculation of titration curves with a high statistical accuracy can be significantly decreased when compared to the original reaction ensemble method. The applicability of our approach is validated by the study of weak polyelectrolytes and their thermodynamic properties.

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

NASA Astrophysics Data System (ADS)

Csernica, Stephen N.

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

Phosphopeptide Enrichment by Covalent Chromatography after Derivatization of Protein Digests Immobilized on Reversed-Phase Supports

PubMed Central

Nika, Heinz; Nieves, Edward; Hawke, David H.; Angeletti, Ruth Hogue

2013-01-01

A rugged sample-preparation method for comprehensive affinity enrichment of phosphopeptides from protein digests has been developed. The method uses a series of chemical reactions to incorporate efficiently and specifically a thiol-functionalized affinity tag into the analyte by barium hydroxide catalyzed β-elimination with Michael addition using 2-aminoethanethiol as nucleophile and subsequent thiolation of the resulting amino group with sulfosuccinimidyl-2-(biotinamido) ethyl-1,3-dithiopropionate. Gentle oxidation of cysteine residues, followed by acetylation of α- and ε-amino groups before these reactions, ensured selectivity of reversible capture of the modified phosphopeptides by covalent chromatography on activated thiol sepharose. The use of C18 reversed-phase supports as a miniaturized reaction bed facilitated optimization of the individual modification steps for throughput and completeness of derivatization. Reagents were exchanged directly on the supports, eliminating sample transfer between the reaction steps and thus, allowing the immobilized analyte to be carried through the multistep reaction scheme with minimal sample loss. The use of this sample-preparation method for phosphopeptide enrichment was demonstrated with low-level amounts of in-gel-digested protein. As applied to tryptic digests of α-S1- and β-casein, the method enabled the enrichment and detection of the phosphorylated peptides contained in the mixture, including the tetraphosphorylated species of β-casein, which has escaped chemical procedures reported previously. The isolates proved highly suitable for mapping the sites of phosphorylation by collisionally induced dissociation. β-Elimination, with consecutive Michael addition, expanded the use of the solid-phase-based enrichment strategy to phosphothreonyl peptides and to phosphoseryl/phosphothreonyl peptides derived from proline-directed kinase substrates and to their O-sulfono- and O-linked β-N-acetylglucosamine (O-GlcNAc)-modified counterparts. Solid-phase enzymatic dephosphorylation proved to be a viable tool to condition O-GlcNAcylated peptide in mixtures with phosphopeptides for selective affinity purification. Acetylation, as an integral step of the sample-preparation method, precluded reduction in recovery of the thiolation substrate caused by intrapeptide lysine-dehydroalanine cross-link formation. The solid-phase analytical platform provides robustness and simplicity of operation using equipment readily available in most biological laboratories and is expected to accommodate additional chemistries to expand the scope of solid-phase serial derivatization for protein structural characterization. PMID:23997662

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.

Method of producing particulate-reinforced composites and composites produced thereby

DOEpatents

Han, Qingyou; Liu, Zhiwei

2013-12-24

A process for producing particle-reinforced composite materials through utilization of an in situ reaction to produce a uniform dispersion of a fine particulate reinforcement phase. The process includes forming a melt of a first material, and then introducing particles of a second material into the melt and subjecting the melt to high-intensity acoustic vibration. A chemical reaction initiates between the first and second materials to produce reaction products in the melt. The reaction products comprise a solid particulate phase, and the high-intensity acoustic vibration fragments and/or separates the reaction products into solid particles that are dispersed in the melt and are smaller than the particles of the second material. Also encompassed are particle-reinforced composite materials produced by such a process.

Method of producing particulate-reinforced composites and composites produced thereby

DOEpatents

Han, Qingyou; Liu, Zhiwei

2015-12-29

A process for producing particle-reinforced composite materials through utilization of an in situ reaction to produce a uniform dispersion of a fine particulate reinforcement phase. The process includes forming a melt of a first material, and then introducing particles of a second material into the melt and subjecting the melt to high-intensity acoustic vibration. A chemical reaction initiates between the first and second materials to produce reaction products in the melt. The reaction products comprise a solid particulate phase, and the high-intensity acoustic vibration fragments and/or separates the reaction products into solid particles that are dispersed in the melt and are smaller than the particles of the second material. Also encompassed are particle-reinforced composite materials produced by such a process.

Elucidation of reaction mechanism involved in the formation of LaNiO3 from XRD and TG analysis

NASA Astrophysics Data System (ADS)

Dharmadhikari, Dipti V.; Athawale, Anjali A.

2013-06-01

The present work is focused on the synthesis and elucidation of reaction mechanism involved in the formation of LaNiO3 with the help of X-ray diffraction (XRD) and thermogravimetric (TG) analysis. LaNiO3 was synthesized by hydrothermal method by heating at 160°C under autogenous pressure for 6h. Pure phase product was obtained after calcining the hydrothermally activated product for 6h at 700°C. The various phases of the product obtained after hydrothermal treatment and calcination followed by the formation of pure phase nanocrystalline lanthanum nickel oxide could be determined from XRD analysis of the samples. The reaction mechanism and phase formation temperature has been interpreted by thermogravimetric analysis of the hydrothermally synthesized product and XRD analysis.

Temperature-dependent structure and phase variation of nickel silicide nanowire arrays prepared by in situ silicidation

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

Liu, Hailong; She, Guangwei, E-mail: shegw@mail.ipc.ac.cn; Mu, Lixuan

Graphical abstract: Display Omitted Highlight: ► Nickel silicides nanowire arrays prepared by a simple in situ silicidation method. ► Phases of nickel silicides could be varied by tuning the reaction temperature. ► A growth model was proposed for the nickel silicides nanowires. ► Diffusion rates of Ni and Si play a critical role for the phase variation. -- Abstract: In this paper, we report an in situ silicidizing method to prepare nickel silicide nanowire arrays with varied structures and phases. The in situ reaction (silicidation) between Si and NiCl{sub 2} led to conversion of Si nanowires to nickel silicide nanowires.more » Structures and phases of the obtained nickel silicides could be varied by changing the reaction temperature. At a relatively lower temperature of 700 °C, the products are Si/NiSi core/shell nanowires or NiSi nanowires, depending on the concentration of NiCl{sub 2} solution. At a higher temperature (800 °C and 900 °C), other phases of the nickel silicides, including Ni{sub 2}Si, Ni{sub 31}Si{sub 12}, and NiSi{sub 2}, were obtained. It is proposed that the different diffusion rates of Ni and Si atoms at different temperatures played a critical role in the formation of nickel silicide nanowires with different phases.« less

Aqueous-organic phase-transfer of highly stable gold, silver, and platinum nanoparticles and new route for fabrication of gold nanofilms at the oil/water interface and on solid supports.

PubMed

Feng, Xingli; Ma, Houyi; Huang, Shaoxin; Pan, Wei; Zhang, Xiaokai; Tian, Fang; Gao, Caixia; Cheng, Yingwen; Luo, Jingli

2006-06-29

A simple but effective aqueous-organic phase-transfer method for gold, silver, and platinum nanoparticles was developed on the basis of the decrease of the PVP's solubility in water with the temperature increase. The present method is superior in the transfer efficiency of highly stable nanoparticles to the common phase-transfer methods. The gold, silver, and platinum nanoparticles transferred to the 1-butanol phase dispersed well, especially silver and platinum particles almost kept the previous particle size. Electrochemical synthesis of gold nanoparticles in an oil-water system was achieved by controlling the reaction temperature at 80 degrees C, which provides great conveniences for collecting metal particles at the oil/water interface and especially for fabricating dense metal nanoparticle films. A technique to fabricate gold nanofilms on solid supports was also established. The shapes and sizes of gold nanoparticles as the building blocks may be controllable through changing reaction conditions.

Solid-state reaction synthesis for mixed-phase Eu3+-doped bismuth molybdate and its luminescence properties

NASA Astrophysics Data System (ADS)

Liang, Danyang; Ding, Yu; Wang, Nan; Cai, Xiaomeng; Li, Jia; Han, Linyu; Wang, Shiqi; Han, Yuanyuan; Jia, Guang; Wang, Liyong

2017-09-01

A method for mixed-phase bismuth molybdate doped with Eu3+ ions was developed by solid-state reaction assisting with polyvinyl alcohol (PVA). The results of powder X-ray diffraction showed a mixed-phase structure and the microscopical characterization technology revealed the formation process with the addition of PVA. As a structure inducer, the PVA molecules played a vital role in the formation of phase structure. The as-obtained Eu3+-doped bismuth molybdates were also characterized by using different spectroscopic techniques including FTIR and photoluminescence (PL). The results show that doping concentration, PVA addition and calcination temperature affect photoluminescence properties remarkably.

Reaction mechanism studies towards effective fabrication of lithium-rich anti-perovskites Li 3OX (X=Cl, Br)

DOE PAGES

Li, Shuai; Zhu, Jinlong; Wang, Yonggang; ...

2015-12-10

Lithium-rich Anti-perovskite (LiRAP), with general formula Li 3OX (X = Cl, Br, I), and recently reported as superionic conductors with 3-dimensional Li + migrating channels, is emerging as a promising candidate for solid electrolyte of all-solid-state LIBs. But, it is still difficult to fabricate pure LiRAP due to the difficulty of the phase formation and moisture-sensitive nature of the products. In this work, we thoroughly studied the formation mechanism of Li 3OCl and Li 3OBr in various solid state reaction routes. We developed different experimental strategies in order to improve the syntheses, in purposes of improved phase stability and large-scalemore » production of LiRAP. One feasible method is to use strongly reductive agents Li metal or LiH to eliminate OH species. The results show that LiH is more effective than Li metal because of negatively charged H - and uniform reaction. The other well-established method is using Li 2O and LiX mixture as reagents to preventing OH phase at the beginning, and using protected ball milling to make fine powders and hence active the reaction. Finally, IR spectroscopy, thermal analyses and first-principle calculation were performed to give indications on the reaction pathway.« less

Synthesis of Y1BaCu3O(x) superconducting powders by intermediate phase reactions

NASA Technical Reports Server (NTRS)

Moure, C.; Fernandez, J. F.; Tartaj, J.; Recio, P.; Duran, P.

1991-01-01

A procedure for synthesizing Y1Ba2Cu3O(x) by solid state reactions was developed. The method is based on the use of barium compounds, previously synthesized, as intermediate phases for the process. The reaction kinetics of this procedure were established between 860 C and 920 C. The crystal structure and the presence of second phases were studied by means of XRD. The sintering behavior and ceramic parameters were also determined. The orthorhombic type-I structure was obtained on the synthesized bodies after a cooling cycle in an air atmosphere. Superconducting transition took place at 91 K. Sintering densities higher than 95 percent D sub th were attained at temperatures below 940 C.

Catalytic decomposition of toxic chemicals over metal-promoted carbon nanotubes.

PubMed

Li, Lili; Han, Changxiu; Han, Xinyu; Zhou, Yixiao; Yang, Li; Zhang, Baogui; Hu, Jianli

2011-01-15

Effective decomposition of toxic gaseous compounds is important for pollution control at many chemical manufacturing plants. This study explores catalytic decomposition of phosphine (PH(3)) using novel metal-promoted carbon nanotubes (CNTs). The cerium-promoted Co/CNTs catalysts (CoCe/CNTs) are synthesized by means of coimpregnation method and reduced by three different methods (H(2), KBH(4), NaH(2)PO(2)·H(2)O/KBH(4)). The morphology, structure, and composition of the catalysts are characterized using a number of analytical instrumentations including high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, BET surface area measurement, and inductively coupled plasma. The activity of the catalysts in PH(3) decomposition reaction is measured and correlated with their surface and structural properties. The characterization results show that the CoCe/CNTs catalyst reduced by H(2) possesses small particles and is shown thermally stable in PH(3) decomposition reaction. The activities of these catalysts are compared and are shown in the following sequence: CoCe/CNTs > Co/CNTs > CoCeBP/CNTs> CoCeB/CNTs. The difference in reduction method results in the formation of different active phases during the PH(3) decomposition reaction. After a catalytic activity test, only the CoP phase is formed on CoCe/CNTs and Co/CNTs catalysts, whereas multiphases CoP, Co(2)P, and Co phases are formed on CoCeBP/CNTs and CoCeB/CNTs. Results show that the CoP phase is formed predominantly on the CoCe/CNTs and Co/CNTs catalysts and is found to likely be the most active phase for this reaction. Furthermore, the CoCe/CNTs catalyst exhibits not only highest activity but also long-term stability in PH(3) decomposition reaction. When operated in a fixed-bed reactor at 360 °C, single-pass PH(3) conversion of about 99.8% can be achieved.

Solution-phase parallel synthesis of aryloxyimino amides via a novel multicomponent reaction among aromatic (Z)-chlorooximes, isocyanides, and electron-deficient phenols.

PubMed

Mercalli, Valentina; Giustiniano, Mariateresa; Del Grosso, Erika; Varese, Monica; Cassese, Hilde; Massarotti, Alberto; Novellino, Ettore; Tron, Gian Cesare

2014-11-10

A library of 41 aryloxyimino amides was prepared via solution phase parallel synthesis by extending the multicomponent reaction of (Z)-chlorooximes and isocyanides to the use of electron-deficient phenols. The resulting aryloxyiminoamide derivatives can be used as intermediates for the synthesis of benzo[d]isoxazole-3-carboxamides, dramatically reducing the number of synthetic steps required by other methods reported in literature.

The effect of B{sub 2}O{sub 3} flux on growth NLBCO superconductor by solid state reaction and wet-mixing methods

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

Suharta, W. G., E-mail: wgsuharta@gmail.com; Wendri, N.; Ratini, N.

The synthesis of B{sub 2}O{sub 3} flux substituted NLBCO superconductor NdBa{sub 1.75}La{sub 0.25}Cu{sub 3}O{sub 7-∂} has been done using solid state reaction and wet-mixing methods in order to obtain homogeneous crystals and single phase. From DTA/TGA characteritations showed the synthesis process by wet-mixing requires a lower temperature than the solid state reaction in growing the superconductor NdBa{sub 1.75}La{sub 0.25}Cu{sub 3}O{sub 7-∂}. Therefore, in this research NdBa{sub 1.75}La{sub 0.25}Cu{sub 3}O{sub 7-∂} sample calcinated at 650°C for wet-mixing method and 820°C for solid state reaction methods. The all samples was sintered at 950°C for ten hours. Crystallinity of the sample was confirmedmore » using X-ray techniques and generally obtained sharp peaks that indicates the sample already well crystallized. Search match analyses for diffraction data gave weight fractions of impurity phase of the solid state reaction method higher than wet-mixing method. In this research showed decreasing the price of the lattice parameter about 1% with the addition of B{sub 2}O{sub 3} flux for the both synthesis process and 2% of wet mixing process for all samples. Characterization using scanning electron microscopy (SEM) showed the distribution of crystal zise for wet-mixing method more homogeneous than solid state reaction method, with he grain size of samples is around 150–250 nm. The results of vibrating sample magnetometer (VSM) showed the paramagnetic properties for all samples.« less

Local bias-induced phase transitions

DOE PAGES

Seal, Katyayani; Baddorf, Arthur P.; Jesse, Stephen; ...

2008-11-27

Electrical bias-induced phase transitions underpin a wide range of applications from data storage to energy generation and conversion. The mechanisms behind these transitions are often quite complex and in many cases are extremely sensitive to local defects that act as centers for local transformations or pinning. Furthermore, using ferroelectrics as an example, we review methods for probing bias-induced phase transitions and discuss the current limitations and challenges for extending the methods to field-induced phase transitions and electrochemical reactions in energy storage, biological and molecular systems.

Effectiveness of using a magnetic spectrograph with the Trojan Horse method

NASA Astrophysics Data System (ADS)

Manwell, S.; Parikh, A.; Chen, A. A.; de Séréville, N.; Adsley, P.; Irvine, D.; Hammache, F.; Stefan, I.; Longland, R. F.; Tomlinson, J.; Morfuace, P.; Le Crom, B.

2018-01-01

The Trojan Horse method relies on performing reactions in a specific kinematic phase space that maximizes contributions of a quasi-free reaction mechanism. The hallmark of this method is that the incident particle can be accelerated to high enough energies to overcome the Coulomb barrier of the target, but once inside the target nucleus the relative motion of the clustered nuclei allows the reaction of interest to proceed at energies below this Coulomb Barrier. This method allows the experimentalist to probe reactions that have significance in astrophysics at low reaction energies that would otherwise be impossible due to the vanishing cross section. Traditionally the Trojan Horse method has been applied with the use of silicon detectors to observe the reaction products. In this study we apply the Trojan Horse method to a well studied reaction to examine the potential benefits of using a splitpole magnetic spectrograph to detect one of the reaction products. We have measure the three body 7Li(d,αn)α reaction to constrain the energy 7Li(d,α)α cross section. Measurements were first made using two silicon detectors, and then by replacing one detector with the magnetic spectrograph. The experimental design, limitations, and early results are discussed.

Chemical Synthesis Accelerated by Paper Spray: The Haloform Reaction

ERIC Educational Resources Information Center

Bain, Ryan M.; Pulliam, Christopher J.; Raab, Shannon A.; Cooks, R. Graham

2016-01-01

In this laboratory, students perform a synthetic reaction in two ways: (i) by traditional bulk-phase reaction and (ii) in the course of reactive paper spray ionization. Mass spectrometry (MS) is used both as an analytical method and a means of accelerating organic syntheses. The main focus of this laboratory exercise is that the same ionization…

Computational methods for reactive transport modeling: An extended law of mass-action, xLMA, method for multiphase equilibrium calculations

NASA Astrophysics Data System (ADS)

Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg; Saar, Martin O.

2016-10-01

We present an extended law of mass-action (xLMA) method for multiphase equilibrium calculations and apply it in the context of reactive transport modeling. This extended LMA formulation differs from its conventional counterpart in that (i) it is directly derived from the Gibbs energy minimization (GEM) problem (i.e., the fundamental problem that describes the state of equilibrium of a chemical system under constant temperature and pressure); and (ii) it extends the conventional mass-action equations with Lagrange multipliers from the Gibbs energy minimization problem, which can be interpreted as stability indices of the chemical species. Accounting for these multipliers enables the method to determine all stable phases without presuming their types (e.g., aqueous, gaseous) or their presence in the equilibrium state. Therefore, the here proposed xLMA method inherits traits of Gibbs energy minimization algorithms that allow it to naturally detect the phases present in equilibrium, which can be single-component phases (e.g., pure solids or liquids) or non-ideal multi-component phases (e.g., aqueous, melts, gaseous, solid solutions, adsorption, or ion exchange). Moreover, our xLMA method requires no technique that tentatively adds or removes reactions based on phase stability indices (e.g., saturation indices for minerals), since the extended mass-action equations are valid even when their corresponding reactions involve unstable species. We successfully apply the proposed method to a reactive transport modeling problem in which we use PHREEQC and GEMS as alternative backends for the calculation of thermodynamic properties such as equilibrium constants of reactions, standard chemical potentials of species, and activity coefficients. Our tests show that our algorithm is efficient and robust for demanding applications, such as reactive transport modeling, where it converges within 1-3 iterations in most cases. The proposed xLMA method is implemented in Reaktoro, a unified open-source framework for modeling chemically reactive systems.

Phase Equilibria of the Ternary Sn-Pb-Co System at 250°C and Interfacial Reactions of Co with Sn-Pb Alloys

NASA Astrophysics Data System (ADS)

Wang, Chao-hong; Kuo, Chun-yi; Yang, Nian-cih

2015-11-01

The isothermal section of the ternary Sn-Pb-Co system at 250°C was experimentally determined through a series of the equilibrated Sn-Pb-Co alloys of various compositions. The equilibrium phases were identified on the basis of compositional analysis. For the Sn-Co intermetallic compounds (IMCs), CoSn3, CoSn2, CoSn and Co3Sn2, the Pb solubility was very limited. There exist five tie-triangle regions. The Co-Pb system involves one monotectic reaction, so the phase separation of liquid alloys near the Co-Pb side occurred prior to solidification. The immiscibility field was also determined. Additionally, interfacial reactions between Co and Sn-Pb alloys were conducted. The reaction phase for the Sn-48 at.%Pb and Sn-58 at.%Pb at 250°C was CoSn3 and CoSn2, respectively. Both of them were simultaneously formed in the Sn-53 at.%Pb/Co. The formed IMCs were closely associated to the phase equilibria relationship of the liquid-CoSn3-CoSn2 tie-triangle. Furthermore, with increasing temperatures, the phase formed in equilibrium with Sn-37 wt.%Pb was found to transit from CoSn3 to CoSn2 at 275°C. We propose a simple method of examining the phase transition temperature in the interfacial reactions to determine the boundaries of the liquid-CoSn3-CoSn2 tie-triangles at different temperatures.

Products and Mechanism of Aerosol Formation from the Reaction of β-Pinene with NO3 Radicals: Role of Oligomer Formation

NASA Astrophysics Data System (ADS)

Claflin, M. S.; Ziemann, P. J.

2017-12-01

Large amounts of organic nitrates have been reported in aerosol analyzed during field studies conducted around the world. Although organic nitrates can be formed in daytime from the oxidation of volatile organic compounds in the presence of NOx, it has recently been proposed that the nighttime reaction of monoterpenes with NO3 radicals may account for a substantial fraction of these compounds. While past studies have made progress quantifying the aerosol forming potential of these reactions, relatively little is known about the gas-phase oxidation mechanism, the identities of stable products, and their fate after they partition into aerosol. In an effort to better understand these reactions, we conducted environmental chamber experiments in which β-pinene was reacted with NO3 radicals and the secondary organic aerosol (SOA) that formed was analyzed online using a thermal desorption particle beam mass spectrometer and offline using a variety of methods. SOA was collected on filters, extracted, and analyzed using derivatization-spectrophotometric methods to quantify carbonyl, hydroxyl, carboxyl, nitrate, peroxide, and ester functional groups; and molecular products were identified and quantified by coupling high performance liquid chromatography with UV-Vis detection and mass spectrometry with electrospray ionization, electron ionization, and chemical ionization. We identified and quantified >98% of the products in the SOA and found that 95% were oligomers formed through hemiacetal and acetal reactions. This information was used to determine the yields of monomer building blocks, which in turn were combined with modeling to estimate branching ratios in the gas-phase oxidation reaction and timescales of oligomer formation within the aerosol. The results of this study highlight several key processes in the formation of SOA from reactions of monoterpenes with NO3 radicals: (1) alkoxy radical chemistry, including the role of ring opening through decomposition (2) particle-phase reactions and (3) formation of separate organic and aqueous phases within aerosol.

pH-Responsive Mercaptoundecanoic Acid Functionalized Gold Nanoparticles and Applications in Catalysis

PubMed Central

Ansar, Siyam M.; Chakraborty, Saptarshi

2018-01-01

Mercaptoundecanoic acid (MUA) functionalized gold nanoparticles (AuNP-MUA) were synthesized and demonstrated to possess pH-triggered aggregation and re-dispersion, as well as the capability of phase transfer between aqueous and organic phases in response to changes in pH. The pH of aggregation for AuNP-MUA is consistent with the pKa of MUA (pH ~4) in solution, while AuNP-MUA phase transition between aqueous and organic phases occurs at pH ~9. The ion pair formation between the amine group in octadecylamine (ODA), the carboxylate group in MUA, and the hydrophobic alkyl chain of ODA facilitates the phase transfer of AuNP-MUA into an organic medium. The AuNP-MUA were investigated as a reusable catalyst in the catalytic reduction of 4-nitrophenol by borohydride—a model reaction for AuNPs. It was determined that 100% MUA surface coverage completely inhibits the catalytic activity of AuNPs. Decreasing the surface coverage was shown to increase catalytic activity, but this decrease also leads to decreased colloidal stability, recoverability, and reusability in subsequent reactions. At 60% MUA surface coverage, colloidal stability and catalytic activity were achieved, but the surface coverage was insufficient to enable redispersion following pH-induced recovery. A balance between AuNP colloidal stability, recoverability, and catalytic activity with reusability was achieved at 90% MUA surface coverage. The AuNP-MUA catalyst can also be recovered at different pH ranges depending on the recovery method employed. At pH ~4, protonation of the MUA results in reduced surface charge and aggregation. At pH ~9, ODA will form an ion-pair with the MUA and induce phase transfer into an immiscible organic phase. Both the pH-triggered aggregation/re-dispersion and aqueous/organic phase transfer methods were employed for catalyst recovery and reuse in subsequent reactions. The ability to recover and reuse the AuNP-MUA catalyst by two different methods and different pH regimes is significant, based on the fact that nanoparticle-catalyzed reactions may occur under different pH conditions. PMID:29772775

A kinetic study of the replacement of calcite marble by fluorite

NASA Astrophysics Data System (ADS)

Trindade Pedrosa, Elisabete; Boeck, Lena; Putnis, Christine V.; Putnis, Andrew

2016-04-01

Replacement reactions are relevant in any situation that involves the reequilibration between a solid and an aqueous fluid phase and are commonly controlled by an interface-coupled dissolution-precipitation mechanism (Putnis and Putnis, 2007). These reactions control many large-scale Earth processes whenever aqueous fluids are available, such as during metamorphism, metasomatism, and weathering. An important consequence of coupled dissolution-precipitation is the generation of porosity in the product phase that then allows the infiltration of the fluid within the mineral being replaced. Understanding the mechanism and kinetics of the replacement of carbonates by fluorite has application in earth sciences and engineering. Fluorite (CaF2) occurs in all kinds of rocks (igneous, sedimentary, and metamorphic) and its origin is commonly associated with hydrothermal fluids. Moreover, calcium carbonate has been suggested as a successful seed material for the sequestration of fluoride from contaminated waters (Waghmare and Arfin, 2015). The aim of the present work is to investigate aspects of the replacement of calcium carbonate by fluorite to better understand the mechanism and kinetics of this reaction. Small cubes (˜ 3 × 3 × 3 mm) of Carrara marble (CaCO3 > 99 %) were cut and reacted with a 4 M ammonium fluoride (NH4F) solution for different times (1 to 48 hours) and temperatures (60, 80, 100, and 140 ° C). The microstructure of the product phases was analysed using SEM. The kinetics of replacement was monitored from the Rietveld analysis of X-ray powder diffraction patterns of the products as a function of temperature and reaction time. After reaction, all samples preserved their size and external morphology (a pseudomorphic replacement) and the product phase (fluorite) was highly porous. The activation energy Ea (kJ/mol) of the replacement reaction was empirically determined by both model-fitting and model-free methods. The isoconversional method yielded an empirical activation energy of 41 kJ/mol, and a statistical approach applied to the model-fitting method revealed that the replacement of Carrara marble by fluorite is better fitted to a diffusion-controlled process. This is consistent with ion diffusion through the fluid phase. These results suggest that the replacement reaction is dependent on the fluid migration rate through the newly formed porosity. Putnis, A., Putnis C.V., 2007. The mechanism of reequilibration of solids in the presence of a fluid phase. Journal of Solid State Chemistry, 180, 1783-1786. Waghmare, S.S., Arfin, T. (2015). Fluoride removal from water by calcium materials: A state-of-the-art review. Int. J. Innov. Res. Sci. Eng. Technol. 4, 8090-8102.

Bayesian Calibration of Thermodynamic Databases and the Role of Kinetics

NASA Astrophysics Data System (ADS)

Wolf, A. S.; Ghiorso, M. S.

2017-12-01

Self-consistent thermodynamic databases of geologically relevant materials (like Berman, 1988; Holland and Powell, 1998, Stixrude & Lithgow-Bertelloni 2011) are crucial for simulating geological processes as well as interpreting rock samples from the field. These databases form the backbone of our understanding of how fluids and rocks interact at extreme planetary conditions. Considerable work is involved in their construction from experimental phase reaction data, as they must self-consistently describe the free energy surfaces (including relative offsets) of potentially hundreds of interacting phases. Standard database calibration methods typically utilize either linear programming or least squares regression. While both produce a viable model, they suffer from strong limitations on the training data (which must be filtered by hand), along with general ignorance of many of the sources of experimental uncertainty. We develop a new method for calibrating high P-T thermodynamic databases for use in geologic applications. The model is designed to handle pure solid endmember and free fluid phases and can be extended to include mixed solid solutions and melt phases. This new calibration effort utilizes Bayesian techniques to obtain optimal parameter values together with a full family of statistically acceptable models, summarized by the posterior. Unlike previous efforts, the Bayesian Logistic Uncertain Reaction (BLUR) model directly accounts for both measurement uncertainties and disequilibrium effects, by employing a kinetic reaction model whose parameters are empirically determined from the experiments themselves. Thus, along with the equilibrium free energy surfaces, we also provide rough estimates of the activation energies, entropies, and volumes for each reaction. As a first application, we demonstrate this new method on the three-phase aluminosilicate system, illustrating how it can produce superior estimates of the phase boundaries by incorporating constraints from all available data, while automatically handling variable data quality due to a combination of measurement errors and kinetic effects.

Molecular dynamics simulation of gas-phase ozone reactions with sabinene and benzene.

PubMed

Ridgway, H F; Mohan, B; Cui, X; Chua, K J; Islam, M R

2017-06-01

Gas-phase reactions of ozone (O 3 ) with volatile organic compounds were investigated both by experiment and molecular simulations. From our experiments, it was found ozone readily reacts with VOC pure components and reduces it effectively. By introducing ozone intermittently, the reaction between VOC and ozone is markedly enhanced. In order to understand the relationship between intermediate reactions and end products, ozone reaction with benzene and alicyclic monoterpene sabinene were simulated via a novel hybrid quantum mechanical/molecular mechanics (QM/MM) algorithm that forced repeated bimolecular collisions. Molecular orbital (MO) rearrangements (manifested as bond dissociation or formation), resulting from the collisions, were computed by semi-empirical unrestricted Hartree-Fock methods (e.g., RM1). A minimum of 975 collisions between ozone and targeted organic species were performed to generate a distribution of reaction products. Results indicated that benzene and sabinene reacted with ozone to produce a range of stable products and intermediates, including carbocations, ring-scission products, as well as peroxy (HO 2 and HO 3 ) and hydroxyl (OH) radicals. Among the stable sabinene products observed included formaldehyde and sabina-ketone, which have been experimentally demonstrated in gas-phase ozonation reactions. Among the benzene ozonation products detected composed of oxygen mono-substituted aromatic C 6 H 5 O, which may undergo further transformation or rearrangement to phenol, benzene oxide or 2,4-cyclohexadienone; a phenomenon which has been experimentally observed in vapor-phase photocatalytic ozonation reactions. Copyright © 2017 Elsevier Inc. All rights reserved.

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

NASA Technical Reports Server (NTRS)

Radhakrishnan, Krishnan; Bittker, David A.

1993-01-01

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

[Preparation of Coated CMC-Fe0 Using Rheological Phase Reaction Method and Research on Degradation of TCE in Water].

PubMed

Fan, Wen-jing; Cheng, Yue; Yu, Shu-zhen; Fan, Xiao-feng

2015-06-01

The coated nanoscale zero-valent iron (coated CMC-Fe0) was synthesized with cheap and environment friendly CMC as the coating agent using rheological phase reaction. The sample was characterized by means of XRD, SEM, TEM and N2 adsorption-stripping and used to study reductive dechlorination of TCE. The experimental results indicated that the removal rate of TCE was about 100% when the CMC-Fe0 dosage was 6 g x L(-1), the initial TCE concentration was 5 mg x L(-1) and the reaction time was 40 h. The TCE degradation reaction of coated CMC-Fe0 followed a pseudo-first-order kinetic model. Finally, the product could be simply recovered.

Method of producing particulate-reinforced composites and composties produced thereby

DOEpatents

Han, Qingyou; Liu, Zhiwei

2013-12-24

A process for producing particle-reinforced composite materials through utilization of an in situ reaction to produce a uniform dispersion of a fine particulate reinforcement phase. The process includes forming a melt of a first material, and then introducing particles of a second material into the melt and subjecting the melt to high-intenisty acoustic vibration. A chemical reaction initiates between the first and second materials to produce reaction products in the melt. The reaciton products comprise a solide particulate phase, and the high-intensity acoustic vibration fragments and/or separates the reaction products into solid particles that are dispersed in the melt and are smaller than the particles of the second material. Also encompassed are particles-reinforced composite materials produced by such a process.

Kinetic phase evolution of spinel cobalt oxide during lithiation

DOE PAGES

Li, Jing; He, Kai; Meng, Qingping; ...

2016-09-15

Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalationmore » reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.« less

Kinetic phase evolution of spinel cobalt oxide during lithiation

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

Li, Jing; He, Kai; Meng, Qingping

Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalationmore » reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.« less

A validated LC method for determination of 2,3-dichlorobenzoic acid and its associated regio isomers.

PubMed

Krishnaiah, Ch; Sri, Khagga Bhavya

2012-05-01

A simple, selective and sensitive gradient reversed-phase liquid chromatography method has been developed for the separation and determination of 2,3-dichlorobenzoic acid, which is an intermediate of the lamotrizine drug substance, and its regio isomers. The separation was achieved on a reversed-phase United States Pharmacopeia L1 (C-18) column using 0.01 M ammonium acetate buffer at pH 2.5 and methanol (50:50 v/v) mixture as mobile phase A and a methanol and water mixture (80:20 v/v) as mobile phase B in a gradient elution at flow rate 1.2 mL/min with ultraviolet detection at 210 nm. The method is found to be selective, precise, linear, accurate and robust. It was used for quality assurance and monitoring the synthetic reactions involved in the process development of lamotrizine. The method is found to be simple, rapid, specific and reliable for the determination of unreacted levels of raw materials and isomers in reaction mixtures and finished product lamotrizine. The method was fully validated as per International Conference of Harmonization guidelines and results from validation confirm that the method is highly suitable for its intended purpose. © The Author [2012]. Published by Oxford University Press. All rights reserved.

A Hybrid Method of Moment Equations and Rate Equations to Modeling Gas-Grain Chemistry

NASA Astrophysics Data System (ADS)

Pei, Y.; Herbst, E.

2011-05-01

Grain surfaces play a crucial role in catalyzing many important chemical reactions in the interstellar medium (ISM). The deterministic rate equation (RE) method has often been used to simulate the surface chemistry. But this method becomes inaccurate when the number of reacting particles per grain is typically less than one, which can occur in the ISM. In this condition, stochastic approaches such as the master equations are adopted. However, these methods have mostly been constrained to small chemical networks due to the large amounts of processor time and computer power required. In this study, we present a hybrid method consisting of the moment equation approximation to the stochastic master equation approach and deterministic rate equations to treat a gas-grain model of homogeneous cold cloud cores with time-independent physical conditions. In this model, we use the standard OSU gas phase network (version OSU2006V3) which involves 458 gas phase species and more than 4000 reactions, and treat it by deterministic rate equations. A medium-sized surface reaction network which consists of 21 species and 19 reactions accounts for the productions of stable molecules such as H_2O, CO, CO_2, H_2CO, CH_3OH, NH_3 and CH_4. These surface reactions are treated by a hybrid method of moment equations (Barzel & Biham 2007) and rate equations: when the abundance of a surface species is lower than a specific threshold, say one per grain, we use the ``stochastic" moment equations to simulate the evolution; when its abundance goes above this threshold, we use the rate equations. A continuity technique is utilized to secure a smooth transition between these two methods. We have run chemical simulations for a time up to 10^8 yr at three temperatures: 10 K, 15 K, and 20 K. The results will be compared with those generated from (1) a completely deterministic model that uses rate equations for both gas phase and grain surface chemistry, (2) the method of modified rate equations (Garrod 2008), which partially takes into account the stochastic effect for surface reactions, and (3) the master equation approach solved using a Monte Carlo technique. At 10 K and standard grain sizes, our model results agree well with the above three methods, while discrepancies appear at higher temperatures and smaller grain sizes.

Effect of salt additives on concrete degradation (Phase II). Executive summary

DOT National Transportation Integrated Search

1995-02-01

This research builds on a previous investigation, which found that corrosion-inhibitor-added deicing salts caused degradation of concrete by both anions and cations. The latest research phase looked at methods to detect the chemical reactions between...

Synthesis of a correcting filter with phase stabilization of the angular velocity of a synchronous motor by the feedback system method

NASA Technical Reports Server (NTRS)

Kazlauskas, K. A.; Kurlavichus, A. I.

1973-01-01

The operating characteristics of a synchronous electric motor are discussed. A system of phase stabilization of the instantaneous angular velocity of rotation of a synchronous-reaction motor is diagrammed. A mathematical model is developed to show the parameters which affect the operation of the motor. The selection of a correcting filter to use with the motor in order to reduce the reaction of the system to interference is explained.

Complex impedance analyses and magnetoelectric effect in ferrite ferroelectric composite ceramics

NASA Astrophysics Data System (ADS)

Patankar, K. K.; Kanade, S. A.; Padalkar, D. S.; Chougule, B. K.

2007-02-01

Magnetoelectric (ME) composites yBa0.8Pb0.2TiO3 (1-y)CuFe2O4 are prepared by ceramic method. The component phases are prepared from two different routes, viz. CuFe2O4 (ferrite phase) is prepared by oxalate precursor route and Ba0.8Pb0.2TiO3 (ferroelectric phase) by solid-state reaction route. No intermediate phases are observed in the composites containing these ferrite and ferroelectric phases. ME conversion factor (measure of ME effect) is found to be enhanced compared to those reported in the composites, in which the component phases were prepared by only one route, i.e. solid-state reaction route. The results on ME conversion are well accounted by measuring the complex impedance and analyzing their Nyquist plots.

MAX phase – Alumina composites via exchange reaction in the M{sub n+1}AlC{sub n} systems (M=Ti, V, Cr, Nb, or Ta)

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

Cuskelly, Dylan T., E-mail: Dylan.cuskelly@uon.edu.au; Kisi, Erich H.; Sugo, Heber O.

2016-01-15

MAX phases have been produced for the first time via an exchange reaction between the M-element oxide and Al leading to an M–Al–C–Al{sub 2}O{sub 3} composite in the V–Al–C, Cr–Al–C, Nb–Al–C and Ta–Al–C systems in addition to the previously known Ti–Al–C system. The reduction reaction was first investigated by forming the binary M–X carbide and then proven to be generic across all M–Al–C systems with the production of the M{sub 2}AlC phase in each case. The work was extended to the other M{sub 3}AlC{sub 2} and M{sub 4}AlC{sub 3} phases in the respective systems, and was successful in 4 ofmore » the 5 cases with moderate yield. - Graphical abstract: A range of M{sub n+1}AX{sub n} phases (M-octahedra with X centres and A layers) were synthesised directly from the M oxide via exchange reactions for the 5 M-elements shown. - Highlights: • Ten M{sub n+1}AlC{sub n} phases were produced from M-oxides via a single step exchange reaction. • Eight of these MAX phases had not been produced via this method before. • Al was found to be a suitable reducing agent in all cases. • The process was also discovered to work under SHS and MASHS conditions.« less

Kinetically-Driven Phase Transformation during Lithiation in Copper Sulfide Nanoflakes

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

He, Kai; Yao, Zhenpeng; Hwang, Sooyeon

Two-dimensional (2D) transition metal chalcogenides have been widely studied and utilized as electrode materials for lithium ion batteries due to their unique layered structures to accommodate reversible lithium insertion. Real-time observation and mechanistic understanding of the phase transformations during lithiation of these materials are critically important for improving battery performance by controlling structures and reaction pathways. Here, we use in situ transmission electron microscopy methods to study the structural, morphological, and chemical evolutions in individual copper sulfide (CuS) nanoflakes during lithiation. We report a highly kinetically driven phase transformation in which lithium ions rapidly intercalate into the 2D van dermore » Waals-stacked interlayers in the initial stage, and further lithiation induces the Cu extrusion via a displacement reaction mechanism that is different from the typical conversion reactions. Density functional theory calculations have confirmed both the thermodynamically favored and the kinetically driven reaction pathways. Lastly, our findings elucidate the reaction pathways of the Li/CuS system under nonequilibrium conditions and provide valuable insight into the atomistic lithiation mechanisms of transition metal sulfides in general.« less

Kinetically-Driven Phase Transformation during Lithiation in Copper Sulfide Nanoflakes

DOE PAGES

He, Kai; Yao, Zhenpeng; Hwang, Sooyeon; ...

2017-08-11

Two-dimensional (2D) transition metal chalcogenides have been widely studied and utilized as electrode materials for lithium ion batteries due to their unique layered structures to accommodate reversible lithium insertion. Real-time observation and mechanistic understanding of the phase transformations during lithiation of these materials are critically important for improving battery performance by controlling structures and reaction pathways. Here, we use in situ transmission electron microscopy methods to study the structural, morphological, and chemical evolutions in individual copper sulfide (CuS) nanoflakes during lithiation. We report a highly kinetically driven phase transformation in which lithium ions rapidly intercalate into the 2D van dermore » Waals-stacked interlayers in the initial stage, and further lithiation induces the Cu extrusion via a displacement reaction mechanism that is different from the typical conversion reactions. Density functional theory calculations have confirmed both the thermodynamically favored and the kinetically driven reaction pathways. Lastly, our findings elucidate the reaction pathways of the Li/CuS system under nonequilibrium conditions and provide valuable insight into the atomistic lithiation mechanisms of transition metal sulfides in general.« less

Preparation of Magnesium, Cobalt and Nickel Ferrite Nanoparticles from Metal Oxides using Deep Eutectic Solvents.

PubMed

Söldner, Anika; Zach, Julia; Iwanow, Melanie; Gärtner, Tobias; Schlosser, Marc; Pfitzner, Arno; König, Burkhard

2016-09-05

Natural deep eutectic solvents (DESs) dissolve simple metal oxides and are used as a reaction medium to synthesize spinel-type ferrite nanoparticles MFe2 O4 (M=Mg, Zn, Co, Ni). The best results for phase-pure spinel ferrites are obtained with the DES consisting of choline chloride (ChCl) and maleic acid. By employing DESs, the reactions proceed at much lower temperatures than usual for the respective solid-phase reactions of the metal oxides and at the same temperatures as synthesis with comparable calcination processes using metal salts. The method therefore reduces the overall required energy for the nanoparticle synthesis. Thermogravimetric analysis shows that the thermolysis process of the eutectic melts in air occurs in one major step. The phase-pure spinel-type ferrite particles are thoroughly characterized by X-ray diffraction, diffuse-reflectance UV/Vis spectroscopy, and scanning electron microscopy. The properties of the obtained nanoparticles are shown to be comparable to those obtained by other methods, illustrating the potential of natural DESs for processing metal oxides. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid state synthesis of poly(dichlorophosphazene)

DOEpatents

Allen, Christopher W.; Hneihen, Azzam S.; Peterson, Eric S.

2001-01-01

A method for making poly(dichlorophosphazene) using solid state reactants is disclosed and described. The present invention improves upon previous methods by removing the need for chlorinated hydrocarbon solvents, eliminating complicated equipment and simplifying the overall process by providing a "single pot" two step reaction sequence. This may be accomplished by the condensation reaction of raw materials in the melt phase of the reactants and in the absence of an environmentally damaging solvent.

Review of Federal Reference Method for Ozone: Nitric Oxide-Chemiluminescence

EPA Science Inventory

•The proposed new FRM measurement principle for ozone is based on quantitative measurement of the chemiluminescence emission from the gas-phase reaction of ozone in an air sample with nitric oxide (NO).•The chemiluminescence from the NO-O3 reaction (with excess NO) is p...

Measurement of phenols dearomatization via electrolysis: the UV-Vis solid phase extraction method.

PubMed

Vargas, Ronald; Borrás, Carlos; Mostany, Jorge; Scharifker, Benjamin R

2010-02-01

Dearomatization levels during electrochemical oxidation of p-methoxyphenol (PMP) and p-nitrophenol (PNP) have been determined through UV-Vis spectroscopy using solid phase extraction (UV-Vis/SPE). The results show that the method is satisfactory to determine the ratio between aromatic compounds and aliphatic acids and reaction kinetics parameters during treatment of wastewater, in agreement with results obtained from numerical deconvolution of UV-Vis spectra. Analysis of solutions obtained from electrolysis of substituted phenols on antimony-doped tin oxide (SnO(2)--Sb) showed that an electron acceptor substituting group favored the aromatic ring opening reaction, preventing formation of intermediate quinone during oxidation. (c) 2009 Elsevier Ltd. All rights reserved.

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.

Pre-Combustion Carbon Dioxide Capture by a New Dual Phase Ceramic-Carbonate Membrane Reactor

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

Lin, Jerry Y. S.

2015-01-31

This report documents synthesis, characterization and carbon dioxide permeation and separation properties of a new group of ceramic-carbonate dual-phase membranes and results of a laboratory study on their application for water gas shift reaction with carbon dioxide separation. A series of ceramic-carbonate dual phase membranes with various oxygen ionic or mixed ionic and electronic conducting metal oxide materials in disk, tube, symmetric, and asymmetric geometric configurations was developed. These membranes, with the thickness of 10 μm to 1.5 mm, show CO 2 permeance in the range of 0.5-5×10 -7 mol·m -2·s -1·Pa -1 in 500-900°C and measured CO 2/N 2more » selectivity of up to 3000. CO 2 permeation mechanism and factors that affect CO 2 permeation through the dual-phase membranes have been identified. A reliable CO 2 permeation model was developed. A robust method was established for the optimization of the microstructures of ceramic-carbonate membranes. The ceramic-carbonate membranes exhibit high stability for high temperature CO 2 separations and water gas shift reaction. Water gas shift reaction in the dual-phase membrane reactors was studied by both modeling and experiments. It is found that high temperature syngas water gas shift reaction in tubular ceramic-carbonate dual phase membrane reactor is feasible even without catalyst. The membrane reactor exhibits good CO 2 permeation flux, high thermal and chemical stability and high thermal shock resistance. Reaction and separation conditions in the membrane reactor to produce hydrogen of 93% purity and CO 2 stream of >95% purity, with 90% CO 2 capture have been identified. Integration of the ceramic-carbonate dual-phase membrane reactor with IGCC process for carbon dioxide capture was analyzed. A methodology was developed to identify optimum operation conditions for a membrane tube of given dimensions that would treat coal syngas with targeted performance. The calculation results show that the dual-phase membrane reactor could improve IGCC process efficiency but the cost of the membrane reactor with membranes having current CO 2 permeance is high. Further research should be directed towards improving the performance of the membranes and developing cost-effective, scalable methods for fabrication of dual-phase membranes and membrane reactors.« less

Liquid and Gas Phase Chemistry of Hypergolic Reactions between MMH and NTO or RFNA

NASA Astrophysics Data System (ADS)

Black, Ariel

Hypergolic systems rely on fuel and oxidizer propellant combinations that spontaneously ignite upon contact. Monomethylhydrazine (MMH) fuel and nitrogen tetroxide (NTO) - based oxidizers embody the state of the art for hypergolic propellants, although the health and safety hazards associated with these propellants demand investigation into less-toxic, high performance alternatives. In order to replicate the combustion characteristics of these highly reactive propellants, a detailed understanding of the full reaction process is necessary. Current reaction mechanisms and hypergolic ignition models generally assume that gas-phase chemistry dominates the interaction since the liquid-phase reactions occur on the order of microseconds. However, condensed-phase reactions produce intermediates integral to gas-phase initiation and development. Additional insight into the physical and chemical processes that dictate this liquid-phase chemistry is therefore essential. Concurrently, further examination of the gas-phase reactions leading to and immediately following ignition is also needed. A method devoted to the determination of the liquid phase hypergolic reaction mechanism and kinematic rate parameters for MMH-NTO and MMH-red fuming nitric acid (RFNA) is presented in this study. MMH-RFNA reaction chemistry is better understood and documented in literature than MMH-NTO and is examined for comparison and validation. Drop on pool experiments at a range of temperatures were initially undertaken using MMH and RFNA and then modified to accommodate the high vapor pressure of NTO. Using a temperature and atmosphere controlled droplet contact chamber, the liquid phases of MMH-RFNA and MMH-NTO were studied by capturing impacts at frame rates from 100,000 to 500,000 fps. This footage allowed for the identification of time delays between droplet contact and initial gas formation, enabling calibration of the Arrhenius pre-exponential factors and activation energies for a global, one-step liquid phase chemical reaction model. These defining constants have never before been experimentally determined for MMH-NTO and can be employed to improve the accuracy of CFD combustion simulations. Induction delay times for MMH-RFNA ranged from 30 to 100 microseconds, agreeing with previously reported data, while MMH-NTO delays varied from 10 to 100 microseconds. Advanced ultraviolet and visible (UV-Vis) spectroscopic techniques were applied to conventional drop test analysis in order to study the emitting species in MMH-NTO and MMH-RFNA combustion reactions. A streak camera coupled with a spectrometer provided temporally resolved spectra for species emitting wavelengths from 250 to 950 nm within a one millimeter diameter point of interest above the reaction. The spectra were compared to known MMH-RFNA gas-phase reaction mechanisms and spectroscopic data reported in literature in an attempt to partially validate the proposed full and reduced MMH-RFNA reaction mechanisms and derive a connection to elementary reactions of MMH-NTO. MMH-NTO consistently produced brighter flames than MMH-RFNA and as such generally generated higher intensity signals for a given spectrometer setting. Both propellant combinations revealed conclusive evidence of OH and NH radicals and probable evidence of CN and/or CH radicals. In most tests OH* yielded the highest intensity signals with both RFNA and NTO. MMH-NTO revealed greater NH* intensity than MMH-RFNA. Additionally, species appeared later but peaked sooner relative to ignition for MMH-RFNA than for MMH-NTO. Efforts to draw correlations between these experimental results and existing reaction mechanisms proved to be challenging and are ongoing. A dominant, high intensity signal characteristic of sodium was an unexpected, but apparently not uncommon, observation, with varying opinions as to its origin.

Modeling chemical reactions for drug design.

PubMed

Gasteiger, Johann

2007-01-01

Chemical reactions are involved at many stages of the drug design process. This starts with the analysis of biochemical pathways that are controlled by enzymes that might be downregulated in certain diseases. In the lead discovery and lead optimization process compounds have to be synthesized in order to test them for their biological activity. And finally, the metabolism of a drug has to be established. A better understanding of chemical reactions could strongly help in making the drug design process more efficient. We have developed methods for quantifying the concepts an organic chemist is using in rationalizing reaction mechanisms. These methods allow a comprehensive modeling of chemical reactivity and thus are applicable to a wide variety of chemical reactions, from gas phase reactions to biochemical pathways. They are empirical in nature and therefore allow the rapid processing of large sets of structures and reactions. We will show here how methods have been developed for the prediction of acidity values and of the regioselectivity in organic reactions, for designing the synthesis of organic molecules and of combinatorial libraries, and for furthering our understanding of enzyme-catalyzed reactions and of the metabolism of drugs.

A Multidimensional B-Spline Correction for Accurate Modeling Sugar Puckering in QM/MM Simulations.

PubMed

Huang, Ming; Dissanayake, Thakshila; Kuechler, Erich; Radak, Brian K; Lee, Tai-Sung; Giese, Timothy J; York, Darrin M

2017-09-12

The computational efficiency of approximate quantum mechanical methods allows their use for the construction of multidimensional reaction free energy profiles. It has recently been demonstrated that quantum models based on the neglect of diatomic differential overlap (NNDO) approximation have difficulty modeling deoxyribose and ribose sugar ring puckers and thus limit their predictive value in the study of RNA and DNA systems. A method has been introduced in our previous work to improve the description of the sugar puckering conformational landscape that uses a multidimensional B-spline correction map (BMAP correction) for systems involving intrinsically coupled torsion angles. This method greatly improved the adiabatic potential energy surface profiles of DNA and RNA sugar rings relative to high-level ab initio methods even for highly problematic NDDO-based models. In the present work, a BMAP correction is developed, implemented, and tested in molecular dynamics simulations using the AM1/d-PhoT semiempirical Hamiltonian for biological phosphoryl transfer reactions. Results are presented for gas-phase adiabatic potential energy surfaces of RNA transesterification model reactions and condensed-phase QM/MM free energy surfaces for nonenzymatic and RNase A-catalyzed transesterification reactions. The results show that the BMAP correction is stable, efficient, and leads to improvement in both the potential energy and free energy profiles for the reactions studied, as compared with ab initio and experimental reference data. Exploration of the effect of the size of the quantum mechanical region indicates the best agreement with experimental reaction barriers occurs when the full CpA dinucleotide substrate is treated quantum mechanically with the sugar pucker correction.

Hydrothermal synthesis of Nd3+-doped heterojunction ms/tz-BiVO4 and its enhanced photocatalytic performance

NASA Astrophysics Data System (ADS)

Chen, Ruizhi; Wang, Weixuan; Jiang, Dongmei; Chu, Xiaoxuan; Ma, Xueming; Zhan, Qingfeng

2018-06-01

BiVO4 photocatalysts with different Nd3+ doping content were prepared by a hydrothermal method with varied hydrothermal reaction time. The effects of Nd3+ doping on phase transformation, morphology, chemical valence, optical properties and photocatalytic activities were investigated. With different reaction time, phase transformation from tetragonal zircon (tz-BiVO4) to monoclinic scheelite (ms-BiVO4) could be found, and Nd3+ doping played a suppressive role in this process. Scanning electron microscopy showed the morphology evolved from irregular structure to rod-like shapes with phase transformation. The photoluminescence induced by Nd3+ doping could be confirmed by UV-vis diffuse reflectance spectra. Photocatalytic performance tests had been performed under simulated solar conditions and sample with 1 at% Nd3+ doping and 5 h reaction time showed the best performance (89% degradation rate in 90 min). The pH also showed great influence on morphology and phase transformation of samples. Finally, the phyotocatalytic mechanism and effects of Nd3+ in phase transformation were discussed.

Detachment of CVD-grown graphene from single crystalline Ni films by a pure gas phase reaction

NASA Astrophysics Data System (ADS)

Zeller, Patrick; Henß, Ann-Kathrin; Weinl, Michael; Diehl, Leo; Keefer, Daniel; Lippmann, Judith; Schulz, Anne; Kraus, Jürgen; Schreck, Matthias; Wintterlin, Joost

2016-11-01

Despite great previous efforts there is still a high need for a simple, clean, and upscalable method for detaching epitaxial graphene from the metal support on which it was grown. We present a method based on a pure gas phase reaction that is free of solvents and polymer supports and avoids mechanical transfer steps. The graphene was grown on 150 nm thick, single crystalline Ni(111) films on Si(111) wafers with YSZ buffer layers. Its quality was monitored by using low energy electron diffraction and scanning tunneling microscopy. The gas phase etching uses a chemical transport reaction, the so-called Mond process, based on the formation of gaseous nickel tetracarbonyl in 1 bar of CO at 75 °C and by adding small amounts of sulfide catalysts. X-ray photoelectron spectroscopy, Raman spectroscopy and scanning electron microscopy were used to characterize the detached graphene. It was found that the method successfully removes the nickel from underneath the graphene layer, so that the graphene lies on the insulating oxide buffer layer. Small residual particles of nickel sulfide and cracks in the obtained graphene layer were identified. The defect concentrations were comparable to graphene samples obtained by wet chemical etching and by the bubbling transfer.

Characterizing fluid dynamics in a bubble column aimed for the determination of reactive mass transfer

NASA Astrophysics Data System (ADS)

Kováts, Péter; Thévenin, Dominique; Zähringer, Katharina

2018-02-01

Bubble column reactors are multiphase reactors that are used in many process engineering applications. In these reactors a gas phase comes into contact with a fluid phase to initiate or support reactions. The transport process from the gas to the liquid phase is often the limiting factor. Characterizing this process is therefore essential for the optimization of multiphase reactors. For a better understanding of the transfer mechanisms and subsequent chemical reactions, a laboratory-scale bubble column reactor was investigated. First, to characterize the flow field in the reactor, two different methods have been applied. The shadowgraphy technique is used for the characterisation of the bubbles (bubble diameter, velocity, shape or position) for various process conditions. This technique is based on particle recognition with backlight illumination, combined with particle tracking velocimetry (PTV). The bubble trajectories in the column can also be obtained in this manner. Secondly, the liquid phase flow has been analysed by particle image velocimetry (PIV). The combination of both methods, delivering relevant information concerning disperse (bubbles) and continuous (liquid) phases, leads to a complete fluid dynamical characterization of the reactor, which is the pre-condition for the analysis of mass transfer between both phases.

Solvent effects and potential of mean force study of the SN2 reaction of CH3+CN‑ in water

NASA Astrophysics Data System (ADS)

Li, Chen; Liu, Peng; Li, Yongfang; Wang, Dunyou

2018-03-01

We used a combined quantum mechanics and molecular mechanics (QM/MM) method to investigate the solvent effects and potential of mean force of the CH3F+CN‑ reaction in water. Comparing to gas phase, the water solution substantially affects the structures of the stationary points along the reaction path. We quantitatively obtained the solvent effects’ contributions to the reaction: 1.7 kcal/mol to the activation barrier and ‑26.0 kcal/mol to the reaction free energy. The potential mean of force calculated with the density functional theory/MM theory has a barrier height at 19.7 kcal/mol, consistent with the experimental result at 23.0 kcal/mol; the calculated reaction free energy at ‑43.5 kcal/mol is also consistent with the one estimated based on the gas-phase data at ‑39.7 kcal/mol. Project supported by the National Natural Science Foundation of China (Grant No. 11774206) and Taishan Scholarship Fund from Shandong Province, China.

Unraveling reaction pathways and specifying reaction kinetics for complex systems.

PubMed

Vinu, R; Broadbelt, Linda J

2012-01-01

Many natural and industrial processes involve a complex set of competing reactions that include several different species. Detailed kinetic modeling of such systems can shed light on the important pathways involved in various transformations and therefore can be used to optimize the process conditions for the desired product composition and properties. This review focuses on elucidating the various components involved in modeling the kinetics of pyrolysis and oxidation of polymers. The elementary free radical steps that constitute the chain reaction mechanism of gas-phase/nonpolar liquid-phase processes are outlined. Specification of the rate coefficients of the various reaction families, which is central to the theme of kinetics, is described. Construction of the reaction network on the basis of the types of end groups and reactive moieties in a polymer chain is discussed. Modeling frameworks based on the method of moments and kinetic Monte Carlo are evaluated using illustrations. Finally, the prospects and challenges in modeling biomass conversion are addressed.

Variational transition state theory: theoretical framework and recent developments.

PubMed

Bao, Junwei Lucas; Truhlar, Donald G

2017-12-11

This article reviews the fundamentals of variational transition state theory (VTST), its recent theoretical development, and some modern applications. The theoretical methods reviewed here include multidimensional quantum mechanical tunneling, multistructural VTST (MS-VTST), multi-path VTST (MP-VTST), both reaction-path VTST (RP-VTST) and variable reaction coordinate VTST (VRC-VTST), system-specific quantum Rice-Ramsperger-Kassel theory (SS-QRRK) for predicting pressure-dependent rate constants, and VTST in the solid phase, liquid phase, and enzymes. We also provide some perspectives regarding the general applicability of VTST.

Methods of making textured catalysts

DOEpatents

Werpy, Todd [West Richland, WA; Frye, Jr., John G.; Wang, Yong [Richland, WA; Zacher, Alan H [Kennewick, WA

2010-08-17

A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

Mesoporous mixed-phase Ga{sub 2}O{sub 3}: Green synthesis and enhanced photocatalytic activity

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

Liu, Jin; The Key Laboratory of Rare Earth Functional Materials and Applications, Zhoukou Normal University, Zhoukou 466001; Zhang, Gaoke, E-mail: gkzhang@whut.edu.cn

2015-08-15

Highlights: • Mixed-phase Ga{sub 2}O{sub 3} was synthesized by a facile and green method. • Mixed-phase Ga{sub 2}O{sub 3} exhibited good photocatalytic activity and stability. • The reactive species in the photocatalytic process were investigated. - Abstract: Mesoporous mixed-phase Ga{sub 2}O{sub 3} was synthesized by calcining the GaOOH precursor. The composition, crystal phase and microstructures of Ga{sub 2}O{sub 3} were characterized in detail. The phase composition of the as-prepared Ga{sub 2}O{sub 3} depended on the calcination temperature and the mixed-phase Ga{sub 2}O{sub 3} was obtained at 600–700 °C. As compared to the pure-phase α-Ga{sub 2}O{sub 3} and β-Ga{sub 2}O{sub 3},more » the mixed-phase Ga{sub 2}O{sub 3} exhibited an enhanced photocatalytic property for the degradation of metronidazole solution. The heterojunction in the mixed-phase Ga{sub 2}O{sub 3} was beneficial to the separation of photogenerated electrons and holes. Moreover, the mixed-phase Ga{sub 2}O{sub 3} possessed mesopore structure, which increased more reaction sites and was in favor of the contact of metronidazole molecules with reaction sites. The recycling experiments show that the mixed-phase Ga{sub 2}O{sub 3} has good stability and can be separated easily from the reaction system.« less

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

NASA Astrophysics Data System (ADS)

Buckley, Jacqueline L.

2010-03-01

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

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

PubMed

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

2018-03-25

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

Green polymer chemistry: Synthesis of poly(disulfide) polymers and networks

NASA Astrophysics Data System (ADS)

Rosenthal-Kim, Emily Quinn

The disulfide group is unique in that it presents a covalent bond that is easily formed and cleaved under certain biological conditions. While the ease of disulfide bond cleavage is often harnessed as a method of biodegradation, the ease of disulfide bond formation as a synthetic strategy is often overlooked. The objective this research was to synthesize poly(disulfide) polymers and disulfide crosslinked networks from a green chemistry approach. The intent of the green chemistry approach was to take advantage of the mild conditions applicable to disulfide bond synthesis from thiols. With anticipated use as biomaterials, it was also desired that the polymer materials could be degraded under biological conditions. Here, a new method of poly(disulfide) polymer synthesis is introduced which was inspired by the reaction conditions and reagents found in Nature. Ambient temperatures and aqueous mixtures were used in the new method. Hydrogen peroxide, one of the Nature's most powerful oxidizing species was used as the oxidant in the new polymerization reaction. The dithiol monomer, 3,6-dioxa-1,8-octanedithiol was first solubilized in triethylamine, which activated the thiol groups and made the monomer water soluble. At room temperature, the organic dithiol/amine solution was then mixed with dilute aqueous hydrogen peroxide (3% by weight) to make the poly(disulfide) polymers. The presence of a two phase system (organic and aqueous phases) was critical to the polymerization reaction. As the reaction progresses, a third, polymer phase appeared. At ambient temperatures and above, this phase separated from the reaction mixture and the polymer product was easily removed from the reaction solution. These polymers reach Mn > 250,000 g/mol in under two hours. Molecular weight distributions were between 1.5 and 2.0. Reactions performed in an ice bath which remain below room temperature contain high molecular weight polymers with Mn ≈ 120,000 g/mol and have a molecular weight distribution of around 1.15. However, the majority of the product consists of low molecular weight cyclic poly(disulfide) oligomers. In reactions maintained below 18°C, the organic components were miscible in the aqueous hydrogen peroxide and a milky emulsion was produced. The polymers were degraded using the disulfide-specific reducing agent, dithiothreitol. Poly(disulfide) polymer networks were also synthesized in a two-phase system. Due to the poor solubility of the crosslinker, trimethylolpropane tris(2-mercaptopropionate, organic solvents were required to obtain consistent networks. The networks were degraded using dithiothreitol in tetrahydrofuran. The networks were stable under aqueous reducing conditions. The disulfide-bearing biochemical, alpha-lipoic acid, was investigated as monomer for the new method of poly(disulfide) polymer synthesis. It was also polymerized thermally and by a new interfacial method that proceeds at the air-water interface. Polymer products were often too large to be characterized by SEC (Mn > 1,000,000 g/mol). A poly(alpha-LA) polymer sample showed mass loss in aqueous solutions of glutathione at pH = 5.2 which was used to model cytosolic conditions. Poly(alpha-LA) was decorated with PEG (2,000 g/mol) in an esterification reaction catalyzed by Candida antarctica lipase B (CALB). The decorated polymers were imaged using AFM which revealed branch-like structures. To make new alpha-lipoic acid based monomers and macromonomers, CALB-catalyzed esterification, was used to conjugate alpha-lipoic acid to a variety of glycols including: diethylene glycol monomethyl ether, tetraethylene glycol, hexaethylene glycol, and poly(ethylene glycol). The products were verified using NMR spectroscopy and mass spectrometry.

Organic aerogel microspheres and fabrication method therefor

DOEpatents

Mayer, S.T.; Kong, F.M.; Pekala, R.W.; Kaschmitter, J.L.

1996-04-16

Organic aerogel microspheres which can be used in capacitors, batteries, thermal insulation, adsorption/filtration media, and chromatographic packings, having diameters ranging from about 1 micron to about 3 mm. The microspheres can be pyrolyzed to form carbon aerogel microspheres. This method involves stirring the aqueous organic phase in mineral oil at elevated temperature until the dispersed organic phase polymerizes and forms nonsticky gel spheres. The size of the microspheres depends on the collision rate of the liquid droplets and the reaction rate of the monomers from which the aqueous solution is formed. The collision rate is governed by the volume ratio of the aqueous solution to the mineral oil and the shear rate, while the reaction rate is governed by the chemical formulation and the curing temperature.

Organic aerogel microspheres and fabrication method therefor

DOEpatents

Mayer, Steven T.; Kong, Fung-Ming; Pekala, Richard W.; Kaschmitter, James L.

1996-01-01

Organic aerogel microspheres which can be used in capacitors, batteries, thermal insulation, adsorption/filtration media, and chromatographic packings, having diameters ranging from about 1 micron to about 3 mm. The microspheres can be pyrolyzed to form carbon aerogel microspheres. This method involves stirring the aqueous organic phase in mineral oil at elevated temperature until the dispersed organic phase polymerizes and forms nonsticky gel spheres. The size of the microspheres depends on the collision rate of the liquid droplets and the reaction rate of the monomers from which the aqueous solution is formed. The collision rate is governed by the volume ratio of the aqueous solution to the mineral oil and the shear rate, while the reaction rate is governed by the chemical formulation and the curing temperature.

The thermochemistry of london dispersion-driven transition metal reactions: getting the 'right answer for the right reason'.

PubMed

Hansen, Andreas; Bannwarth, Christoph; Grimme, Stefan; Petrović, Predrag; Werlé, Christophe; Djukic, Jean-Pierre

2014-10-01

Reliable thermochemical measurements and theoretical predictions for reactions involving large transition metal complexes in which long-range intramolecular London dispersion interactions contribute significantly to their stabilization are still a challenge, particularly for reactions in solution. As an illustrative and chemically important example, two reactions are investigated where a large dipalladium complex is quenched by bulky phosphane ligands (triphenylphosphane and tricyclohexylphosphane). Reaction enthalpies and Gibbs free energies were measured by isotherm titration calorimetry (ITC) and theoretically 'back-corrected' to yield 0 K gas-phase reaction energies (ΔE). It is shown that the Gibbs free solvation energy calculated with continuum models represents the largest source of error in theoretical thermochemistry protocols. The ('back-corrected') experimental reaction energies were used to benchmark (dispersion-corrected) density functional and wave function theory methods. Particularly, we investigated whether the atom-pairwise D3 dispersion correction is also accurate for transition metal chemistry, and how accurately recently developed local coupled-cluster methods describe the important long-range electron correlation contributions. Both, modern dispersion-corrected density functions (e.g., PW6B95-D3(BJ) or B3LYP-NL), as well as the now possible DLPNO-CCSD(T) calculations, are within the 'experimental' gas phase reference value. The remaining uncertainties of 2-3 kcal mol(-1) can be essentially attributed to the solvation models. Hence, the future for accurate theoretical thermochemistry of large transition metal reactions in solution is very promising.

Catalyst and method for aqueous phase reactions

DOEpatents

Elliott, Douglas C.; Hart, Todd R.

1999-01-01

The present invention is a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional metal deposited onto the support in a second dispersed phase. The additional metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase without substantially affecting the catalytic activity, thereby increasing the life time of the catalyst.

Reaction Dynamics Following Ionization of Ammonia Dimer Adsorbed on Ice Surface.

PubMed

Tachikawa, Hiroto

2016-09-22

The ice surface provides an effective two-dimensional reaction field in interstellar space. However, how the ice surface affects the reaction mechanism is still unknown. In the present study, the reaction of an ammonia dimer cation adsorbed both on water ice and cluster surface was theoretically investigated using direct ab initio molecular dynamics (AIMD) combined with our own n-layered integrated molecular orbital and molecular mechanics (ONIOM) method, and the results were compared with reactions in the gas phase and on water clusters. A rapid proton transfer (PT) from NH3(+) to NH3 takes place after the ionization and the formation of intermediate complex NH2(NH4(+)) is found. The reaction rate of PT was significantly affected by the media connecting to the ammonia dimer. The time of PT was calculated to be 50 fs (in the gas phase), 38 fs (on ice), and 28-33 fs (on water clusters). The dissociation of NH2(NH4(+)) occurred on an ice surface. The reason behind the reaction acceleration on an ice surface is discussed.

Free energy from molecular dynamics with multiple constraints

NASA Astrophysics Data System (ADS)

den Otter, W. K.; Briels, W. J.

In molecular dynamics simulations of reacting systems, the key step to determining the equilibrium constant and the reaction rate is the calculation of the free energy as a function of the reaction coordinate. Intuitively the derivative of the free energy is equal to the average force needed to constrain the reaction coordinate to a constant value, but the metric tensor effect of the constraint on the sampled phase space distribution complicates this relation. The appropriately corrected expression for the potential of mean constraint force method (PMCF) for systems in which only the reaction coordinate is constrained was published recently. Here we will consider the general case of a system with multiple constraints. This situation arises when both the reaction coordinate and the 'hard' coordinates are constrained, and also in systems with several reaction coordinates. The obvious advantage of this method over the established thermodynamic integration and free energy perturbation methods is that it avoids the cumbersome introduction of a full set of generalized coordinates complementing the constrained coordinates. Simulations of n -butane and n -pentane in vacuum illustrate the method.

How Accurate Are Transition States from Simulations of Enzymatic Reactions?

PubMed Central

2015-01-01

The rate expression of traditional transition state theory (TST) assumes no recrossing of the transition state (TS) and thermal quasi-equilibrium between the ground state and the TS. Currently, it is not well understood to what extent these assumptions influence the nature of the activated complex obtained in traditional TST-based simulations of processes in the condensed phase in general and in enzymes in particular. Here we scrutinize these assumptions by characterizing the TSs for hydride transfer catalyzed by the enzyme Escherichia coli dihydrofolate reductase obtained using various simulation approaches. Specifically, we compare the TSs obtained with common TST-based methods and a dynamics-based method. Using a recently developed accurate hybrid quantum mechanics/molecular mechanics potential, we find that the TST-based and dynamics-based methods give considerably different TS ensembles. This discrepancy, which could be due equilibrium solvation effects and the nature of the reaction coordinate employed and its motion, raises major questions about how to interpret the TSs determined by common simulation methods. We conclude that further investigation is needed to characterize the impact of various TST assumptions on the TS phase-space ensemble and on the reaction kinetics. PMID:24860275

Experimental and theoretical studies on gas-phase reactions of NO3 radicals with three methoxyphenols: Guaiacol, creosol, and syringol

NASA Astrophysics Data System (ADS)

Yang, Bo; Zhang, Haixu; Wang, Youfeng; Zhang, Peng; Shu, Jinian; Sun, Wanqi; Ma, Pengkun

2016-01-01

Methoxyphenols, lignin pyrolysis products, are major biomass combustion components and are considered potential tracers for wood smoke emissions. Their atmospheric reactivity, however, has not been well characterized. Guaiacol, creosol, and syringol are three typical methoxyphenols generated in relatively high concentrations in fresh wood smoke. In this study, the gas-phase reactions of NO3 radicals with these methoxyphenols were investigated using a laboratory-built vacuum ultraviolet photoionization gas time-of-flight mass spectrometer (VUV-GTOFMS) and off-line GC-MS. By combining experimental and theoretical methods, 4-nitroguaiacol, 6-nitroguaiacol, and 4,6-dinitroguaiacol were determined as the primary degradation products for guaiacol; similarly, 6-nitrocreosol and 3-nitrosyringol were identified for creosol and syringol, respectively. Using the relative rate method, rate constants at 298 K and 1 atm for the gas-phase reactions of guaiacol, creosol, and syringol with NO3 radicals were measured to be 3.2 × 10-12, 2.4 × 10-13, and 4.0 × 10-13 cm3 molecule-1 s-1, respectively. At a typical tropospheric concentration of NO3 radicals (5 × 108 molecule cm-3), atmospheric lifetimes for guaiacol, creosol, and syringol toward NO3 radicals were 0.2, 2.3, and 1.4 h, respectively. These results indicate that the reaction with NO3 radicals can be a major sink for methoxyphenols at night.

Geometric phase effects in ultracold collisions of H/D with rotationally excited HD

NASA Astrophysics Data System (ADS)

Kendrick, Brian K.; Croft, James F. E.; Hazra, Jisha; Balakrishnan, N.

2017-04-01

Quantum reactive scattering calculations for the H/D + HD(v = 4 , j = 1 , 2) -> H/D + HD(v', j') and H + H2(v = 4 , j = 1 , 2) -> H + H2(v', j') exchange reactions are presented for the ground electronic state of H3. A numerically exact three-dimensional time-independent scattering method based on hyperspherical coordinates is used to compute rotationally resolved reaction cross sections and non-thermal rate coefficients for collision energies between 1 μK and 100 K . The geometric (Berry) phase associated with the D3h conical intersection in H3 is included using a U(1) vector (gauge) potential approach. It is shown that the geometric phase leads to a significant (up to three orders of magnitude) enhancement or suppression of the ultracold reaction rate coefficients depending upon whether the interference between the reaction pathways encircling the conical intersection is constructive or destructive. The nature of the interference is governed by a newly discovered mechanism which leads to an effective quantization of the ultracold scattering phase shifts. Interesting behavior due to rotational excitation of the HD and H2 is observed which might be exploited by experimentalists to control the reaction outcome. This work was supported in part by NSF Grant PHY-1505557 (N.B.) and ARO MURI Grant No. W911NF-12-1-0476 (N.B.), and DOE LDRD Grant No. 20170221ER (B.K.).

Increased alloimmunisation and transfusion reaction reporting in patients with solid-phase panreactivity.

PubMed

Olofson, Andrea M; Chandler, Rachael M; Marx-Wood, Cynthia R; Babcock, Craig A; Dunbar, Nancy M

2017-11-01

Automated solid-phase antibody screening uses red blood cell (RBC) membranes immobilised on polystyrene test wells to detect RBC specific antibodies. Despite its time-saving and labour-saving benefits, this method produces a higher rate of nonspecific reactivity compared with manual screening. Solid-phase panreactivity (SPP) is characterised by panreactivity (ie, all test cells reacting) in solid-phase testing accompanied by a negative autocontrol and a lack of reactivity when the same screening cells are tested in tube. The mechanisms underlying SPP and its clinical significance remain unclear. The goals of this study were to describe the prevalence of SPP at our institution and determine the alloimmunisation and transfusion reaction rates within this population. Data were collected on all patients undergoing type and screen testing over a 6-year period. Study patients undergoing subsequent transfusion were evaluated for reported transfusion reactions and development of new alloantibodies. Of the 76 051 patients studied, 0.7% demonstrated SPP of which 11% developed new alloantibodies. The transfusion reaction reporting rate among patients with SPP was 2%. Our data suggest that patients with SPP have higher rates of reported transfusion reactions and alloantibody development compared with those without SPP. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

Textured catalysts and methods of making textured catalysts

DOEpatents

Werpy, Todd [West Richland, WA; Frye, Jr., John G.; Wang, Yong [Richland, WA; Zacher, Alan H [Kennewick, WA

2007-03-06

A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

A novel differential electrochemical mass spectrometry method to determine the product distribution from parasitic Methanol oxidation reaction on oxygen reduction reaction catalysts

NASA Astrophysics Data System (ADS)

Jurzinsky, Tilman; Kurzhals, Philipp; Cremers, Carsten

2018-06-01

The oxygen reduction reaction is in research focus since several decades due to its importance for the overall fuel cell performance. In direct methanol fuel cells, the crossover of methanol and its subsequent parasitic oxidation are main issues when it comes to preventing fuel cell performance losses. In this work, we present a novel differential electrochemical mass spectrometry method to evaluate oxygen reduction reaction catalysts on their tolerance to methanol being present at the cathode. Besides this, the setup allows to measure under more realistic fuel cell conditions than typical rotating disc electrode measurements, because the oxygen reduction reaction is evaluated in gaseous phase and a gas diffusion electrode is used as working electrode. Due to the new method, it was possible to investigate the oxygen reduction reaction on two commonly used catalysts (Pt/C and Pt3Co/C) in absence and presence of methanol. It was found, that Pt3Co/C is less prone to parasitic current losses due to methanol oxidation reaction. By connecting a mass spectrometer to the electrochemical cell, the new method allows to determine the products formed on the catalysts due to parasitic methanol electrooxidation.

21 CFR 184.1005 - Acetic acid.

Code of Federal Regulations, 2014 CFR

2014-04-01

... synthesis. The principal synthetic methods currently employed are oxidation of acetaldehyde derived from ethylene, liquid phase oxidation of butane, and reaction of carbon monoxide with methanol derived from...

Flow chemistry: intelligent processing of gas-liquid transformations using a tube-in-tube reactor.

PubMed

Brzozowski, Martin; O'Brien, Matthew; Ley, Steven V; Polyzos, Anastasios

2015-02-17

CONSPECTUS: The previous decade has witnessed the expeditious uptake of flow chemistry techniques in modern synthesis laboratories, and flow-based chemistry is poised to significantly impact our approach to chemical preparation. The advantages of moving from classical batch synthesis to flow mode, in order to address the limitations of traditional approaches, particularly within the context of organic synthesis are now well established. Flow chemistry methodology has led to measurable improvements in safety and reduced energy consumption and has enabled the expansion of available reaction conditions. Contributions from our own laboratories have focused on the establishment of flow chemistry methods to address challenges associated with the assembly of complex targets through the development of multistep methods employing supported reagents and in-line monitoring of reaction intermediates to ensure the delivery of high quality target compounds. Recently, flow chemistry approaches have addressed the challenges associated with reactions utilizing reactive gases in classical batch synthesis. The small volumes of microreactors ameliorate the hazards of high-pressure gas reactions and enable improved mixing with the liquid phase. Established strategies for gas-liquid reactions in flow have relied on plug-flow (or segmented flow) regimes in which the gas plugs are introduced to a liquid stream and dissolution of gas relies on interfacial contact of the gas bubble with the liquid phase. This approach confers limited control over gas concentration within the liquid phase and is unsuitable for multistep methods requiring heterogeneous catalysis or solid supported reagents. We have identified the use of a gas-permeable fluoropolymer, Teflon AF-2400, as a simple method of achieving efficient gas-liquid contact to afford homogeneous solutions of reactive gases in flow. The membrane permits the transport of a wide range of gases with significant control of the stoichiometry of reactive gas in a given reaction mixture. We have developed a tube-in-tube reactor device consisting of a pair of concentric capillaries in which pressurized gas permeates through an inner Teflon AF-2400 tube and reacts with dissolved substrate within a liquid phase that flows within a second gas impermeable tube. This Account examines our efforts toward the development of a simple, unified methodology for the processing of gaseous reagents in flow by way of development of a tube-in-tube reactor device and applications to key C-C, C-N, and C-O bond forming and hydrogenation reactions. We further describe the application to multistep reactions using solid-supported reagents and extend the technology to processes utilizing multiple gas reagents. A key feature of our work is the development of computer-aided imaging techniques to allow automated in-line monitoring of gas concentration and stoichiometry in real time. We anticipate that this Account will illustrate the convenience and benefits of membrane tube-in-tube reactor technology to improve and concomitantly broaden the scope of gas/liquid/solid reactions in organic synthesis.

Theoretical investigation of the gas-phase reactions of CrO(+) with ethylene.

PubMed

Scupp, Thomas M; Dudley, Timothy J

2010-01-21

The potential energy surfaces associated with the reactions of chromium oxide cation (CrO(+)) with ethylene have been characterized using density functional, coupled-cluster, and multireference methods. Our calculations show that the most probable reaction involves the formation of acetaldehyde and Cr(+) via a hydride transfer involving the metal center. Our calculations support previous experimental hypotheses that a four-membered ring intermediate plays an important role in the reactivity of the system. We have also characterized a number of viable reaction pathways that lead to other products, including ethylene oxide. Due to the experimental observation that CrO(+) can activate carbon-carbon bonds, a reaction pathway involving C-C bond cleavage has also been characterized. Since many of the reactions involve a change in the spin state in going from reactants to products, locations of these spin surface crossings are presented and discussed. The applicability of methods based on Hartree-Fock orbitals is also discussed.

Postmarket Drug Surveillance Without Trial Costs: Discovery of Adverse Drug Reactions Through Large-Scale Analysis of Web Search Queries

PubMed Central

Gabrilovich, Evgeniy

2013-01-01

Background Postmarket drug safety surveillance largely depends on spontaneous reports by patients and health care providers; hence, less common adverse drug reactions—especially those caused by long-term exposure, multidrug treatments, or those specific to special populations—often elude discovery. Objective Here we propose a low cost, fully automated method for continuous monitoring of adverse drug reactions in single drugs and in combinations thereof, and demonstrate the discovery of heretofore-unknown ones. Methods We used aggregated search data of large populations of Internet users to extract information related to drugs and adverse reactions to them, and correlated these data over time. We further extended our method to identify adverse reactions to combinations of drugs. Results We validated our method by showing high correlations of our findings with known adverse drug reactions (ADRs). However, although acute early-onset drug reactions are more likely to be reported to regulatory agencies, we show that less acute later-onset ones are better captured in Web search queries. Conclusions Our method is advantageous in identifying previously unknown adverse drug reactions. These ADRs should be considered as candidates for further scrutiny by medical regulatory authorities, for example, through phase 4 trials. PMID:23778053

Silica hydride intermediate for octadecylsilica and phenyl bonded phase preparation via heterogeneous hydrosilation in supercritical carbon dioxide.

PubMed

Scully, N M; Ashu-Arrah, B A; Nagle, A P; Omamogho, J O; O'Sullivan, G P; Friebolin, V; Dietrich, B; Albert, K; Glennon, J D

2011-04-15

Investigations into the preparation of silica hydride intermediate in supercritical carbon dioxide (sc-CO(2)) that avoids the use of organic solvents such as toluene or dioxane are described. The effects of reaction temperature, pressure and time on the surface coverage of the supercritical fluid generated silica hydride intermediate were studied. Under optimised supercritical conditions of 120°C, 483 bar and 3 h reaction time, silica hydride (Si-H) conversion efficiencies of ca. 40% were achieved for the hydride intermediate prepared from a monofunctional silane reagent (dimethylmethoxysilane). Si-H conversion efficiencies (as determined from (29)Si CP-MAS NMR spectral analysis) for the hydride intermediate prepared from triethoxysilane (TES) in sc-CO(2) were found to be comparable to those obtained using a TES silanisation approach in an organic solvent. (13)C and (29)Si CP-MAS-NMR spectroscopy was employed to provide a complete structural assignment of the silica hydride intermediates. Furthermore, supercritical CO(2) was subsequently employed as a reaction medium for the heterogenous hydrosilation of silica hydride with octadecene and with styrene, in the presence of a free radical initiator. These supercritical fluid generated reversed-phase materials were prepared in a substantially reduced reaction time (3 h) compared to organic solvent based methods (100 h reaction time). Silica functionalisation in sc-CO(2) presents an efficient and clean alternative to organic solvent based methods for the preparation of important silica hydride intermediate and silica bonded stationary phases via a hydrosilation approach. Copyright © 2010 Elsevier B.V. All rights reserved.

21 CFR 184.1005 - Acetic acid.

Code of Federal Regulations, 2012 CFR

2012-04-01

... carbohydrates or by organic synthesis. The principal synthetic methods currently employed are oxidation of acetaldehyde derived from ethylene, liquid phase oxidation of butane, and reaction of carbon monoxide with...

21 CFR 184.1005 - Acetic acid.

Code of Federal Regulations, 2013 CFR

2013-04-01

... carbohydrates or by organic synthesis. The principal synthetic methods currently employed are oxidation of acetaldehyde derived from ethylene, liquid phase oxidation of butane, and reaction of carbon monoxide with...

Molten salt synthesis of nanocrystalline phase of high dielectric constant material CaCu3Ti4O12.

PubMed

Prakash, B Shri; Varma, K B R

2008-11-01

Nanocrystalline powders of giant dielectric constant material, CaCu3Ti4O12 (CCTO), have been prepared successfully by the molten salt synthesis (MSS) using KCl at 750 degrees C/10 h, which is significantly lower than the calcination temperature (approximately 1000 degrees C) that is employed to obtain phase pure CCTO in the conventional solid-state reaction route. The water washed molten salt synthesized powder, characterized by X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), and Transmission electron microscopy (TEM) confirmed to be a phase pure CCTO associated with approximately 150 nm sized crystallites of nearly spherical shape. The decrease in the formation temperature/duration of CCTO in MSS method was attributed to an increase in the diffusion rate or a decrease in the diffusion length of reacting ions in the molten salt medium. As a consequence of liquid phase sintering, pellets of as-synthesized KCl containing CCTO powder exhibited higher sinterability and grain size than that of KCl free CCTO samples prepared by both MSS method and conventional solid-state reaction route. The grain size and the dielectric constant of KCl containing CCTO ceramics increased with increasing sintering temperature (900 degrees C-1050 degrees C). Indeed the dielectric constants of these ceramics were higher than that of KCl free CCTO samples prepared by both MSS method and those obtained via the solid-state reaction route and sintered at the same temperature. Internal barrier layer capacitance (IBLC) model was invoked to correlate the observed dielectric constant with the grain size in these samples.

The effect of phase change materials on the frontal polymerization of a triacrylate

NASA Astrophysics Data System (ADS)

Viner, Veronika G.; Pojman, John A.; Golovaty, Dmitry

2010-06-01

The production of smoke and fumes is a major obstacle to the practical use of thermal frontal polymerization. The front temperature and the amount of smoking can be reduced by adding inert fillers, such as clay and silica, to the reactive mixture. Here we investigate the possibility of incorporating inert materials that melt (so-called phase change materials) to the mixture. By performing both experiments and mathematical modeling, we demonstrate that, in addition to the standard parameters of frontal polymerization, the front temperature and velocity depend on the melting point and heat of fusion of the phase change material. We use the method of matched asymptotic expansions to develop an explicit expression for the velocity of the reaction front. The expression demonstrates that the behavior of the front is determined by the difference between the reaction temperature and the melting temperature, with the front being slower and cooler if melting occurs farther ahead of the reaction front. The theoretical trends are hard to confirm directly because different characteristics of the phase change material cannot be varied separately.

Estimated congener specific gas-phase atmospheric behavior and fractionation of perfluoroalkyl compounds: rates of reaction with atmospheric oxidants, air-water partitioning, and wet/dry deposition lifetimes.

PubMed

Rayne, Sierra; Forest, Kaya; Friesen, Ken J

2009-08-01

A quantitative structure-activity model has been validated for estimating congener specific gas-phase hydroxyl radical reaction rates for perfluoroalkyl sulfonic acids (PFSAs), carboxylic acids (PFCAs), aldehydes (PFAls) and dihydrates, fluorotelomer olefins (FTOls), alcohols (FTOHs), aldehydes (FTAls), and acids (FTAcs), and sulfonamides (SAs), sulfonamidoethanols (SEs), and sulfonamido carboxylic acids (SAAs), and their alkylated derivatives based on calculated semi-empirical PM6 method ionization potentials. Corresponding gas-phase reaction rates with nitrate radicals and ozone have also been estimated using the computationally derived ionization potentials. Henry's law constants for these classes of perfluorinated compounds also appear to be reasonably approximated by the SPARC software program, thereby allowing estimation of wet and dry atmospheric deposition rates. Both congener specific gas-phase atmospheric and air-water interface fractionation of these compounds is expected, complicating current source apportionment perspectives and necessitating integration of such differential partitioning influences into future multimedia models. The findings will allow development and refinement of more accurate and detailed local through global scale atmospheric models for the atmospheric fate of perfluoroalkyl compounds.

Recovery of organic acids

DOEpatents

Verser, Dan W.; Eggeman, Timothy J.

2009-10-13

A method is disclosed for the recovery of an organic acid from a dilute salt solution in which the cation of the salt forms an insoluble carbonate salt. A tertiary amine and CO.sub.2 are introduced to the solution to form the insoluble carbonate salt and a complex between the acid and an amine. A water immiscible solvent, such as an alcohol, is added to extract the acid/amine complex from the dilute salt solution to a reaction phase. The reaction phase is continuously dried and a product between the acid and the solvent, such as an ester, is formed.

Recovery of organic acids

DOEpatents

Verser, Dan W [Menlo Park, CA; Eggeman, Timothy J [Lakewood, CO

2011-11-01

A method is disclosed for the recovery of an organic acid from a dilute salt solution in which the cation of the salt forms an insoluble carbonate salt. A tertiary amine and CO.sub.2 are introduced to the solution to form the insoluble carbonate salt and a complex between the acid and an amine. A water immiscible solvent, such as an alcohol, is added to extract the acid/amine complex from the dilute salt solution to a reaction phase. The reaction phase is continuously dried and a product between the acid and the solvent, such as an ester, is formed.

An easy access to nanocrystalline alkaline earth metal fluorides - just by shaking

NASA Astrophysics Data System (ADS)

Dreger, M.; Scholz, G.; Kemnitz, E.

2012-04-01

High energy ball milling as fast, direct and solvent free method allows an easy access to nanocrystalline alkaline earth metal fluorides MF2 (M: Mg, Ca, Sr, Ba). Comparable metal sources (acetates, carbonates, hydroxides, alkoxides) were used for the reaction with NH4F as fluorinating agent. Even very simple manual shaking experiments between NH4F and the corresponding hydroxides in the stoichiometric ratio (M:F = 1:2, M: Ca, Sr, Ba) give phase pure fluorides. Moreover, comparable classical thermal reactions in closed crucibles at higher temperatures provide phase pure crystalline fluorides in nearly all cases as well.

Travelling fronts of the CO oxidation on Pd(111) with coverage-dependent diffusion

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

Cisternas, Jaime, E-mail: jecisternas@miuandes.cl; Karpitschka, Stefan; Wehner, Stefan

2014-10-28

In this work, we study a surface reaction on Pd(111) crystals under ultra-high-vacuum conditions that can be modeled by two coupled reaction-diffusion equations. In the bistable regime, the reaction exhibits travelling fronts that can be observed experimentally using photo electron emission microscopy. The spatial profile of the fronts reveals a coverage-dependent diffusivity for one of the species. We propose a method to solve the nonlinear eigenvalue problem and compute the direction and the speed of the fronts based on a geometrical construction in phase-space. This method successfully captures the dependence of the speed on control parameters and diffusivities.

Experimental investigation of the phase equilibria and thermodynamic assessment in the U-Ga and U-Al-Ga systems

NASA Astrophysics Data System (ADS)

Moussa, Chantal; Berche, Alexandre; Barbosa, José; Pasturel, Mathieu; Stepnik, Bertrand; Tougait, Olivier

2018-02-01

The phase relations in the binary U-Ga and ternary U-Al-Ga systems were established as an isopleth section and two isothermal sections at 900 K and 1150 K for the whole concentration range, respectively. They were experimentally determined by means of powder and single crystal XRD, SEM-EDS analyses on both as-cast and heat-treated samples and DTA measurements. Both systems were thermodynamically assessed using the Calphad method based on the available data, i.e. phase relations and thermodynamic properties. The new description of the U-Ga phase diagram improves the composition-temperature description for most of invariant reactions. The U-Al-Ga system is characterized by large ternary extensions of the binary phases and the absence of ternary intermediate phase at both 900 K and 1150 K. These experimental results are nicely reproduced by the Calphad assessment, allowing to extract the thermodynamic parameters further used to calculate the liquidus projection and the invariant reactions along with their temperature.

A study of hydriding kinetics of metal hydrides using a physically based model

NASA Astrophysics Data System (ADS)

Voskuilen, Tyler G.

The reaction of hydrogen with metals to form metal hydrides has numerous potential energy storage and management applications. The metal hydrogen system has a high volumetric energy density and is often reversible with a high cycle life. The stored hydrogen can be used to produce energy through combustion, reaction in a fuel cell, or electrochemically in metal hydride batteries. The high enthalpy of the metal-hydrogen reaction can also be used for rapid heat removal or delivery. However, improving the often poor gravimetric performance of such systems through the use of lightweight metals usually comes at the cost of reduced reaction rates or the requirement of pressure and temperature conditions far from the desired operating conditions. In this work, a 700 bar Sievert system was developed at the Purdue Hydrogen Systems Laboratory to study the kinetic and thermodynamic behavior of high pressure hydrogen absorption under near-ambient temperatures. This system was used to determine the kinetic and thermodynamic properties of TiCrMn, an intermetallic metal hydride of interest due to its ambient temperature performance for vehicular applications. A commonly studied intermetallic hydride, LaNi5, was also characterized as a base case for the phase field model. The analysis of the data obtained from such a system necessitate the use of specialized techniques to decouple the measured reaction rates from experimental conditions. These techniques were also developed as a part of this work. Finally, a phase field model of metal hydride formation in mass-transport limited interstitial solute reactions based on the regular solution model was developed and compared with measured kinetics of LaNi5 and TiCrMn. This model aided in the identification of key reaction features and was used to verify the proposed technique for the analysis of gas-solid reaction rates determined volumetrically. Additionally, the phase field model provided detailed quantitative predictions of the effects of multidimensional phase growth and transitions between rate-limiting processes on the experimentally determined reaction rates. Unlike conventional solid state reaction analysis methods, this model relies fully on rate parameters based on the physical mechanisms occurring in the hydride reaction and can be extended to reactions in any dimension.

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

NASA Astrophysics Data System (ADS)

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

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

Synthesis of YAG nanopowder by the co-precipitation method: Influence of pH and study of the reaction mechanisms

NASA Astrophysics Data System (ADS)

Marlot, Caroline; Barraud, Elodie; Le Gallet, Sophie; Eichhorn, Marc; Bernard, Frédéric

2012-07-01

YAG nanopowders with an average grain size of 30 nm have been successfully synthesized by the co-precipitation method using nitrates with precipitant of ammonium hydrogen carbonate. The influence of precipitation conditions such as pH, aging time and calcination temperature on the formation of secondary phases has been studied. The accurate control of pH value at every stage of precipitation process is crucial to avoid the presence of YAM (Yttrium Aluminium Monoclinic, Y4Al2O9) and yttrium oxide (Y2O3) after calcination. The reaction mechanisms have been investigated using different techniques such as infrared spectroscopy, x-ray diffraction and thermal analyses. The YAG phase is formed around 1050 °C passing through an intermediate phase called YAP (Yttrium Aluminium Perovskite, YAlO3). Local chemical heterogeneities are responsible for the deviation of the Y:Al ratio and the formation of YAP during heat treatment.

Low temperature synthesis & characterization of lead-free BCZT ceramics using molten salt method

NASA Astrophysics Data System (ADS)

Jai Shree, K.; Chandrakala, E.; Das, Dibakar

2018-04-01

Piezoelectric properties are greatly influenced by the synthesis route, microstructure, stoichiometry of the chemical composition, purity of the starting materials. In this study, molten salt method was used to prepare lead-free BCZT ceramics. Molten salt method is one of the simplestmethods to prepare chemically-purified, single phase powders in high yield often at lower temperatures and shorten reaction time. Calcination of the molten salt synthesized powders resulted in asingle-phase perovskite structure at 1000 °C which is ˜ 350 °C less than the conventional solid-sate reaction method. With increasing calcination temperature the average template size was increased (˜ 0.5-2 µm). Formation of well dispersive templates improves the sinterability at lower temperatures. Lead-free BCZT ceramics sintered at 1500 °C for 2 h resulted in homogenous and highly dense microstructure with ˜92% of the theoretical density and a grain size of ˜ 35 µm. This highly dense microstructure could enhance the piezoelectric properties of the system.

Dual phase multiplex polymerase chain reaction

DOEpatents

Pemov, Alexander [Charlottesville, VA; Bavykin, Sergei [Darien, IL

2008-10-07

Highly specific and sensitive methods were developed for multiplex amplification of nucleic acids on supports such as microarrays. Based on a specific primer design, methods include five types of amplification that proceed in a reaction chamber simultaneously. These relate to four types of multiplex amplification of a target DNA on a solid support, directed by forward and reverse complex primers immobilized to the support and a fifth type--pseudo-monoplex polymerase chain reaction (PCR) of multiple targets in solution, directed by a single pair of unbound universal primers. The addition of the universal primers in the reaction mixture increases the yield over the traditional "bridge" amplification on a solid support by approximately ten times. Methods that provide multitarget amplification and detection of as little as 0.45-4.5.times.10.sup.-12 g (equivalent to 10.sup.2-10.sup.3 genomes) of a bacterial genomic DNA are disclosed.

Laser pyrolysis fabrication of ferromagnetic gamma'-Fe4N and FeC nanoparticles

NASA Technical Reports Server (NTRS)

Grimes, C. A.; Qian, D.; Dickey, E. C.; Allen, J. L.; Eklund, P. C.

2000-01-01

Using the laser pyrolysis method, single phase gamma'-Fe4N nanoparticles were prepared by a two step method involving preparation of nanoscale iron oxide and a subsequent gas-solid nitridation reaction. Single phase Fe3C and Fe7C3 could be prepared by laser pyrolysis from Fe(CO)5 and 3C2H4 directly. Characterization techniques such as XRD, TEM and vibrating sample magnetometer were used to measure phase structure, particle size and magnetic properties of these nanoscale nitride and carbide particles. c2000 American Journal of Physics.

Solid-Phase Radioimmunoassay of Total and Influenza-Specific Immunoglobulin G

PubMed Central

Daugharty, Harry; Warfield, Donna T.; Davis, Marianne L.

1972-01-01

An antigen-antibody system of polystyrene tubes coated with immunoglobulin antibody was used for quantitating immunoglobulins. A similar radioimmunoassay method was adapted for a viral antigen-antibody system. The viral system can be used for quantitating viruses and for measuring virus-specific antibodies by reacting with 125iodine-labeled anti-immunoglobulin G (IgG). Optimal conditions for coating the solid phase, specificity of the immune reaction, and other kinetics and sensitivities of the assay method were investigated. Comparison of direct and indirect methods of assaying for immunoglobulins or viral antibody indicates that the indirect method is more sensitive and can quantitate a minimum of 0.037 μg of IgG per ml. Results of solid-phase radioimmunoassay for influenza antibody correlate well with hemagglutinin antibody titers but not with complement-fixing antibody titers. Radioimmunoassay results for influenza antibody by solid phase are likewise in agreement with results by the carrier precipitate radioimmunoassay method. The simplicity, reproducibility, and versatility of the solid-phase procedure make it diagnostically useful. PMID:5062884

Rhenium/Oxygen Interactions at Elevated Temperatures

NASA Technical Reports Server (NTRS)

Jacobson, Nathan; Myers, Dwight; Zhu, Dong-Ming; Humphrey, Donald

2000-01-01

The oxidation of pure rhenium is examined from 600-1400 C in oxygen/argon mixtures. Linear weight loss kinetics are observed. Gas pressures, flow rates, and temperatures are methodically varied to determine the rate controlling steps. The reaction at 600 and 800 C appears to be controlled by a chemical reaction step at the surface; whereas the higher temperature reactions appear to be controlled by gas phase diffusion of oxygen to the rhenium surface. Attack of the rhenium appears to be along grain boundaries and crystallographic planes.

pH Triggered Recovery and Reuse of Thiolated Poly(acrylic acid) Functionalized Gold Nanoparticles with Applications in Colloidal Catalysis.

PubMed

Ansar, Siyam M; Fellows, Benjamin; Mispireta, Patrick; Mefford, O Thompson; Kitchens, Christopher L

2017-08-08

Thiolated poly(acrylic acid) (PAA-SH) functionalized gold nanoparticles were explored as a colloidal catalyst with potential application as a recoverable catalyst where the PAA provides pH-responsive dispersibility and phase transfer capability between aqueous and organic media. This system demonstrates complete nanoparticle recovery and redispersion over multiple reaction cycles without changes in nanoparticle morphology or reduction in conversion. The catalytic activity (rate constant) was reduced in subsequent reactions when recovery by aggregation was employed, despite unobservable changes in morphology or dispersibility. When colloidal catalyst recovery employed a pH induced phase transfer between two immiscible solvents, the catalytic activity of the recovered nanoparticles was unchanged over four cycles, maintaining the original rate constant and 100% conversion. The ability to recover and reuse colloidal catalysts by aggregation/redispersion and phase transfer methods that occur at low and high pH, respectively, could be used for different gold nanoparticle catalyzed reactions that occur at different pH conditions.

Wet-chemical synthesis of different bismuth telluride nanoparticles using metal organic precursors - single source vs. dual source approach.

PubMed

Bendt, Georg; Weber, Anna; Heimann, Stefan; Assenmacher, Wilfried; Prymak, Oleg; Schulz, Stephan

2015-08-28

Thermolysis of the single source precursor (Et2Bi)2Te in DIPB at 80 °C yielded phase-pure Bi4Te3 nanoparticles, while mixtures of Bi4Te3 and elemental Bi were formed at higher temperatures. In contrast, cubic Bi2Te particles were obtained by thermal decomposition of Et2BiTeEt in DIPB. Moreover, a dual source approach (hot injection method) using the reaction of Te(SiEt3)2 and Bi(NMe2)3 was applied for the synthesis of different pure Bi-Te phases including Bi2Te, Bi4Te3 and Bi2Te3, which were characterized by PXRD, REM, TEM and EDX. The influence of reaction temperature, precursor molar ratio and thermolysis conditions on the resulting material phase was verified. Moreover, reactions of alternate bismuth precursors such as Bi(NEt2)3, Bi(NMeEt)3 and BiCl3 with Te(SiEt3)2 were investigated.

Fabrication of Ni-silicide/Si heterostructured nanowire arrays by glancing angle deposition and solid state reaction.

PubMed

Hsu, Hsun-Feng; Huang, Wan-Ru; Chen, Ting-Hsuan; Wu, Hwang-Yuan; Chen, Chun-An

2013-05-10

This work develops a method for growing Ni-silicide/Si heterostructured nanowire arrays by glancing angle Ni deposition and solid state reaction on ordered Si nanowire arrays. Samples of ordered Si nanowire arrays were fabricated by nanosphere lithography and metal-induced catalytic etching. Glancing angle Ni deposition deposited Ni only on the top of Si nanowires. When the annealing temperature was 500°C, a Ni3Si2 phase was formed at the apex of the nanowires. The phase of silicide at the Ni-silicide/Si interface depended on the diameter of the Si nanowires, such that epitaxial NiSi2 with a {111} facet was formed at the Ni-silicide/Si interface in Si nanowires with large diameter, and NiSi was formed in Si nanowires with small diameter. A mechanism that is based on flux divergence and a nucleation-limited reaction is proposed to explain this phenomenon of size-dependent phase formation.

Fabrication of Ni-silicide/Si heterostructured nanowire arrays by glancing angle deposition and solid state reaction

PubMed Central

2013-01-01

This work develops a method for growing Ni-silicide/Si heterostructured nanowire arrays by glancing angle Ni deposition and solid state reaction on ordered Si nanowire arrays. Samples of ordered Si nanowire arrays were fabricated by nanosphere lithography and metal-induced catalytic etching. Glancing angle Ni deposition deposited Ni only on the top of Si nanowires. When the annealing temperature was 500°C, a Ni3Si2 phase was formed at the apex of the nanowires. The phase of silicide at the Ni-silicide/Si interface depended on the diameter of the Si nanowires, such that epitaxial NiSi2 with a {111} facet was formed at the Ni-silicide/Si interface in Si nanowires with large diameter, and NiSi was formed in Si nanowires with small diameter. A mechanism that is based on flux divergence and a nucleation-limited reaction is proposed to explain this phenomenon of size-dependent phase formation. PMID:23663726

Method for loading resin beds

DOEpatents

Notz, Karl J.; Rainey, Robert H.; Greene, Charles W.; Shockley, William E.

1978-01-01

An improved method of preparing nuclear reactor fuel by carbonizing a uranium loaded cation exchange resin provided by contacting a H.sup.+ loaded resin with a uranyl nitrate solution deficient in nitrate, comprises providing the nitrate deficient solution by a method comprising the steps of reacting in a reaction zone maintained between about 145.degree.-200.degree. C, a first aqueous component comprising a uranyl nitrate solution having a boiling point of at least 145.degree. C with a second aqueous component to provide a gaseous phase containing HNO.sub.3 and a reaction product comprising an aqueous uranyl nitrate solution deficient in nitrate.

The degradation mechanism of phenol induced by ozone in wastes system.

PubMed

Youmin, Sun; Xiaohua, Ren; Zhaojie, Cui; Guiqin, Zhang

2012-08-01

A distinct understanding for the degradation mechanism of phenol induced by ozone is very essential because the ozonation process, one of the advanced oxidation processes (AOPs), is attractive and popular in wastewater treatment. In the present work, the detailed reactions of ozone and phenol are investigated employing the density functional theory B3LYP method with the 6-311++G (d, p) basis set. The profiles of the potential energy surface are constructed and the possible reaction pathways are indicated. These detailed calculation results suggest two degradation reaction mechanisms. One is phenolic H atom abstraction mechanism, and the other is cyclo-addition and ring-opening mechanism. Considering the effect of solvent water, the calculated energy barriers and reaction enthalpies for the reaction of O3 and phenol in water phase are both lower than those in gas phase, though the degradation mechanisms are not changed. This reveals that these degradation reactions are more favorable in the water solvent. The main reaction products are C(6)H(5)OO· radical, a crucial precursor for forming PCDD/Fs and one ring-opening product, which are in good agreement with the experimental observations.

Nuclear fuel alloys or mixtures and method of making thereof

DOEpatents

Mariani, Robert Dominick; Porter, Douglas Lloyd

2016-04-05

Nuclear fuel alloys or mixtures and methods of making nuclear fuel mixtures are provided. Pseudo-binary actinide-M fuel mixtures form alloys and exhibit: body-centered cubic solid phases at low temperatures; high solidus temperatures; and/or minimal or no reaction or inter-diffusion with steel and other cladding materials. Methods described herein through metallurgical and thermodynamics advancements guide the selection of amounts of fuel mixture components by use of phase diagrams. Weight percentages for components of a metallic additive to an actinide fuel are selected in a solid phase region of an isothermal phase diagram taken at a temperature below an upper temperature limit for the resulting fuel mixture in reactor use. Fuel mixtures include uranium-molybdenum-tungsten, uranium-molybdenum-tantalum, molybdenum-titanium-zirconium, and uranium-molybdenum-titanium systems.

Theory and computation of non-RRKM lifetime distributions and rates in chemical systems with three or more degrees of freedom

NASA Astrophysics Data System (ADS)

Gabern, Frederic; Koon, Wang S.; Marsden, Jerrold E.; Ross, Shane D.

2005-11-01

The computation, starting from basic principles, of chemical reaction rates in realistic systems (with three or more degrees of freedom) has been a longstanding goal of the chemistry community. Our current work, which merges tube dynamics with Monte Carlo methods provides some key theoretical and computational tools for achieving this goal. We use basic tools of dynamical systems theory, merging the ideas of Koon et al. [W.S. Koon, M.W. Lo, J.E. Marsden, S.D. Ross, Heteroclinic connections between periodic orbits and resonance transitions in celestial mechanics, Chaos 10 (2000) 427-469.] and De Leon et al. [N. De Leon, M.A. Mehta, R.Q. Topper, Cylindrical manifolds in phase space as mediators of chemical reaction dynamics and kinetics. I. Theory, J. Chem. Phys. 94 (1991) 8310-8328.], particularly the use of invariant manifold tubes that mediate the reaction, into a tool for the computation of lifetime distributions and rates of chemical reactions and scattering phenomena, even in systems that exhibit non-statistical behavior. Previously, the main problem with the application of tube dynamics has been with the computation of volumes in phase spaces of high dimension. The present work provides a starting point for overcoming this hurdle with some new ideas and implements them numerically. Specifically, an algorithm that uses tube dynamics to provide the initial bounding box for a Monte Carlo volume determination is used. The combination of a fine scale method for determining the phase space structure (invariant manifold theory) with statistical methods for volume computations (Monte Carlo) is the main contribution of this paper. The methodology is applied here to a three degree of freedom model problem and may be useful for higher degree of freedom systems as well.

Determination of NH2 concentration on 3-aminopropyl tri-ethoxy silane layers and cyclopropylamine plasma polymers by liquid-phase derivatization with 5-iodo 2-furaldehyde

NASA Astrophysics Data System (ADS)

Manakhov, Anton; Čechal, Jan; Michlíček, Miroslav; Shtansky, Dmitry V.

2017-08-01

The quantification of concentration of primary amines, e.g. in plasma polymerized layers is a very important task for surface analysis. However, the commonly used procedure, such as gas phase derivatization with benzaldehydes, shows several drawbacks, the most important of which are the side reaction effects. In the present study we propose and validate a liquid phase derivatization using 5-iodo 2-furaldehyde (IFA). It was demonstrated that the content of NH2 groups can be determined from the atomic concentrations measured by X-ray photoelectron spectroscopy (XPS), in particular from the ratio of I 3d and N 1s peak intensities. First, we demonstrate the method on a prototypical system such as 3-aminopropyl tri-ethoxy silane (APTES) layer. Here the XPS analysis carried out after reaction of APTES layer with IFA gives the fraction of primary amines (NH2/N) of 38.3 ± 7.9%. Comparing this value with that obtained by N 1s curve fitting of APTES layer giving 40.9 ± 9.5% of amine groups, it can be concluded that all primary amines were derivatized by reaction with IFA. The second system to demonstrate the method comprises cyclopropylamine (CPA) plasma polymers that were free from conjugated imines. In this case the method gives the NH2 fraction ∼8.5%. This value is closely matching the NH2/N ratio estimated by 4-trifluoromethyl benzaldehyde (TFBA) derivatization. The reaction of IFA with CPA plasma polymer exhibiting high density of conjugated imines revealed the NH2/N fraction of ∼10.8%. This value was significantly lower compared to 17.3% estimated by TFBA derivatization. As the overestimated density of primary amines measured by TFBA derivatization is probably related to the side reaction of benzaldehydes with conjugated imines, the proposed IFA derivatization of primary amines can be an alternative procedure for the quantification of surface amine groups.

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

NASA Astrophysics Data System (ADS)

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

2015-09-01

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

Computation of Kinetics for the Hydrogen/Oxygen System Using the Thermodynamic Method

NASA Technical Reports Server (NTRS)

Marek, C. John

1996-01-01

A new method for predicting chemical rate constants using thermodynamics has been applied to the hydrogen/oxygen system. This method is based on using the gradient of the Gibbs free energy and a single proportionality constant D to determine the kinetic rate constants. Using this method the rate constants for any gas phase reaction can be computed from thermodynamic properties. A modified reaction set for the H/O system is determined. A11 of the third body efficiencies M are taken to be unity. Good agreement was obtained between the thermodynamic method and the experimental shock tube data. In addition, the hydrogen bromide experimental data presented in previous work is recomputed with M's of unity.

Simultaneous determination of Cr(iii) and Cr(vi) using reversed-phased ion-pairing liquid chromatography with dynamic reaction cell inductively coupled plasma mass spectrometry

USGS Publications Warehouse

Wolf, R.E.; Morrison, J.M.; Goldhaber, M.B.

2007-01-01

A method for the simultaneous determination of Cr(iii) and Cr(vi) species in waters, soil leachates and synthetic bio-fluids is described. The method uses reversed-phase ion-pairing liquid chromatography to separate the chromium species and a dynamic reaction cell (DRC??) equipped ICP-MS for detection of chromium. Separation of the chromium species is carried out in less than 2 min. Cr(iii) is complexed with ethylenediaminetetraacetic acid (EDTA) prior to separation by mixing samples with the mobile phase containing 2.0 mM tetrabutylammonium hydroxide (TBAOH), 0.5 mM EDTA (dipotassium salt), and 5% (vol/vol) methanol, adjusted to pH 7.6. The interfering 40Ar 12C+ background peak at mass 52 was reduced by over four orders of magnitude to less than 200 cps by using 0.65 mL min-1 ammonia as a reaction gas and an RPq setting on the DRC of 0.75. Method detection limits (MDLs) of 0.09 ??g L-1 for Cr(iii) and 0.06 ??g L-1 for Cr(vi) were obtained based on peak areas at mass 52 for 50 ??L injections of low level spikes. Reproducibility at 2 ??g L-1 was 3% RSD for 5 replicate injections. The tolerance of the method to various levels of common cations and anions found in natural waters and to matrix constituents found in soil leachates and simulated gastric and lung fluids was tested by performing spike recovery calculations for a variety of samples. ?? The Royal Society of Chemistry.

User's guide to PHREEQC, a computer program for speciation, reaction-path, advective-transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, D.L.

1995-01-01

PHREEQC is a computer program written in the C pwgranuning language that is designed to perform a wide variety of aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations, (2) reaction-path and advective-transport calculations involving specified irreversible reactions, mixing of solutions, mineral and gas equilibria surface-complex-ation reactions, and ion-exchange reactions, and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for composition differences between waters, within specified compositional uncertainties. PHREEQC is derived from the Fortran program PHREEQE, but it has been completely rewritten in C with the addition many new capabilities. New features include the capabilities to use redox couples to distribute redox elements among their valence states in speciation calculations; to model ion-exchange and surface-compiexation reactions; to model reactions with a fixed-pressure, multicomponent gas phase (that is, a gas bubble); to calculate the mass of water in the aqueous phase during reaction and transport calculations; to keep track of the moles of minerals present in the solid phases and determine antomaticaHy the thermodynamically stable phase assemblage; to simulate advective transport in combination with PHREEQC's reaction-modeling capability; and to make inverse modeling calculations that allow for uncertainties in the analytical data. The user interface is improved through the use of a simplified approach to redox reactions, which includes explicit mole-balance equations for hydrogen and oxygen; the use of a revised input that is modular and completely free format; and the use of mineral names and standard chemical symbolism rather than index numbers. The use of (2 eliminates nearly all limitations on army sizes, including numbers of elements, aqueous species, solutions, phases, and lengths of character strings. A new equation solver that optimizes a set of equalities subject to both equality and inequality constraints is used to determine the thermodynamically stable set of phases in equilibrium with a solution. A more complete Newton-Raphson formulation, master-species switching, and scaling of the algebraic equations reduce the number of failures of the nunmrical method in PHREEQC relative to PHREEQE. This report presents the equations that are the basis for chemical equilibrium and inverse-modeling calculations in PHREEQC, describes the input for the program, and presents twelve examples that demonstrate most of the program's capabilities.

Controlled multistep synthesis in a three-phase droplet reactor

PubMed Central

Nightingale, Adrian M.; Phillips, Thomas W.; Bannock, James H.; de Mello, John C.

2014-01-01

Channel-fouling is a pervasive problem in continuous flow chemistry, causing poor product control and reactor failure. Droplet chemistry, in which the reaction mixture flows as discrete droplets inside an immiscible carrier liquid, prevents fouling by isolating the reaction from the channel walls. Unfortunately, the difficulty of controllably adding new reagents to an existing droplet stream has largely restricted droplet chemistry to simple reactions in which all reagents are supplied at the time of droplet formation. Here we describe an effective method for repeatedly adding controlled quantities of reagents to droplets. The reagents are injected into a multiphase fluid stream, comprising the carrier liquid, droplets of the reaction mixture and an inert gas that maintains a uniform droplet spacing and suppresses new droplet formation. The method, which is suited to many multistep reactions, is applied to a five-stage quantum dot synthesis wherein particle growth is sustained by repeatedly adding fresh feedstock. PMID:24797034

A Contribution to the Kinetic Study of the Metatectic Reaction U+U$sub 3$Si$sub 2$$Yields$U$sub 3$Si; CONTRIBUTION AL ESTUDIO CINETICO DE LA REACCION METATECTICA U+U$sub 3$Si$sub 2$$Yields$U$sub 3$Si

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

Ruiperez, J.A.; Hernandez, J.A.E.

1962-01-01

An experimental study was made to decide upon the advantages and drawbacks of the different methods and reagents employed in the metallography of U-Si alloys. It has been observed that all samples thermally treated to the epsilon-phase undergo a coalescence of the U/sub 3/Si/sub 2/ particles. The coalescence decreases the surface available for reaction and consequently the reaction rate. The growth of the U/sub 3/Si/sub 2/ phase particles was determined as a function of time and temperature. To obtain samples with nuclei sufficiently isolated so that the U/sub 3/Si rings will not interfere their respective growth, the conditions that regulatemore » coalescence, Si content and thermal treatment, were determined. Data rel1tive to the growth of the U/sub 3/ Si phase-rings were obtained. Curves relating growth, time, and temperature are presented. The parameters that define the diffusion regulated reaction can be deduced from these curves. (auth)« less

Growth of a decagonal Al 70Ni 15Co 15 single quasicrystal by the Czochralski method

NASA Astrophysics Data System (ADS)

Jeong, H. T.; Kim, S. H.; Kim, W. T.; Kim, D. H.; Inkson, B. J.

2000-07-01

Single decagonal quasicrystals of Al 70Ni 15Co 15 were grown by the Czochralski method at Ar atmosphere. The grown crystals were of single decagonal phase without any secondary phases due to the peritectic reaction and contained a large single quasicrystal of cm order size. The high quality and single quasicrystallinity of them were examined by the Laue transmission photography, single crystal X-ray diffraction, and high-resolution electron microscopy investigations.

Surface chemistry in photodissociation regions

NASA Astrophysics Data System (ADS)

Esplugues, G. B.; Cazaux, S.; Meijerink, R.; Spaans, M.; Caselli, P.

2016-06-01

Context. The presence of dust can strongly affect the chemical composition of the interstellar medium. We model the chemistry in photodissociation regions (PDRs) using both gas-phase and dust-phase chemical reactions. Aims: Our aim is to determine the chemical compositions of the interstellar medium (gas/dust/ice) in regions with distinct (molecular) gas densities that are exposed to radiation fields with different intensities. Methods: We have significantly improved the Meijerink PDR code by including 3050 new gas-phase chemical reactions and also by implementing surface chemistry. In particular, we have included 117 chemical reactions occurring on grain surfaces covering different processes, such as adsorption, thermal desorption, chemical desorption, two-body reactions, photo processes, and cosmic-ray processes on dust grains. Results: We obtain abundances for different gas and solid species as a function of visual extinction, depending on the density and radiation field. We also analyse the rates of the formation of CO2 and H2O ices in different environments. In addition, we study how chemistry is affected by the presence/absence of ice mantles (bare dust or icy dust) and the impact of considering different desorption probabilities. Conclusions: The type of substrate (bare dust or icy dust) and the probability of desorption can significantly alter the chemistry occurring on grain surfaces, leading to differences of several orders of magnitude in the abundances of gas-phase species, such as CO, H2CO, and CH3OH. The type of substrate, together with the density and intensity of the radiation field, also determine the threshold extinction to form ices of CO2 and H2O. We also conclude that H2CO and CH3OH are mainly released into the gas phase of low, far-ultraviolet illuminated PDRs through chemical desorption upon two-body surface reactions, rather than through photodesorption.

Pressure Dependence of Gas-Phase Reaction Rates

ERIC Educational Resources Information Center

De Persis, Stephanie; Dollet, Alain; Teyssandier, Francis

2004-01-01

It is presented that only simple concepts, mainly taken from activated-complex or transition-state theory, are required to explain and analytically describe the influence of pressure on gas-phase reaction kinetics. The simplest kind of elementary gas-phase reaction is a unimolecular decomposition reaction.

Validated Spectrophotometric and RP-HPLC-DAD Methods for the Determination of Ursodeoxycholic Acid Based on Derivatization with 2-Nitrophenylhydrazine.

PubMed

El-Kafrawy, Dina S; Belal, Tarek S; Mahrous, Mohamed S; Abdel-Khalek, Magdi M; Abo-Gharam, Amira H

2017-05-01

This work describes the development, validation, and application of two simple, accurate, and reliable methods for the determination of ursodeoxycholic acid (UDCA) in bulk powder and in pharmaceutical dosage forms. The carboxylic acid group in UDCA was exploited for the development of these novel methods. Method 1 is the colorimetric determination of the drug based on its reaction with 2-nitrophenylhydrazine hydrochloride in the presence of a water-soluble carbodiimide coupler [1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride] and pyridine to produce an acid hydrazide derivative, which ionizes to yield an intense violet color with maximum absorption at 553 nm. Method 2 uses reversed-phase HPLC with diode-array detection for the determination of UDCA after precolumn derivatization using the same reaction mentioned above. The acid hydrazide reaction product was separated using a Pinnacle DB C8 column (4.6 × 150 mm, 5 μm particle size) and a mobile phase consisting of 0.01 M acetate buffer (pH 3)-methanol-acetonitrile (30 + 30 + 40, v/v/v) isocratically pumped at a flow rate of 1 mL/min. Ibuprofen was used as the internal standard (IS). The peaks of the reaction product and IS were monitored at 400 nm. Different experimental parameters for both methods were carefully optimized. Analytical performance of the developed methods were statistically validated for linearity, range, precision, accuracy, specificity, robustness, LOD, and LOQ. Calibration curves showed good linear relationships for concentration ranges 32-192 and 60-600 μg/mL for methods 1 and 2, respectively. The proposed methods were successfully applied for the assay of UDCA in bulk form, capsules, and oral suspension with good accuracy and precision. Assay results were statistically compared with a reference pharmacopeial HPLC method, and no significant differences were observed between proposed and reference methods.

Free-energy based pair-additive potentials for bulk Ni-Al systems: Application to study Ni-Al reactive alloying

NASA Astrophysics Data System (ADS)

Izvekov, Sergei; Rice, Betsy M.

2012-09-01

We present new numerical pair-additive Al, Ni, and Al-Ni potentials by force-matching (FM) ionic force and virial data from single (bulk liquid) phase ab initio molecular dynamics (MD) simulations using the Born-Oppenheimer method. The potentials are represented by piece-wise functions (splines) and, therefore, are not constrained to a particular choice of analytical functional form. The FM method with virial constraint naturally yields a potential which maps out the ionic free-energy surface of the reference ensemble. To further improve the free energetics of the FM ensemble, the FM procedure is modified to bias the potentials to reproduce the experimental melting temperatures of the reference (FCC-Al, FCC-Ni, B2-NiAl) phases, the only macroscopic data included in the fitting set. The performance of the resultant potentials in simulating bulk metallic phases is then evaluated. The new model is applied to perform MD simulations of self-propagating exothermic reaction in Ni-Al bilayers at P = 0-5 GPa initiated at T = 1300 K. Consistent with experimental observations, the new model describes realistically a sequence of peritectic phase transformations throughout the reaction and at a realistic rate. The reaction proceeds through interlayer diffusion of Al and Ni atoms at the interface with formation of B2-NiAl in the Al melt. Such material responses have, in the past, been proven to be difficult to observe with then-existing potentials.

Optical properties of hydrothermally synthesized TGA-capped CdS nanoparticles: controlling crystalline size and phase

NASA Astrophysics Data System (ADS)

Tavakoli Banizi, Zoha; Seifi, Majid

2017-10-01

TGA-capped CdS nanoparticles were obtained in the presence of thioglycolic acid (TGA) as capping agent via a facile hydrothermal method at relatively low temperature and over a short duration. As-synthesized TGA-capped CdS nanoparticles were characterized by x-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectra, photoluminescence spectroscopy, Ultraviolet-visible spectroscopy and energy-dispersive x-ray spectroscopy. The products had spherical shapes, although their crystalline size and phase was dependent on temperature and time of the reaction. Photoluminescence spectra showed that the fluorescence intensity decreased when increasing the reaction time and temperature.

Formation of III–V ternary solid solutions on GaAs and GaSb plates via solid-phase substitution reactions

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

Vasil’ev, V. I.; Gagis, G. S., E-mail: galina.gagis@gmail.com; Kuchinskii, V. I.

2015-07-15

Processes are considered in which ultrathin layers of III–V ternary solid solutions are formed via the delivery of Group-V element vapors to GaAs and GaSb semiconductor plates, with solid-phase substitution reactions occurring in the surface layers of these plates. This method can form defect-free GaAs{sup 1–x}P{sup x}, GaAs{sup x}Sb{sup 1–x}, and GaP{sup x}Sb{sup 1–x} layers with thicknesses of 10–20 nm and a content x of the embedded components of up to 0.04.

Phase formation and UV luminescence of Gd3+ doped perovskite-type YScO3

NASA Astrophysics Data System (ADS)

Shimizu, Yuhei; Ueda, Kazushige

2016-10-01

Synthesis of pure and Gd3+doped perovskite-type YScO3 was attempted by a polymerized complex (PC) method and solid state reaction (SSR) method. Crystalline phases and UV luminescence of samples were examined with varying heating temperatures. The perovskite-type single phase was not simply formed in the SSR method, as reported in some literatures, and two cubic C-type phases of starting oxide materials remained forming slightly mixed solid solutions. UV luminescence of Gd3+ doped samples increased with an increase in heating temperatures and volume of the perovskite-type phase. In contrast, a non-crystalline precursor was crystallized to a single C-type phase at 800 °C in the PC method forming a completely mixed solid solution. Then, the phase of perovskite-type YScO3 formed at 1200 °C and its single phase was obtained at 1400 °C. It was revealed that high homogeneousness of cations was essential to generate the single perovskite-phase of YScO3. Because Gd3+ ions were also dissolved into the single C-type phase in Gd3+ doped samples, intense UV luminescence was observed above 800 °C in both C-type phase and perovskite-type phase.

Multiple Reaction Geobarometry for Gabbroic Rocks

NASA Astrophysics Data System (ADS)

Ziberna, L.; Green, E. C. R.; Blundy, J. D.

2016-12-01

Gabbroic rocks are fundamental constituents of the Earth's crust. Given that they can form over a wide range of depths, from the base of the crust to shallow magma storage zones, estimating the pressure (P) of formation of any gabbroic rock found either in exposed crustal sections or as xenolith included in magmas is critically important. Model errors of commonly used geobarometers for gabbroic rocks are > 3 kbar (standard error of estimate), which is unhelpfully high considering the typical P range to be investigated (e.g., < 10 kbar for island arcs). Most likely, the difficulty to extract a clear P signal is partly related to the fact that most thermobarometers use either empirical formulations based on the composition of a single phase, or a single reaction involving only two phases, the latter being often characterized by a relatively low volume change. A multiple-reaction approach employing an internally consistent thermodynamic dataset potentially offers more precise results, as it allows all of the pressure and temperature information in a mineral assemblage for which thermodynamic models exist to be used simultaneously. In this work we evaluated the reliability of the average P method (avP; a multiple-reaction method included in thermocalc; Powell & Holland, 2008, J. Metamorphic Geol. 26, 155-179), applied using some of the latest internally-consistent dataset and activity-composition relations (e.g., Green et al. 2016; doi:10.1111/jmg.12211). The avP method uses a least square minimization technique to calculate the optimal P, taking into account the correlated uncertainties in the pressures predicted by each reaction in an independent set. We tested the method and thermodynamic models using a dataset of phase equilibrium experiments in basaltic systems and well-equilibrated natural samples from a variety of geodynamic settings. We then made minor modifications to the activity-composition models and thermodynamic properties of clinopyroxene and spinel in order to improve the accuracy and precision of the results given by avP. Thanks to the careful selection of experimental data and assessment of the diagnostic utilities in thermocalc, our approach is capable of calculating pressures with 1σ uncertainties < 1.5 kbar for natural assemblages equilibrated in the range 1.0-9.0 kbar.

HPLC method for rapidly following biodiesel fuel transesterification reaction progress using a core-shell column.

PubMed

Allen, Samuel J; Ott, Lisa S

2012-07-01

There are a wide and growing variety of feedstocks for biodiesel fuel. Most commonly, these feedstocks contain triglycerides which are transesterified into the fatty acid alkyl esters (FAAEs) which comprise biodiesel fuel. While the tranesterification reaction itself is simple, monitoring the reaction progress and reaction products is not. Gas chromatography-mass spectrometry is useful for assessing the FAAE products, but does not directly address either the tri-, di-, or monoglycerides present from incomplete transesterification or the free fatty acids which may also be present. Analysis of the biodiesel reaction mixture is complicated by the solubility and physical property differences among the components of the tranesterification reaction mixture. In this contribution, we present a simple, rapid HPLC method which allows for monitoring all of the main components in a biodiesel fuel transesterification reaction, with specific emphasis on the ability to monitor the reaction as a function of time. The utilization of a relatively new, core-shell stationary phase for the HPLC column allows for efficient separation of peaks with short elution times, saving both time and solvent.

Dramatically different kinetics and mechanism at solid/liquid and solid/gas interfaces for catalytic isopropanol oxidation over size-controlled platinum nanoparticles.

PubMed

Wang, Hailiang; Sapi, Andras; Thompson, Christopher M; Liu, Fudong; Zherebetskyy, Danylo; Krier, James M; Carl, Lindsay M; Cai, Xiaojun; Wang, Lin-Wang; Somorjai, Gabor A

2014-07-23

We synthesize platinum nanoparticles with controlled average sizes of 2, 4, 6, and 8 nm and use them as model catalysts to study isopropanol oxidation to acetone in both the liquid and gas phases at 60 °C. The reaction at the solid/liquid interface is 2 orders of magnitude slower than that at the solid/gas interface, while catalytic activity increases with the size of platinum nanoparticles for both the liquid-phase and gas-phase reactions. The activation energy of the gas-phase reaction decreases with the platinum nanoparticle size and is in general much higher than that of the liquid-phase reaction which is largely insensitive to the size of catalyst nanoparticles. Water substantially promotes isopropanol oxidation in the liquid phase. However, it inhibits the reaction in the gas phase. The kinetic results suggest different mechanisms between the liquid-phase and gas-phase reactions, correlating well with different orientations of IPA species at the solid/liquid interface vs the solid/gas interface as probed by sum frequency generation vibrational spectroscopy under reaction conditions and simulated by computational calculations.

“Towards building better linkages between aqueous phase ...

EPA Pesticide Factsheets

Currently, CMAQ’s aqueous phase chemistry routine (AQCHEM-base) assumes Henry’s Law equilibrium and employs a forward Euler method to solve a small set of oxidation equations, considering the additional processes of aitken scavenging and wet deposition in series and employing a bisection method to calculate H+ concentrations. With potentially hundreds of reactions that may be important in cloud water and only seven reactions in the current model, expansion of the existing mechanism is an important area of investigation. However, with the current mechanism hardwired into the solver code, the module is difficult to expand with additional chemistry. It also ignores the impacts of mass transfer limitations on cloud chemistry which may be significant. Here, the Kinetic PreProcessor has been applied to generate a Rosenbrock solver for the CMAQ v5.0.1 aqueous phase chemistry mechanism. The module has been updated to simultaneously solve kinetic mass transfer between the phases, dissociation/association, chemical kinetics, Aitken scavenging, and wet deposition. This will allow for easier expansion of the chemical mechanism in the future and a better link between aqueous phase chemistry and droplet microphysics. The National Exposure Research Laboratory (NERL) Atmospheric Modeling and Analysis Division (AMAD) conducts research in support of EPA mission to protect human health and the environment. AMAD research program is engaged in developing and evaluating pre

Fischer Indole Synthesis in the Gas Phase, the Solution Phase, and at the Electrospray Droplet Interface.

PubMed

Bain, Ryan M; Ayrton, Stephen T; Cooks, R Graham

2017-07-01

Previous reports have shown that reactions occurring in the microdroplets formed during electrospray ionization can, under the right conditions, exhibit significantly greater rates than the corresponding bulk solution-phase reactions. The observed acceleration under electrospray ionization could result from a solution-phase, a gas-phase, or an interfacial reaction. This study shows that a gas-phase ion/molecule (or ion/ion) reaction is not responsible for the observed rate enhancement in the particular case of the Fischer indole synthesis. The results show that the accelerated reaction proceeds in the microdroplets, and evidence is provided that an interfacial process is involved. Graphical Abstract .

On the Possibility of Studying the Reactions of the Thermal Decomposition of Energy Substances by the Methods of High-Resolution Terahertz Spectroscopy

NASA Astrophysics Data System (ADS)

Vaks, V. L.; Domracheva, E. G.; Chernyaeva, M. B.; Pripolzin, S. I.; Revin, L. S.; Tretyakov, I. V.; Anfertyev, V. A.; Yablokov, A. A.; Lukyanenko, I. A.; Sheikov, Yu. V.

2018-02-01

We show prospects for using the method of high-resolution terahertz spectroscopy for a continuous analysis of the decomposition products of energy substances in the gas phase (including short-lived ones) in a wide temperature range. The experimental setup, which includes a terahertz spectrometer for studying the thermal decomposition reactions, is described. The results of analysis of the gaseous decomposition products of energy substances by the example of ammonium nitrate heated from room temperature to 167°C are presented.

A smog chamber comparison of a microfluidic derivatization measurement of gas-phase glyoxal and methylglyoxal with other analytical techniques

NASA Astrophysics Data System (ADS)

Pang, X.; Lewis, A. C.; Richard, A.; Baeza-Romero, M. T.; Adams, T. J.; Ball, S. M.; Daniels, M. J. S.; Goodall, I. C. A.; Monks, P. S.; Peppe, S.; Ródenas García, M.; Sánchez, P.; Muñoz, A.

2013-06-01

A microfluidic lab-on-a-chip derivatization technique has been developed to measure part per billion volume (ppbV) mixing ratios of gaseous glyoxal (GLY) and methylglyoxal (MGLY), and the method compared with other techniques in a smog chamber experiment. The method uses o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA) as a derivatization reagent and a microfabricated planar glass micro-reactor comprising an inlet, gas and fluid splitting and combining channels, mixing junctions, and a heated capillary reaction microchannel. The enhanced phase contact area-to-volume ratio and the high heat transfer rate in the micro-reactor result in a fast and highly efficient derivatization reaction, generating an effluent stream ready for direct introduction to a gas chromatograph-mass spectrometer (GC-MS). A linear response for GLY was observed over a calibration range 0.7 to 400 ppbV, and for MGLY of 1.2 to 300 ppbV, when derivatized under optimal reaction conditions. The method detection limits (MDLs) were 80 pptV and 200 pptV for GLY and MGLY respectively, calculated as 3 times the standard deviation of the S/N of the blank sample chromatograms. These MDLs are below or close to typical concentrations in clean ambient air. The feasibility of the technique was assessed by applying the methodology under controlled conditions to quantify of α-dicarbonyls formed during the photo-oxidation of isoprene in a large scale outdoor atmospheric simulation chamber (EUPHORE). Good general agreement was seen between microfluidic measurements and Fourier Transform Infra Red (FTIR), Broad Band Cavity Enhanced Absorption Spectroscopy (BBCEAS) and a detailed photochemical chamber box modelling calculation for both GLY and MGLY. Less good agreement was found with Proton-Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS) and Solid Phase Microextraction (SPME) derivatization methods for MGLY measurement.

Macroscopic aspects of interfacial reactions

NASA Technical Reports Server (NTRS)

Heckel, R. W.

1976-01-01

The extent of interdiffusion and formation of new phases is determined by the constitution diagram of the alloy system, the interdiffusion coefficients of the phases present, and the thermal conditions (temperature and time) associated with the bonding process and/or subsequent use of the bonded structure. In many instance, the kinetics of interdiffusion and phase formation can be predicted from known parameters using numerical methods and computer techniques. Predictions are compared with experimentally determined parameters for a variety of metallurgical alloy systems.

C-Terminal Protein Characterization by Mass Spectrometry: Isolation of C-Terminal Fragments from Cyanogen Bromide-Cleaved Protein

PubMed Central

Nika, Heinz; Hawke, David H.; Angeletti, Ruth Hogue

2014-01-01

A sample preparation method for protein C-terminal peptide isolation from cyanogen bromide (CNBr) digests has been developed. In this strategy, the analyte was reduced and carboxyamidomethylated, followed by CNBr cleavage in a one-pot reaction scheme. The digest was then adsorbed on ZipTipC18 pipette tips for conjugation of the homoserine lactone-terminated peptides with 2,2′-dithiobis (ethylamine) dihydrochloride, followed by reductive release of 2-aminoethanethiol from the derivatives. The thiol-functionalized internal and N-terminal peptides were scavenged on activated thiol sepharose, leaving the C-terminal peptide in the flow-through fraction. The use of reversed-phase supports as a venue for peptide derivatization enabled facile optimization of the individual reaction steps for throughput and completeness of reaction. Reagents were replaced directly on the support, allowing the reactions to proceed at minimal sample loss. By this sequence of solid-phase reactions, the C-terminal peptide could be recognized uniquely in mass spectra of unfractionated digests by its unaltered mass signature. The use of the sample preparation method was demonstrated with low-level amounts of a whole, intact model protein. The C-terminal fragments were retrieved selectively and efficiently from the affinity support. The use of covalent chromatography for C-terminal peptide purification enabled recovery of the depleted material for further chemical and/or enzymatic manipulation. The sample preparation method provides for robustness and simplicity of operation and is anticipated to be expanded to gel-separated proteins and in a scaled-up format to high-throughput protein profiling in complex biological mixtures. PMID:24688319

Combustion of bulk titanium in oxygen

NASA Technical Reports Server (NTRS)

Clark, A. F.; Moulder, J. C.; Runyan, C. C.

1975-01-01

The combustion of bulk titanium in one atmosphere oxygen is studied using laser ignition and several analytical techniques. These were high-speed color cinematography, time and space resolved spectra in the visible region, metallography (including SEM) of specimens quenched in argon gas, X-ray and chemical product analyses, and a new optical technique, the Hilbert transform method. The cinematographic application of this technique for visualizing phase objects in the combustion zone is described. The results indicate an initial vapor phase reaction immediately adjacent to the molten surface but as the oxygen uptake progresses the evaporation approaches the point of congruency and a much reduced evaporation rate. This and the accumulation of the various soluble oxides soon drive the reaction zone below the surface where gas formation causes boiling and ejection of particles. The buildup of rutile cuts off the oxygen supply and the reaction ceases.

Three-Component Reaction Discovery Enabled by Mass Spectrometry of Self-Assembled Monolayers

PubMed Central

Montavon, Timothy J.; Li, Jing; Cabrera-Pardo, Jaime R.; Mrksich, Milan; Kozmin, Sergey A.

2011-01-01

Multi-component reactions have been extensively employed in many areas of organic chemistry. Despite significant progress, the discovery of such enabling transformations remains challenging. Here, we present the development of a parallel, label-free reaction-discovery platform, which can be used for identification of new multi-component transformations. Our approach is based on the parallel mass spectrometric screening of interfacial chemical reactions on arrays of self-assembled monolayers. This strategy enabled the identification of a simple organic phosphine that can catalyze a previously unknown condensation of siloxy alkynes, aldehydes and amines to produce 3-hydroxy amides with high efficiency and diastereoselectivity. The reaction was further optimized using solution phase methods. PMID:22169871

Advanced deposition model for thermal activated chemical vapor deposition

NASA Astrophysics Data System (ADS)

Cai, Dang

Thermal Activated Chemical Vapor Deposition (TACVD) is defined as the formation of a stable solid product on a heated substrate surface from chemical reactions and/or dissociation of gaseous reactants in an activated environment. It has become an essential process for producing solid film, bulk material, coating, fibers, powders and monolithic components. Global market of CVD products has reached multi billions dollars for each year. In the recent years CVD process has been extensively used to manufacture semiconductors and other electronic components such as polysilicon, AlN and GaN. Extensive research effort has been directed to improve deposition quality and throughput. To obtain fast and high quality deposition, operational conditions such as temperature, pressure, fluid velocity and species concentration and geometry conditions such as source-substrate distance need to be well controlled in a CVD system. This thesis will focus on design of CVD processes through understanding the transport and reaction phenomena in the growth reactor. Since the in situ monitor is almost impossible for CVD reactor, many industrial resources have been expended to determine the optimum design by semi-empirical methods and trial-and-error procedures. This approach has allowed the achievement of improvements in the deposition sequence, but begins to show its limitations, as this method cannot always fulfill the more and more stringent specifications of the industry. To resolve this problem, numerical simulation is widely used in studying the growth techniques. The difficulty of numerical simulation of TACVD crystal growth process lies in the simulation of gas phase and surface reactions, especially the latter one, due to the fact that very limited kinetic information is available in the open literature. In this thesis, an advanced deposition model was developed to study the multi-component fluid flow, homogeneous gas phase reactions inside the reactor chamber, heterogeneous surface reactions on the substrate surface, conductive, convective, inductive and radiative heat transfer, species transport and thereto-elastic stress distributions. Gas phase and surface reactions are studied thermodynamically and kinetically. Based on experimental results, detailed reaction mechanisms are proposed and the deposition rates are predicted. The deposition model proposed could be used for other experiments with similar operating conditions. Four different growth systems are presented in this thesis to discuss comprehensive transport phenomena in crystal growth from vapor. The first is the polysilicon bulk growth by modified Siemens technique in which a silicon tube is used as the starting material. The research effort has been focused on system design, geometric and operating parameters optimization, and heterogeneous and homogeneous silane pyrolysis analysis. The second is the GaN thin film growth by iodine vapor phase epitaxy technique. Heat and mass transport is studied analytically and numerically. Gas phase and surface reactions are analyzed thermodynamically and kinetically. Quasi-equilibrium and kinetic deposition models are developed to predict the growth rate. The third one is the AlN thin film growth by halide vapor phase epitaxy technique. The effects of gas phase and surface reactions on the crystal growth rate and deposition uniformity are studied. The last one is the AlN sublimation growth system. The research effort has been focused on the effect of thermal environment evolution on the crystal growth process. The thermoelastic stress formed in the as-grown AlN crystal is also calculated.

An extensible framework for capturing solvent effects in computer generated kinetic models.

PubMed

Jalan, Amrit; West, Richard H; Green, William H

2013-03-14

Detailed kinetic models provide useful mechanistic insight into a chemical system. Manual construction of such models is laborious and error-prone, which has led to the development of automated methods for exploring chemical pathways. These methods rely on fast, high-throughput estimation of species thermochemistry and kinetic parameters. In this paper, we present a methodology for extending automatic mechanism generation to solution phase systems which requires estimation of solvent effects on reaction rates and equilibria. The linear solvation energy relationship (LSER) method of Abraham and co-workers is combined with Mintz correlations to estimate ΔG(solv)°(T) in over 30 solvents using solute descriptors estimated from group additivity. Simple corrections are found to be adequate for the treatment of radical sites, as suggested by comparison with known experimental data. The performance of scaled particle theory expressions for enthalpic-entropic decomposition of ΔG(solv)°(T) is also presented along with the associated computational issues. Similar high-throughput methods for solvent effects on free-radical kinetics are only available for a handful of reactions due to lack of reliable experimental data, and continuum dielectric calculations offer an alternative method for their estimation. For illustration, we model liquid phase oxidation of tetralin in different solvents computing the solvent dependence for ROO• + ROO• and ROO• + solvent reactions using polarizable continuum quantum chemistry methods. The resulting kinetic models show an increase in oxidation rate with solvent polarity, consistent with experiment. Further work needed to make this approach more generally useful is outlined.

Numerical Computation of Flame Spread over a Thin Solid in Forced Concurrent Flow with Gas-phase Radiation

NASA Technical Reports Server (NTRS)

Jiang, Ching-Biau; T'ien, James S.

1994-01-01

Excerpts from a paper describing the numerical examination of concurrent-flow flame spread over a thin solid in purely forced flow with gas-phase radiation are presented. The computational model solves the two-dimensional, elliptic, steady, and laminar conservation equations for mass, momentum, energy, and chemical species. Gas-phase combustion is modeled via a one-step, second order finite rate Arrhenius reaction. Gas-phase radiation considering gray non-scattering medium is solved by a S-N discrete ordinates method. A simplified solid phase treatment assumes a zeroth order pyrolysis relation and includes radiative interaction between the surface and the gas phase.

Isoprene/methyl acrylate Diels-Alder reaction in supercritical carbon dioxide

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

Lin, B.; Akgerman, A.

1999-12-01

The Diels-Alder reaction between isoprene and methyl acrylate was carried out in supercritical carbon dioxide in the temperature range 110--140 C and the pressure range 95.2--176.9 atm in a 300 cm{sup 3} autoclave. The high-pressure phase behavior of the reaction mixture in the vicinity of its critical region was determined in a mixed vessel with a sight window to ensure that all the experiments were performed in the supercritical single-phase region. Kinetic data were obtained at different temperatures, pressures, and reaction times. It was observed that in the vicinity of the critical point the reaction rate constant decreases with increasingmore » pressure. It was also determined that the reaction selectivity does not change with operating conditions. Transition-state theory was used to explain the effect of pressure on reaction rate and product selectivity. Additional experiments were conducted at constant temperature but different phase behaviors (two-phase region, liquid phase, supercritical phase) by adjusting the initial composition and pressure. It was shown that the highest reaction rate is in the supercritical region.« less

Mechanistic Studies Of Combustion And Structure Formation During Combustion Synthesis Of Advanced Materials: Phase Separation Mechanism For Bio-Alloys

NASA Technical Reports Server (NTRS)

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

2003-01-01

Among all implant materials, Co-Cr-Mo alloys demonstrate perhaps the most useful balance of resistance to corrosion, fatigue and wear, along with strength and biocompatibility [1]. Currently, these widely used alloys are produced by conventional furnace technology. Owing to high melting points of the main alloy elements (e.g. Tm.p.(Co) 1768 K), high-temperature furnaces and long process times (several hours) are required. Therefore, attempts to develop more efficient and flexible methods for production of such alloys with superior properties are of great interest. The synthesis of materials using combustion phenomena is an advanced approach in powder metallurgy [2]. The process is characterized by unique conditions involving extremely fast heating rates (up to 10(exp 6 K/s), high temperatures (up to 3500 K), and short reaction times (on the order of seconds). As a result, combustion synthesis (CS) offers several attractive advantages over conventional metallurgical processing and alloy development technologies. The foremost is that solely the heat of chemical reaction (instead of an external source) supplies the energy for the synthesis. Also, simple equipment, rather than energy-intensive high-temperature furnaces, is sufficient. This work was devoted to experiments on CS of Co-based alloys by utilizing thermite (metal oxide-reducing metal) reactions, where phase separation subsequently produces materials with tailored compositions and properties. Owing to high reaction exothermicity, the CS process results in a significant increase of temperature (up to 3000 C), which is higher than melting points of all products. Since the products differ in density, phase separation may be a gravitydriven process: the heavy (metallic phase) settles while the light (slag) phase floats. The goal was to determine if buoyancy is indeed the major mechanism that controls phase segregation.

Geochemical modeling of reactions and partitioning of trace metals and radionuclides during titration of contaminated acidic sediments.

PubMed

Zhang, Fan; Luo, Wensui; Parker, Jack C; Spalding, Brian P; Brooks, Scott C; Watson, David B; Jardine, Philip M; Gu, Baohua

2008-11-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This studywas undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cation exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/ dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO4(2-) for contaminated sediments indicated close agreement suggesting that the model could potentially be used to predictthe acid-base behavior of the sediment-solution system under variable pH conditions.

LSENS, The NASA Lewis Kinetics and Sensitivity Analysis Code

NASA Technical Reports Server (NTRS)

Radhakrishnan, K.

2000-01-01

A general chemical kinetics and sensitivity analysis code for complex, homogeneous, gas-phase reactions is described. The main features of the code, LSENS (the NASA Lewis kinetics and sensitivity analysis code), are its flexibility, efficiency and convenience in treating many different chemical reaction models. The models include: static system; steady, one-dimensional, inviscid flow; incident-shock initiated reaction in a shock tube; and a perfectly stirred reactor. In addition, equilibrium computations can be performed for several assigned states. An implicit numerical integration method (LSODE, the Livermore Solver for Ordinary Differential Equations), which works efficiently for the extremes of very fast and very slow reactions, is used to solve the "stiff" ordinary differential equation systems that arise in chemical kinetics. For static reactions, the code uses the decoupled direct method to calculate sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of dependent variables and/or the rate coefficient parameters. Solution methods for the equilibrium and post-shock conditions and for perfectly stirred reactor problems are either adapted from or based on the procedures built into the NASA code CEA (Chemical Equilibrium and Applications).

Biphasic catalysis in water/carbon dioxide micellar systems

DOEpatents

Jacobson, Gunilla B.; Tumas, William; Johnston, Keith P.

2002-01-01

A process is provided for catalyzing an organic reaction to form a reaction product by placing reactants and a catalyst for the organic reaction, the catalyst of a metal complex and at least one ligand soluble within one of the phases of said aqueous biphasic system, within an aqueous biphasic system including a water phase, a dense phase fluid, and a surfactant adapted for forming an emulsion or microemulsion within the aqueous biphasic system, the reactants soluble within one of the phases of the aqueous biphasic system and convertible in the presence of the catalyst to a product having low solubility in the phase in which the catalyst is soluble; and, maintaining the aqueous biphasic system under pressures, at temperatures, and for a period of time sufficient for the organic reaction to occur and form the reaction product and to maintain sufficient density on the dense phase fluid, the reaction product characterized as having low solubility in the phase in which the catalyst is soluble.

Synthesis and DFT calculations of some 2-aminothiazoles

NASA Astrophysics Data System (ADS)

Rezania, Jafar; Behzadi, Hadi; Shockravi, Abbas; Ehsani, Morteza; Akbarzadeh, Elahe

2018-04-01

A series of 2-aminothiazole derivatives have been synthesized by the reaction of acetyl compounds with thiourea and iodine as catalyst under solvent-free condition, a green chemistry method. The quantum chemical calculations at the DFT/B3LYP level of theory in gas phase were carried out for starting acetyl derivatives. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) and related reactivity descriptor of acetyl derivatives, as well as, enthalpy of reactions are calculated in order to investigate the reaction properties of acetyl compounds and yields of the reactions. The calculated reactivity descriptors are well correlated to activity of different acetyl derivatives.

Cutaneous irritancy of an ibuprofen medicated plaster in healthy volunteers.

PubMed

Maganji, Manisha; Connolly, Mark P; Bhatt, Aomesh

2018-04-01

To assess the irritation and contact sensitization potential of a 200 mg ibuprofen medicated plaster. This double-blind, phase-1 placebo controlled study had two phases; the induction phase to evaluate the irritant potential of continuous application of the plaster, and the challenge phase to assess contact sensitivity (allergy). The cumulative irritancy potential was evaluated using an adaptation of the Shelanski method. Healthy adults (≥18 years of age) (N = 210) were treated simultaneously with one ibuprofen medicated and one placebo plaster applied in a randomized fashion to either the left or right side of the lower back. During the induction phase, plasters were applied on Days 1, 3, 5, 8, 10, 12, 15, 17, and 19 and the final plaster removed on Day 22. At each scheduled visit plasters and applications sites were assessed for degree of adhesion and skin irritation (score of 1 = no irritation to 7 = strong reaction spreading beyond test sites), respectively. The challenge phase followed a two-week washout period. A plaster was applied on Day 36 for 48 h and assessment occurred on Days 38, 39, and 40. The mean cumulative irritation score during the induction phase was lower for the ibuprofen medicated plaster than the placebo plaster (0.32 vs. 1.23, respectively). Three (1.4%) subjects experience a dermal reaction of grade ≥3 for the ibuprofen medicated plaster compared with 27 (12.7%) for the placebo plaster. Following challenge with ibuprofen or placebo plasters, 12 subjects (6.2%) with the ibuprofen medicated plaster and four (2.2%) with the placebo plaster had skin reaction of assessment grade higher than the induction phase. One subject for the ibuprofen and two for the placebo plaster had reactions with grade >2. No subjects showed an increase in sensitization on Day 39 or 40 compared with Day 38. The findings indicate that the both the irritancy and contact sensitization of the ibuprofen medicated plaster is acceptable.

Revised users manual, Pulverized Coal Gasification or Combustion: 2-dimensional (87-PCGC-2): Final report, Volume 2. [87-PCGC-2

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

Smith, P.J.; Smoot, L.D.; Brewster, B.S.

1987-12-01

A two-dimensional, steady-state model for describing a variety of reactive and non-reactive flows, including pulverized coal combustion and gasification, is presented. Recent code revisions and additions are described. The model, referred to as 87-PCGC-2, is applicable to cylindrical axi-symmetric systems. Turbulence is accounted for in both the fluid mechanics equations and the combustion scheme. Radiation from gases, walls, and particles is taken into account using either a flux method or discrete ordinates method. The particle phase is modeled in a Lagrangian framework, such that mean paths of particle groups are followed. Several multi-step coal devolatilization schemes are included along withmore » a heterogeneous reaction scheme that allows for both diffusion and chemical reaction. Major gas-phase reactions are modeled assuming local instantaneous equilibrium, and thus the reaction rates are limited by the turbulent rate mixing. A NO/sub x/ finite rate chemistry submodel is included which integrates chemical kinetics and the statistics of the turbulence. The gas phase is described by elliptic partial differential equations that are solved by an iterative line-by-line technique. Under-relaxation is used to achieve numerical stability. The generalized nature of the model allows for calculation of isothermal fluid mechanicsgaseous combustion, droplet combustion, particulate combustion and various mixtures of the above, including combustion of coal-water and coal-oil slurries. Both combustion and gasification environments are permissible. User information and theory are presented, along with sample problems. 106 refs.« less

Nickel-Aluminum Layered Double Hydroxide Coating on the Surface of Conductive Substrates by Liquid Phase Deposition.

PubMed

Maki, Hideshi; Takigawa, Masashi; Mizuhata, Minoru

2015-08-12

The direct synthesis of the adhered Ni-Al LDH thin film onto the surface of electrically conductive substrates by the liquid phase deposition (LPD) reaction is carried out for the development of the positive electrode. The complexation and solution equilibria of the dissolved species in the LPD reaction have been clarified by a theoretical approach, and the LPD reaction conditions for the Ni-Al LDH depositions are shown to be optimized by controlling the fluoride ion concentration and the pH of the LPD reaction solutions. The yields of metal oxides and hydroxides by the LPD method are very sensitive to the supersaturation state of the hydroxide in the reaction solution. The surfaces of conductive substrates are completely covered by the minute mesh-like Ni-Al LDH thin film; furthermore, there is no gap between the surfaces of conductive substrates and the deposited Ni-Al LDH thin film. The active material layer thickness was able to be controlled within the range from 100 nm to 1 μm by the LPD reaction time. The high-crystallinity and the arbitrary-thickness thin films on the conductive substrate surface will be beneficial for the interface control of charge transfer reaction fields and the internal resistance reduction of various secondary batteries.

High temperature lubricating process

DOEpatents

Taylor, R.W.; Shell, T.E.

1979-10-04

It has been difficult to provide adequate lubrication for load bearing, engine components when such engines are operating in excess of about 475/sup 0/C. The present invention is a process for providing a solid lubricant on a load bearing, solid surface, such as in an engine being operated at temperatures in excess of about 475/sup 0/C. The process comprises contacting and maintaining the following steps: a gas phase is provided which includes at least one component reactable in a temperature dependent reaction to form a solid lubricant; the gas phase is contacted with the load bearing surface; the load bearing surface is maintained at a temperature which causes reaction of the gas phase component and the formation of the solid lubricant; and the solid lubricant is formed directly on the load bearing surface. The method is particularly suitable for use with ceramic engines.

High temperature lubricating process

DOEpatents

Taylor, Robert W.; Shell, Thomas E.

1982-01-01

It has been difficult to provide adaquate lubrication for load bearing, engine components when such engines are operating in excess of about 475.degree. C. The present invention is a process for providing a solid lubricant on a load bearing, solid surface (14), such as in an engine (10) being operated at temperatures in excess of about 475.degree. C. The process comprises contacting and maintaining steps. A gas phase (42) is provided which includes at least one component reactable in a temperature dependent reaction to form a solid lubricant. The gas phase is contacted with the load bearing surface. The load bearing surface is maintained at a temperature which causes reaction of the gas phase component and the formation of the solid lubricant. The solid lubricant is formed directly on the load bearing surface. The method is particularly suitable for use with ceramic engines.

A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical

NASA Astrophysics Data System (ADS)

Shaw, Jacob T.; Lidster, Richard T.; Cryer, Danny R.; Ramirez, Noelia; Whiting, Fiona C.; Boustead, Graham A.; Whalley, Lisa K.; Ingham, Trevor; Rickard, Andrew R.; Dunmore, Rachel E.; Heard, Dwayne E.; Lewis, Ally C.; Carpenter, Lucy J.; Hamilton, Jacqui F.; Dillon, Terry J.

2018-03-01

Gas-phase rate coefficients are fundamental to understanding atmospheric chemistry, yet experimental data are not available for the oxidation reactions of many of the thousands of volatile organic compounds (VOCs) observed in the troposphere. Here, a new experimental method is reported for the simultaneous study of reactions between multiple different VOCs and OH, the most important daytime atmospheric radical oxidant. This technique is based upon established relative rate concepts but has the advantage of a much higher throughput of target VOCs. By evaluating multiple VOCs in each experiment, and through measurement of the depletion in each VOC after reaction with OH, the OH + VOC reaction rate coefficients can be derived. Results from experiments conducted under controlled laboratory conditions were in good agreement with the available literature for the reaction of 19 VOCs, prepared in synthetic gas mixtures, with OH. This approach was used to determine a rate coefficient for the reaction of OH with 2,3-dimethylpent-1-ene for the first time; k = 5.7 (±0.3) × 10-11 cm3 molecule-1 s-1. In addition, a further seven VOCs had only two, or fewer, individual OH rate coefficient measurements available in the literature. The results from this work were in good agreement with those measurements. A similar dataset, at an elevated temperature of 323 (±10) K, was used to determine new OH rate coefficients for 12 aromatic, 5 alkane, 5 alkene and 3 monoterpene VOC + OH reactions. In OH relative reactivity experiments that used ambient air at the University of York, a large number of different VOCs were observed, of which 23 were positively identified. Due to difficulties with detection limits and fully resolving peaks, only 19 OH rate coefficients were derived from these ambient air samples, including 10 reactions for which data were previously unavailable at the elevated reaction temperature of T = 323 (±10) K.

Comparative study on thermodynamic characteristics of AgCuZnSn brazing alloys

NASA Astrophysics Data System (ADS)

Wang, Xingxing; Li, Shuai; Peng, Jin

2018-01-01

AgCuZnSn brazing alloys were prepared based on the BAg50CuZn filler metal through electroplating diffusion process, and melting alloying method. The thermodynamics of phase transformations of those fillers were analyzed by non-isothermal differentiation and integration methods of thermal analysis kinetics. In this study, it was demonstrated that as the Sn content increased, the reaction fractional integral curves of AgCuZnSn fillers from solid to liquid became straighter at the endothermic peak. Under the same Sn contents, the reaction fractional integral curve of the Sn-plated filler metal was straighter, and the phase transformation activation energy was higher compared to the traditional silver filler metal. At the 7.2 wt% Sn content, the activation energies and pre-exponential factors of the two fillers reached the maximum, then the phase transformation rate equations of the Sn-plated silver filler and the traditional filler were determined as: k = 1.41 × 1032exp(-5.56 × 105/RT), k = 7.29 × 1020exp(-3.64 × 105/RT), respectively.

Evaluation and Comparison of Chemiluminescence and UV Photometric Methods for Measuring Ozone Concentrations in Ambient Air

EPA Science Inventory

The current Federal Reference Method (FRM) for measuring concentrations of ozone in ambient air is based on the dry, gas-phase, chemiluminescence reaction between ethylene (C₂H₄) and any ozone (O₃) that may be p...

A composite phase diagram of structure H hydrates using Schreinemakers' geometric approach

USGS Publications Warehouse

Mehta, A.P.; Makogon, T.Y.; Burruss, R.C.; Wendlandt, R.F.; Sloan, E.D.

1996-01-01

A composite phase diagram is presented for Structure H (sH) clathrate hydrates. In this work, we derived the reactions occurring among the various phases along each four-phase (Ice/Liquid water, liquid hydrocarbon, vapor, and hydrate) equilibrium line. A powerful method (though seldom used in chemical engineering) for multicomponent equilibria developed by Schreinemakers is applied to determine the relative location of all quadruple (four-phase) lines emanating from three quintuple (five-phase) points. Experimental evidence validating the approximate phase diagram is also provided. The use of Schreinemakers' rules for the development of the phase diagram is novel for hydrates, but these rules may be extended to resolve the phase space of other more complex systems commonly encountered in chemical engineering.

Coherent diffractive imaging of solid state reactions in zinc oxide crystals

NASA Astrophysics Data System (ADS)

Leake, Steven J.; Harder, Ross; Robinson, Ian K.

2011-11-01

We investigated the doping of zinc oxide (ZnO) microcrystals with iron and nickel via in situ coherent x-ray diffractive imaging (CXDI) in vacuum. Evaporated thin metal films were deposited onto the ZnO microcrystals. A single crystal was selected and tracked through annealing cycles. A solid state reaction was observed in both iron and nickel experiments using CXDI. A combination of the shrink wrap and guided hybrid-input-output phasing methods were applied to retrieve the electron density. The resolution was 33 nm (half order) determined via the phase retrieval transfer function. The resulting images are nevertheless sensitive to sub-angstrom displacements. The exterior of the microcrystal was found to degrade dramatically. The annealing of ZnO microcrystals coated with metal thin films proved an unsuitable doping method. In addition the observed defect structure of one crystal was attributed to the presence of an array of defects and was found to change upon annealing.

A novel method for the synthesis of zirconia powder

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

Bohe, A.E.; Pasquevich, D.M.

A novel method for the synthesis of zirconia powder is presented in this paper. The formation of fine particles of zirconia takes place when metallic zirconium and hematite are heated in the presence of gaseous chlorine. The overall process, which can be described by the following reaction: 3 Zr(s) + 2 Fe{sub 2}O{sub 3}(s) {r_arrow} 3 ZrO{sub 2}(s) + 4 Fe(s), occurs by a mass-transport mechanism through the vapor phase between 723 and 1223 K. The vapor-mass transport among the solid species takes place by means of zirconium and iron chlorides. The fundamentals of synthesis are discussed on the basismore » of a detailed thermodynamic analysis of reactions involved in the process, as well as by a characterization of the solid phases formed at various temperatures at XRD and SEM examinations.« less

Phase-space reaction network on a multisaddle energy landscape: HCN isomerization.

PubMed

Li, Chun-Biu; Matsunaga, Yasuhiro; Toda, Mikito; Komatsuzaki, Tamiki

2005-11-08

By using the HCN/CNH isomerization reaction as an illustrative vehicle of chemical reactions on multisaddle energy landscapes, we give explicit visualizations of molecular motions associated with a straight-through reaction tube in the phase space inside which all reactive trajectories pass from one basin to another, with eliminating recrossing trajectories in the configuration space. This visualization provides us with a chemical intuition of how chemical species "walk along" the reaction-rate slope in the multidimensional phase space compared with the intrinsic reaction path in the configuration space. The distinct nonergodic features in the two different HCN and CNH wells can be easily demonstrated by a section of Poincare surface of section in those potential minima, which predicts in a priori the pattern of trajectories residing in the potential well. We elucidate the global phase-space structure which gives rise to the non-Markovian dynamics or the dynamical correlation of sequential multisaddle chemical reactions. The phase-space structure relevant to the controllability of the product state in chemical reactions is also discussed.

Feasibility Study of Vapor-Mist Phase Reaction Lubrication Using a Thioether Liquid

NASA Technical Reports Server (NTRS)

Morales, Wilfredo; Handschuh, Robert F.; Krantz, Timothy L.

2007-01-01

A primary technology barrier preventing the operation of gas turbine engines and aircraft gearboxes at higher temperatures is the inability of currently used liquid lubricants to survive at the desired operating conditions over an extended time period. Current state-of-the-art organic liquid lubricants rapidly degrade at temperatures above 300 C; hence, another form of lubrication is necessary. Vapor or mist phase reaction lubrication is a unique, alternative technology for high temperature lubrication. The majority of past studies have employed a liquid phosphate ester that was vaporized or misted, and delivered to bearings or gears where the phosphate ester reacted with the metal surfaces generating a solid lubricious film. This method resulted in acceptable operating temperatures suggesting some good lubrication properties, but the continuous reaction between the phosphate ester and the iron surfaces led to wear rates unacceptable for gas turbine engine or aircraft gearbox applications. In this study, an alternative non-phosphate liquid was used to mist phase lubricate a spur gearbox rig operating at 10,000 rpm under highly loaded conditions. After 21 million shaft revolutions of operation the gears exhibited only minor wear.

Synthesis design of Y3Al5O12: Ce3+ phosphor for fabrication of ceramic converter in automotive application

NASA Astrophysics Data System (ADS)

Kwon, Seok Bin; Choi, Seung Hee; Yoo, Jung Hyeon; Jeong, Seong Guk; Song, Young Hyun; Yoon, Dae Ho

2018-06-01

A cellulose-assisted, liquid-phase precursor (LPP) was used to synthesize a YAG phosphor radiating near 530 nm with a particle size of 400 nm, which may be implemented in many applications. The mixture of the materials was homogeneous, and the cellulose-assisted LPP method involved a liquid-phase reaction at a lower temperature compared to a solid-state reaction (SSR). The reaction was performed at 1200, 1300 and 1400 °C, and the composition ratio of the samples was controlled based on yttrium (L1: 2.7, L2: 2.8, L3: 2.9, L4: 2.95, and L5: 3.1 M). ∼400 nm particles were obtained at 1200 °C and ∼1 μm at 1300 °C. At 1200 °C, the PL intensity was the highest in the Y3.1Al5O12 sample. At 1300 and 1400 °C, the strongest intensity was evident in the Y2.9Al5O12 sample. The XRD patterns for all temperatures showed a YAG phase in JCPDS.

Microstructures and Properties of Plasma Sprayed Ni Based Coatings Reinforced by TiN/C1-xNxTi Generated from In-Situ Solid-Gas Reaction.

PubMed

Wang, Wenquan; Li, Wenmo; Xu, Hongyong

2017-07-11

The strengthening hard phases TiN/C 1- x N x Ti were generated by in-situ solid-gas reaction in Ni-based composite coatings prepared using a plasma spray welding process to reinforce the wear resistance of the coatings. The microstructures and properties of the coatings were investigated. The results showed that the coatings mainly consisted of phases such as TiN, C 1- x N x Ti, TiC, etc. A small amount of CrB, M₇C₃, and M 23 C₆ were also detected in the coatings by micro-analysis method. Compared with the originally pure NiCrBSi coatings, the hardness of the NiCrBSi coatings reinforced by in-situ solid-gas reaction was 900 HV 0.5 , increased by more than 35%. Consequently, the wear resistance of the reinforced coatings was greatly improved due to the finely and uniformly dispersed hard phases mentioned above. The weight losses after wear test for the two kinds of coatings were 15 mg and 8 mg, respectively.

Theoretical calculations of homogeneous catalysis in the gas phase: elimination kinetics of 2,2-dimethoxypropane in the presence of HCl, F3CCOOH and CH3COOH

NASA Astrophysics Data System (ADS)

Guerra, Raul J.; Lezama, Jesus; Cordova-Sintjago, Tania; Chuchani, Gabriel

2018-05-01

The mechanisms of gas-phase elimination kinetics of 2,2-dimethoxypropane in the presence of hydrogen chloride, trifluoroacetic acid and acetic acid were studied using Moller Plesset, ab initio combined method Complete Basis Set (CBS)-QB3 and various density functional theory methods with 6-311G(d,p) and 6-311++G(d,p) basis sets. The M06-2X/6-311++G(d,p) method provided reasonable agreement with the experimental enthalpy and energy of activation. Formation of 2-methoxypropene and methanol products occurs through six-membered cyclic ring transition state (TS) structure. The TS was characterised by single imaginary frequency, and confirmed through intrinsic reaction coordinate (IRC) calculations. The IRC calculations suggest the development of a van der Waal complex between the 2, 2-dimethoxy propane and the acid catalyst, leading to the TS formation. The process of decomposition in the absence of the acid catalyst requires much higher temperature with an energy of activation above 200 kJ/mol. This fact appears to be a consequence of a four-membered cyclic TS-type of mechanism in the non-catalysed reaction. Structural parameters, analyses of natural bond orbital charges and bond orders of the acid-catalysed elimination reactions in this study suggest that the polarisation of the C-O bond, in the direction Cδ+-Oδ-, is rate-determining in the TS. These reactions are non-synchronous concerted polar in nature.

Ultrasound-assisted phase-transfer catalysis method in an aqueous medium to promote the Knoevenagel reaction: advantages over the conventional and microwave-assisted solvent-free/catalyst-free method.

PubMed

De-la-Torre, Pedro; Osorio, Edison; Alzate-Morales, Jans H; Caballero, Julio; Trilleras, Jorge; Astudillo-Saavedra, Luis; Brito, Iván; Cárdenas, Alejandro; Quiroga, Jairo; Gutiérrez, Margarita

2014-09-01

Given the broad spectrum of uses of acrylonitrile derivatives as fluorescent probes, AChE inhibitors, and others, it is necessary to find easy, efficient and simple methods to synthesize and diversify these compounds. We report the results of a comparative study of the effects of three techniques on the reactions between heterocyclic aldehydes and 2-(benzo[d]thiazol-2-yl)acetonitrile: stirring; ultrasound coupled to PTC conditions (US-PTC); and MW irradiation (MWI) under solvent and catalyst-free conditions. The effects of conditions on reaction parameters were evaluated and compared in terms of reaction time, yield, purity and outcomes. The US-PTC method is more efficient than the MWI and conventional methods. The reaction times were considerably shorter, with high yields (>90%) and good levels of purity. In addition, X-ray diffraction analysis and quantum mechanical calculations, at the level of density functional theory (DFT), ratify obtaining acrylonitrile isomers with E configurations. The crystal structure of 3c is stabilized by weak C-Ho⋯N intermolecular interactions (Ho⋯NC=2.45 Å, Co⋯NC=3.348(3) Å, Ho⋯NC=162°), forming centrosymmetric ring R2(2) (20) along the crystallographic a axis. Copyright © 2014 Elsevier B.V. All rights reserved.

Effects of Molar Ratios and Sintering Times on Crystal Structures and Surface Morphology of Nd1+xFeO3 Oxide Alloy Prepared by using Solid Reaction Method

NASA Astrophysics Data System (ADS)

Sujiono, E. H.; Agus, J.; Samnur, S.; Triyana, K.

2018-05-01

The effects of molar ratios and sintering times on crystal structures and surface morphology on NdFeO3 oxide alloy have been studied. NdFeO3 oxide alloy formed by chemical preparation with solid reaction method using raw oxide Fe2O3 (99.9 %) and Nd2O3 (99.9 %) powders. In this article we reported the effects of molar ratios x = (–0.1, –0.2 and –0.3) and sintering times for 15 h and 20 h on crystal structures and surface morphology of Nd1+xFeO3 synthesized by solid-state reaction method. The results indicate that variation of molar ratio and sintering time has influenced the FWHM, crystalline size and grain size. The Nd1+xFeO3 have a major phase is NdFeO3, and other minor phases are Fe2O3, Nd2O3 and Nd(OH)3. The dominant intensity of hkl (121) with a value in FWHM, crystallite size, and grain size an indication the results will be applied as a gas sensor material as the focus of the further study.

A Disposable Microfluidic Device with a Screen Printed Electrode for Mimicking Phase II Metabolism

PubMed Central

Vasiliadou, Rafaela; Nasr Esfahani, Mohammad Mehdi; Brown, Nathan J.; Welham, Kevin J.

2016-01-01

Human metabolism is investigated using several in vitro methods. However, the current methodologies are often expensive, tedious and complicated. Over the last decade, the combination of electrochemistry (EC) with mass spectrometry (MS) has a simpler and a cheaper alternative to mimic the human metabolism. This paper describes the development of a disposable microfluidic device with a screen-printed electrode (SPE) for monitoring phase II GSH reactions. The proposed chip has the potential to be used as a primary screening tool, thus complementing the current in vitro methods. PMID:27598162

Liquid-liquid and solid-phase extractions of phenols from virgin olive oil and their separation by chromatographic and electrophoretic methods.

PubMed

Bendini, Alessandra; Bonoli, Matteo; Cerretani, Lorenzo; Biguzzi, Barbara; Lercker, Giovanni; Toschi, Tullia Gallina

2003-01-24

The high oxidative stability of virgin olive oil is related to its high monounsaturated/polyunsaturated ratio and to the presence of antioxidant compounds, such as tocopherols and phenols. In this paper, the isolation of phenolic compounds from virgin olive oil, by different methods, was tested and discussed. Particularly liquid-liquid and solid-phase extraction methods were compared, assaying, for the latter, three stationary phases (C8, C18 and Diol) and several elution mixtures. Quantification of phenolic and o-diphenolic substances in the extracts was performed by the traditional Folin-Ciocalteau method and the sodium molybdate reaction, respectively. Furthermore, the quantification of phenolic compounds in the extracts and in a standard mixture was carried out both with diode array and mass spectrometric detection and capillary zone electrophoresis.

Calcite phase determination of CaCO3 nanoparticles synthesized by one step drying method

NASA Astrophysics Data System (ADS)

Sulimai, N. H.; Rani, Rozina Abdul; Khusaimi, Z.; Abdullah, S.; Salifairus, M. J.; Alrokayan, Salman; Khan, Haseeb; Rusop, M.

2018-05-01

Calcium Carbonate (CaCO3) is a type of carbonic salt. It exist naturally as white odourless solid and may also be synthesized by chemical reactions. This work studies one-step precipitation of CaCO3 that was prepared by novel method of one-step precipitation method. The method was then proceeded by different types of drying. The first type is by normal drying in oven whereas the second type is with the presence of hydrothermal influence. From the results, precipitated CaCO3 dried by normal drying method produces CaCO3 with two polymorphs present; calcite and vaterite. Normal drying at 500°C has no vaterite phase left. Drying by hydrothermal precipitated CaCO3 has Nitrogen (N) left on the surfaces of the precipitated CaCO3. This work successfully identified calcite phase in the precipitated CaCO3.

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

PubMed

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

2008-02-15

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

Morphology and conductivity study of solid electrolyte Li{sub 3}PO{sub 4}

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

Prayogi, Lugas Dwi, E-mail: ldprayodi@gmail.com; Faisal, Muhamad; Kartini, Evvy, E-mail: kartini@batan.go.id

2016-02-08

The comparison between two different methods of synthesize of solid electrolyte Li{sub 3}PO{sub 4} as precursor material for developing lithium ion battery, has been performed. The first method is to synthesize Li{sub 3}PO{sub 4} prepared by wet chemical reaction from LiOH and H{sub 3}PO{sub 4} which provide facile, abundant available resource, low cost, and low toxicity. The second method is solid state reaction prepared by Li{sub 2}CO{sub 3} and NH{sub 4}H{sub 2}PO{sub 4.} In addition, the possible morphology identification of comparison between two different methods will also be discussed. The composition, morphology, and additional identification phase and another compound ofmore » Li{sub 3}PO{sub 4} powder products from two different reaction are characterized by SEM, EDS, and EIS. The Li{sub 3}PO{sub 4} powder produced from wet reaction and solid state reaction have an average diameter of 0.834 – 7.81 µm and 2.15 – 17.3 µm, respectively. The density of Li{sub 3}PO{sub 4} prepared by wet chemical reaction is 2.238 gr/cm{sup 3}, little bit lower than the sample prepared by solid state reaction which density is 2.3560 gr/cm{sup 3}. The EIS measurement result shows that the conductivity of Li{sub 3}PO{sub 4} is 1.7 x 10{sup −9} S.cm{sup −1} for wet chemical reaction and 1.8 x 10{sup −10} S.cm{sup −1} for solid state reaction. The conductivity of Li{sub 3}PO{sub 4} is not quite different between those two samples even though they were prepared by different method of synthesize.« less

Visualization of electrochemically driven solid-state phase transformations using operando hard X-ray spectro-imaging

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

Li, Linsen; Chen-Wiegart, Yu-chen Karen; Wang, Jiajun

In situ techniques with high temporal, spatial and chemical resolution are key to understand ubiquitous solid-state phase transformations, which are crucial to many technological applications. Hard X-ray spectro-imaging can visualize electrochemically driven phase transformations but demands considerably large samples with strong absorption signal so far. Here we show a conceptually new data analysis method to enable operando visualization of mechanistically relevant weakly absorbing samples at the nanoscale and study electrochemical reaction dynamics of iron fluoride, a promising high-capacity conversion cathode material. In two specially designed samples with distinctive microstructure and porosity, we observe homogeneous phase transformations during both discharge andmore » charge, faster and more complete Li-storage occurring in porous polycrystalline iron fluoride, and further, incomplete charge reaction following a pathway different from conventional belief. In conclusion, these mechanistic insights provide guidelines for designing better conversion cathode materials to realize the promise of high-capacity lithium-ion batteries.« less

Visualization of electrochemically driven solid-state phase transformations using operando hard X-ray spectro-imaging

DOE PAGES

Li, Linsen; Chen-Wiegart, Yu-chen Karen; Wang, Jiajun; ...

2015-04-20

In situ techniques with high temporal, spatial and chemical resolution are key to understand ubiquitous solid-state phase transformations, which are crucial to many technological applications. Hard X-ray spectro-imaging can visualize electrochemically driven phase transformations but demands considerably large samples with strong absorption signal so far. Here we show a conceptually new data analysis method to enable operando visualization of mechanistically relevant weakly absorbing samples at the nanoscale and study electrochemical reaction dynamics of iron fluoride, a promising high-capacity conversion cathode material. In two specially designed samples with distinctive microstructure and porosity, we observe homogeneous phase transformations during both discharge andmore » charge, faster and more complete Li-storage occurring in porous polycrystalline iron fluoride, and further, incomplete charge reaction following a pathway different from conventional belief. In conclusion, these mechanistic insights provide guidelines for designing better conversion cathode materials to realize the promise of high-capacity lithium-ion batteries.« less

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

NASA Astrophysics Data System (ADS)

Piersall, Shannon D.; Anderson, James B.

1991-07-01

In applications to several simple reaction systems we have explored a ``direct simulation'' method for predicting and understanding the behavior of gas phase chemical reaction systems. This Monte Carlo method, originated by Bird, has been found remarkably successful in treating a number of difficult problems in rarefied dynamics. Extension to chemical reactions offers a powerful tool for treating reaction systems with nonthermal distributions, with coupled gas-dynamic and reaction effects, with emission and adsorption of radiation, and with many other effects difficult to treat in any other way. The usual differential equations of chemical kinetics are eliminated. For a bimolecular reaction of the type A+B→C+D with a rate sufficiently low to allow a continued thermal equilibrium of reactants we find that direct simulation reproduces the expected second order kinetics. Simulations for a range of temperatures yield the activation energies expected for the reaction models specified. For faster reactions under conditions leading to a depletion of energetic reactant species, the expected slowing of reaction rates and departures from equilibrium distributions are observed. The minimum sample sizes required for adequate simulations are as low as 1000 molecules for these cases. The calculations are found to be simple and straightforward for the homogeneous systems considered. Although computation requirements may be excessively high for very slow reactions, they are reasonably low for fast reactions, for which nonequilibrium effects are most important.

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.

Method for rapid, controllable growth and thickness, of epitaxial silicon films

DOEpatents

Wang, Qi [Littleton, CO; Stradins, Paul [Golden, CO; Teplin, Charles [Boulder, CO; Branz, Howard M [Boulder, CO

2009-10-13

A method of producing epitaxial silicon films on a c-Si wafer substrate using hot wire chemical vapor deposition by controlling the rate of silicon deposition in a temperature range that spans the transition from a monohydride to a hydrogen free silicon surface in a vacuum, to obtain phase-pure epitaxial silicon film of increased thickness is disclosed. The method includes placing a c-Si substrate in a HWCVD reactor chamber. The method also includes supplying a gas containing silicon at a sufficient rate into the reaction chamber to interact with the substrate to deposit a layer containing silicon thereon at a predefined growth rate to obtain phase-pure epitaxial silicon film of increased thickness.

Nuclear ``pasta'' phase within density dependent hadronic models

NASA Astrophysics Data System (ADS)

Avancini, S. S.; Brito, L.; Marinelli, J. R.; Menezes, D. P.; de Moraes, M. M. W.; Providência, C.; Santos, A. M.

2009-03-01

In the present paper, we investigate the onset of the “pasta” phase with different parametrizations of the density dependent hadronic model and compare the results with one of the usual parametrizations of the nonlinear Walecka model. The influence of the scalar-isovector virtual δ meson is shown. At zero temperature, two different methods are used, one based on coexistent phases and the other on the Thomas-Fermi approximation. At finite temperature, only the coexistence phases method is used. npe matter with fixed proton fractions and in β equilibrium are studied. We compare our results with restrictions imposed on the values of the density and pressure at the inner edge of the crust, obtained from observations of the Vela pulsar and recent isospin diffusion data from heavy-ion reactions, and with predictions from spinodal calculations.

Advanced Multi-phase Flow CFD Model Development for Solid Rocket Motor Flowfield Analysis

NASA Technical Reports Server (NTRS)

Liaw, Paul; Chen, Yen-Sen

1995-01-01

A Navier-Stokes code, finite difference Navier-Stokes (FDNS), is used to analyze the complicated internal flowfield of the SRM (solid rocket motor) to explore the impacts due to the effects of chemical reaction, particle dynamics, and slag accumulation on the solid rocket motor (SRM). The particulate multi-phase flowfield with chemical reaction, particle evaporation, combustion, breakup, and agglomeration models are included in present study to obtain a better understanding of the SRM design. Finite rate chemistry model is applied to simulate the chemical reaction effects. Hermsen correlation model is used for the combustion simulation. The evaporation model introduced by Spalding is utilized to include the heat transfer from the particulate phase to the gase phase due to the evaporation of the particles. A correlation of the minimum particle size for breakup expressed in terms of the Al/Al2O3 surface tension and shear force was employed to simulate the breakup of particles. It is assumed that the breakup occurs when the Weber number exceeds 6. A simple L agglomeration model is used to investigate the particle agglomeration. However, due to the large computer memory requirements for the agglomeration model, only 2D cases are tested with the agglomeration model. The VOF (Volume of Fluid) method is employed to simulate the slag buildup in the aft-end cavity of the redesigned solid rocket motor (RSRM). Monte Carlo method is employed to calculate the turbulent dispersion effect of the particles. The flowfield analysis obtained using the FDNS code in the present research with finite rate chemical reaction, particle evaporation, combustion, breakup, agglomeration, and VOG models will provide a design guide for the potential improvement of the SRM including the use of materials and the shape of nozzle geometry such that a better performance of the SRM can be achieved. The simulation of the slag buildup in the aft-end cavity can assist the designer to improve the design of the RSRM geometry.

Computation of the phase response curve: a direct numerical approach.

PubMed

Govaerts, W; Sautois, B

2006-04-01

Neurons are often modeled by dynamical systems--parameterized systems of differential equations. A typical behavioral pattern of neurons is periodic spiking; this corresponds to the presence of stable limit cycles in the dynamical systems model. The phase resetting and phase response curves (PRCs) describe the reaction of the spiking neuron to an input pulse at each point of the cycle. We develop a new method for computing these curves as a by-product of the solution of the boundary value problem for the stable limit cycle. The method is mathematically equivalent to the adjoint method, but our implementation is computationally much faster and more robust than any existing method. In fact, it can compute PRCs even where the limit cycle can hardly be found by time integration, for example, because it is close to another stable limit cycle. In addition, we obtain the discretized phase response curve in a form that is ideally suited for most applications. We present several examples and provide the implementation in a freely available Matlab code.

Mechanism and microstructures in Ga2O3 pseudomartensitic solid phase transition.

PubMed

Zhu, Sheng-Cai; Guan, Shu-Hui; Liu, Zhi-Pan

2016-07-21

Solid-to-solid phase transition, although widely exploited in making new materials, challenges persistently our current theory for predicting its complex kinetics and rich microstructures in transition. The Ga2O3α-β phase transformation represents such a common but complex reaction with marked change in cation coordination and crystal density, which was known to yield either amorphous or crystalline products under different synthetic conditions. Here we, via recently developed stochastic surface walking (SSW) method, resolve for the first time the atomistic mechanism of Ga2O3α-β phase transformation, the pathway of which turns out to be the first reaction pathway ever determined for a new type of diffusionless solid phase transition, namely, pseudomartensitic phase transition. We demonstrate that the sensitivity of product crystallinity is caused by its multi-step, multi-type reaction pathway, which bypasses seven intermediate phases and involves all types of elementary solid phase transition steps, i.e. the shearing of O layers (martensitic type), the local diffusion of Ga atoms (reconstructive type) and the significant lattice dilation (dilation type). While the migration of Ga atoms across the close-packed O layers is the rate-determining step and yields "amorphous-like" high energy intermediates, the shearing of O layers contributes to the formation of coherent biphase junctions and the presence of a crystallographic orientation relation, (001)α//(201[combining macron])β + [120]α//[13[combining macron]2]β. Our experiment using high-resolution transmission electron microscopy further confirms the theoretical predictions on the atomic structure of biphase junction and the formation of (201[combining macron])β twin, and also discovers the late occurrence of lattice expansion in the nascent β phase that grows out from the parent α phase. By distinguishing pseudomartensitic transition from other types of mechanisms, we propose general rules to predict the product crystallinity of solid phase transition. The new knowledge on the kinetics of pseudomartensitic transition complements the theory of diffusionless solid phase transition.

Real-Time Optical Monitoring of Flow Kinetics and Gas Phase Reactions Under High-Pressure OMCVD Conditions

NASA Technical Reports Server (NTRS)

Dietz, N.; McCall, S.; Bachmann, K. J.

2001-01-01

This contribution addresses the real-time optical characterization of gas flow and gas phase reactions as they play a crucial role for chemical vapor phase depositions utilizing elevated and high pressure chemical vapor deposition (HPCVD) conditions. The objectives of these experiments are to validate on the basis of results on real-time optical diagnostics process models simulation codes, and provide input parameter sets needed for analysis and control of chemical vapor deposition at elevated pressures. Access to microgravity is required to retain high pressure conditions of laminar flow, which is essential for successful acquisition and interpretation of the optical data. In this contribution, we describe the design and construction of the HPCVD system, which include access ports for various optical methods of real-time process monitoring and to analyze the initial stages of heteroepitaxy and steady-state growth in the different pressure ranges. To analyze the onset of turbulence, provisions are made for implementation of experimental methods for in-situ characterization of the nature of flow. This knowledge will be the basis for the design definition of experiments under microgravity, where gas flow conditions, gas phase and surface chemistry, might be analyzed by remote controlled real-time diagnostics tools, developed in this research project.

Hybrid quantum and classical methods for computing kinetic isotope effects of chemical reactions in solutions and in enzymes.

PubMed

Gao, Jiali; Major, Dan T; Fan, Yao; Lin, Yen-Lin; Ma, Shuhua; Wong, Kin-Yiu

2008-01-01

A method for incorporating quantum mechanics into enzyme kinetics modeling is presented. Three aspects are emphasized: 1) combined quantum mechanical and molecular mechanical methods are used to represent the potential energy surface for modeling bond forming and breaking processes, 2) instantaneous normal mode analyses are used to incorporate quantum vibrational free energies to the classical potential of mean force, and 3) multidimensional tunneling methods are used to estimate quantum effects on the reaction coordinate motion. Centroid path integral simulations are described to make quantum corrections to the classical potential of mean force. In this method, the nuclear quantum vibrational and tunneling contributions are not separable. An integrated centroid path integral-free energy perturbation and umbrella sampling (PI-FEP/UM) method along with a bisection sampling procedure was summarized, which provides an accurate, easily convergent method for computing kinetic isotope effects for chemical reactions in solution and in enzymes. In the ensemble-averaged variational transition state theory with multidimensional tunneling (EA-VTST/MT), these three aspects of quantum mechanical effects can be individually treated, providing useful insights into the mechanism of enzymatic reactions. These methods are illustrated by applications to a model process in the gas phase, the decarboxylation reaction of N-methyl picolinate in water, and the proton abstraction and reprotonation process catalyzed by alanine racemase. These examples show that the incorporation of quantum mechanical effects is essential for enzyme kinetics simulations.

Coupled enzyme reactions performed in heterogeneous reaction media: experiments and modeling for glucose oxidase and horseradish peroxidase in a PEG/citrate aqueous two-phase system.

PubMed

Aumiller, William M; Davis, Bradley W; Hashemian, Negar; Maranas, Costas; Armaou, Antonios; Keating, Christine D

2014-03-06

The intracellular environment in which biological reactions occur is crowded with macromolecules and subdivided into microenvironments that differ in both physical properties and chemical composition. The work described here combines experimental and computational model systems to help understand the consequences of this heterogeneous reaction media on the outcome of coupled enzyme reactions. Our experimental model system for solution heterogeneity is a biphasic polyethylene glycol (PEG)/sodium citrate aqueous mixture that provides coexisting PEG-rich and citrate-rich phases. Reaction kinetics for the coupled enzyme reaction between glucose oxidase (GOX) and horseradish peroxidase (HRP) were measured in the PEG/citrate aqueous two-phase system (ATPS). Enzyme kinetics differed between the two phases, particularly for the HRP. Both enzymes, as well as the substrates glucose and H2O2, partitioned to the citrate-rich phase; however, the Amplex Red substrate necessary to complete the sequential reaction partitioned strongly to the PEG-rich phase. Reactions in ATPS were quantitatively described by a mathematical model that incorporated measured partitioning and kinetic parameters. The model was then extended to new reaction conditions, i.e., higher enzyme concentration. Both experimental and computational results suggest mass transfer across the interface is vital to maintain the observed rate of product formation, which may be a means of metabolic regulation in vivo. Although outcomes for a specific system will depend on the particulars of the enzyme reactions and the microenvironments, this work demonstrates how coupled enzymatic reactions in complex, heterogeneous media can be understood in terms of a mathematical model.

Separation and determination of synthetic impurities of difloxacin by reversed-phase high-performance liquid chromatography.

PubMed

Rao, R Nageswara; Nagaraju, V

2004-11-19

A simple and rapid reversed-phase high-performance liquid chromatographic method for separation and determination of process-related impurities of difloxacin (DFL) was developed. The separation was achieved on a reversed-phase C(18) column using methanol-water-acetic acid (78:21.9:0.1, v/v/v) as a mobile solvent at a flow rate of 1.0 ml/min at 28 degrees C using UV detection at 230 nm. It was linear over a range of 0.03 x 10(-6) to 1.60 x 10(-6)g for process related impurities and 0.05 x 10(-6) to 2.40 x 10(-6)g for difloxacin. The detection limits were 0.009 x 10(-6) to 0.024 x 10(-6)g for all the compounds examined. The recoveries were found to be in the range of 97.6-102.0% for impurities as well as difloxacin. The precision and robustness of the method were evaluated. It was used for not only quality assurance, but also monitoring the synthetic reactions involved in the process development work of difloxacin. The method was found to be specific, precise and reliable for the determination of unreacted levels of raw materials, intermediates in the reaction mixtures and the finished products of difloxacin.

Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase

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

Shan, Junjun; Zhang, Shiran; Choksi, Tej

2016-12-05

Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis weremore » explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.« less

Performance of the Proposed New Federal Reference Methods for Measuring Ozone Concentrations in Ambient Air

EPA Science Inventory

The current Federal Reference Method (FRM) for measuring concentrations of ozone in ambient air, described in EPA regulations at 40 CFR Part 50, Appendix D, is based on the dry, gas-phase, chemiluminescence reaction between ethylene (C₂H₄) and any ozone (O

Graft polymerization of wood sawdust and peat with ethylene carbonate. A novel method for the preparation of supports with enhanced mechanical properties to be used in biofiltration of organic vapors.

PubMed

Hernández-Meléndez, O; Peydecastaing, J; Bárzana, E; Vaca-Garcia, C; Hernández-Luna, M; Borredon, M E

2009-01-01

The graft polymerization reaction between ethylene carbonate (EC) and scots pine sawdust (SPS) or peat moss (PM) offers a solvent-free approach to the simple and inexpensive aliphatic derivatization of these lignocellulosic fibers. This reaction was studied with liquid or vapor EC phases in three different reactor configurations: batch stirred (BSR), semi-continuous stirred (SSR) and continuous tubular in the gas phase (CVTR). The use of a vapor phase allowed a satisfactory grafting yield and minimal production of non-grafted polyol by-products. The crosslinking agent 4,4'-methylenebis(phenylisocyanate) (MDI) achieved superior characteristics to form shaped tablets resistant to water disaggregation, a high water retention capacity and high compression strength, characteristics that conventional organic supports like PM or PM-polyurethane foam mixtures used in biofiltration of waste gases do not completely possess.

Electrically controlled microvalves to integrate microchip polymerase chain reaction and capillary electrophoresis.

PubMed

Kaigala, Govind V; Hoang, Viet N; Backhouse, Christopher J

2008-07-01

Microvalves are key in realizing portable miniaturized diagnostic platforms. We present a scalable microvalve that integrates well with standard lab on a chip (LOC) implementations, yet which requires essentially no external infrastructure for its operation. This electrically controlled, phase-change microvalve is used to integrate genetic amplification and analysis via capillary electrophoresis--the basis of many diagnostics. The microvalve is actuated using a polymer (polyethylene glycol, PEG) that exhibits a large volumetric change between its solid and liquid phases. Both the phase change of the PEG and the genetic amplification via polymerase chain reaction (PCR) are thermally controlled using thin film resistive elements that are patterned using standard microfabrication methods. By contrast with many other valve technologies, these microvalves and their control interface scale down in size readily. The novelty here lies in the use of fully integrated microvalves that require only electrical connections to realize a portable and inexpensive genetic analysis platform.

The local and systemic side-effects of venom and inhaled-allergen subcutaneous immunotherapy.

PubMed

Adamic, Katja; Zidarn, Mihaela; Bajrovic, Nissera; Erzen, Renato; Kopac, Peter; Music, Ema

2009-01-01

Although immunotherapy is effective in allergic rhinitis, conjunctivitis, asthma and stinging insect hypersensitivity, it carries a risk of anaphylactic reactions. In a 4-year retrospective survey, we investigated 1257 adult patients who had received venom or inhaled-allergen subcutaneous immunotherapy. The dose-increase phase was performed as the 2-day rush protocol for venom immunotherapy and the 6-week protocol for inhaled-allergen immunotherapy. A total of 904 patients received venom immunotherapy and 353 patients inhaled-allergen immunotherapy. The prevalence of systemic reactions was 13.6%. The frequency of systemic reactions was higher during the maintenance phase than in the dose-increase phase (9.6% vs. 5.9%) and was highest in both phases of treatment with honeybee venom (P < 0.001). The majority of systemic reactions were mild. Five (0.4%) patients had reaction with a fall of blood pressure and were treated with adrenaline. There was no fatal outcome. The systemic side-effects during the dose-increase phase of venom immunotherapy occurred at a median dose of 46 microg (range 2-100 microg). Large local reactions occurred in 13.9% of patients without any significant difference between the allergens. We have shown that systemic reactions are not rare even during maintenance phase in patients with a well tolerated dose-increase phase of treatment. The most prominent risk factor for systemic reactions was immunotherapy with honeybee extract.

Native Chemical Ligation Strategy to Overcome Side Reactions during Fmoc-Based Synthesis of C-Terminal Cysteine-Containing Peptides.

PubMed

Lelièvre, Dominique; Terrier, Victor P; Delmas, Agnès F; Aucagne, Vincent

2016-03-04

The Fmoc-based solid phase synthesis of C-terminal cysteine-containing peptides is problematic, due to side reactions provoked by the pronounced acidity of the Cα proton of cysteine esters. We herein describe a general strategy consisting of the postsynthetic introduction of the C-terminal Cys through a key chemoselective native chemical ligation reaction with N-Hnb-Cys peptide crypto-thioesters. This method was successfully applied to the demanding peptide sequences of two natural products of biological interest, giving remarkably high overall yields compared to that of a state of the art strategy.

Low-temperature rapid synthesis and superconductivity of Fe-based oxypnictide superconductors.

PubMed

Fang, Ai-Hua; Huang, Fu-Qiang; Xie, Xiao-Ming; Jiang, Mian-Heng

2010-03-17

Fe-based oxypnictide superconductors were successfully synthesized at lower reaction temperatures and with shorter reaction times made possible by starting with less stable compounds, which provide a larger driving force for reactions. Using ball-milled powders of intermediate compounds, phase-pure superconductors with T(c) above 50 K were synthesized at 1173 K in 20 min. This method is particularly advantageous for retaining F, a volatile dopant that enhances superconductivity. Bulk superconductivity and high upper critical fields up to 392 T in Sm(0.85)Nd(0.15)FeAsO(0.85)F(0.15) were demonstrated.

Gas-phase ion/ion reactions of peptides and proteins: acid/base, redox, and covalent chemistries

PubMed Central

Prentice, Boone M.

2013-01-01

Gas-phase ion/ion reactions are emerging as useful and flexible means for the manipulation and characterization of peptide and protein biopolymers. Acid/base-like chemical reactions (i.e., proton transfer reactions) and reduction/oxidation (redox) reactions (i.e., electron transfer reactions) represent relatively mature classes of gas-phase chemical reactions. Even so, especially in regards to redox chemistry, the widespread utility of these two types of chemistries is undergoing rapid growth and development. Additionally, a relatively new class of gas-phase ion/ion transformations is emerging which involves the selective formation of functional-group-specific covalent bonds. This feature details our current work and perspective on the developments and current capabilities of these three areas of ion/ion chemistry with an eye towards possible future directions of the field. PMID:23257901

Gas-phase ion/ion reactions of peptides and proteins: acid/base, redox, and covalent chemistries.

PubMed

Prentice, Boone M; McLuckey, Scott A

2013-02-01

Gas-phase ion/ion reactions are emerging as useful and flexible means for the manipulation and characterization of peptide and protein biopolymers. Acid/base-like chemical reactions (i.e., proton transfer reactions) and reduction/oxidation (redox) reactions (i.e., electron transfer reactions) represent relatively mature classes of gas-phase chemical reactions. Even so, especially in regards to redox chemistry, the widespread utility of these two types of chemistries is undergoing rapid growth and development. Additionally, a relatively new class of gas-phase ion/ion transformations is emerging which involves the selective formation of functional-group-specific covalent bonds. This feature details our current work and perspective on the developments and current capabilities of these three areas of ion/ion chemistry with an eye towards possible future directions of the field.

Contact structure for use in catalytic distillation

DOEpatents

Jones, Jr., Edward M.

1984-01-01

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

Confocal Raman microscopy for monitoring chemical reactions on single optically trapped, solid-phase support particles.

PubMed

Houlne, Michael P; Sjostrom, Christopher M; Uibel, Rory H; Kleimeyer, James A; Harris, Joel M

2002-09-01

Optical trapping of small structures is a powerful tool for the manipulation and investigation of colloidal and particulate materials. The tight focus excitation requirements of optical trapping are well suited to confocal Raman microscopy. In this work, an inverted confocal Raman microscope is developed for studies of chemical reactions on single, optically trapped particles and applied to reactions used in solid-phase peptide synthesis. Optical trapping and levitation allow a particle to be moved away from the coverslip and into solution, avoiding fluorescence interference from the coverslip. More importantly, diffusion of reagents into the particle is not inhibited by a surface, so that reaction conditions mimic those of particles dispersed in solution. Optical trapping and levitation also maintain optical alignment, since the particle is centered laterally along the optical axis and within the focal plane of the objective, where both optical forces and light collection are maximized. Hour-long observations of chemical reactions on individual, trapped silica particles are reported. Using two-dimensional least-squares analysis methods, the Raman spectra collected during the course of a reaction can be resolved into component contributions. The resolved spectra of the time-varying species can be observed, as they bind to or cleave from the particle surface.

The phase stability of Ca2TiO4 and related Ruddlesden-Popper phases

NASA Astrophysics Data System (ADS)

Ramadan, Amr H. H.; Hesselmann, Linda; De Souza, Roger A.

2015-11-01

The Ruddlesden-Popper phases of the Ca-Ti-O system, Can+1TinO3n+1, are investigated by means of atomistic simulations employing empirical pair potentials. The stability of the phases is examined in terms of various reaction schemes: the formation from the binary oxides, the addition of the perovskite oxide to a given phase, and the reaction between perovskite and rock-salt oxides. The energies of these reactions are compared with results previously obtained for the Ruddlesden-Popper phases of the Sr-Ti-O system. The importance of the disproportionation reaction of the various R-P phases in both Ca and Sr systems is also emphasized. The results obtained are in good agreement with experimental observations regarding both systems.

Phase Equilibria of the Sn-Ni-Si Ternary System and Interfacial Reactions in Sn-(Cu)/Ni-Si Couples

NASA Astrophysics Data System (ADS)

Fang, Gu; Chen, Chih-chi

2015-07-01

Interfacial reactions in Sn/Ni-4.5 wt.%Si and Sn-Cu/Ni-4.5 wt.%Si couples at 250°C, and Sn-Ni-Si ternary phase equilibria at 250°C were investigated in this study. Ni-Si alloys, which are nonmagnetic, can be regarded as a diffusion barrier layer material in flip chip packaging. Solder/Ni-4.5 wt.%Si interfacial reactions are crucial to the reliability of soldered joints. Phase equilibria information is essential for development of solder/Ni-Si materials. No ternary compound is present in the Sn-Ni-Si ternary system at 250°C. Extended solubility of Si in the phases Ni3Sn2 and Ni3Sn is 3.8 and 6.1 at.%, respectively. As more Si dissolves in these phases their lattice constants decrease. No noticeable ternary solubility is observed for the other intermetallics. Interfacial reactions in solder/Ni-4.5 wt.%Si are similar to those for solder/Ni. Si does not alter the reaction phases. No Si solubility in the reaction phases was detected, although rates of growth of the reaction phases were reduced. Because the alloy Ni-4.5 wt.%Si reacts more slowly with solders than pure Ni, the Ni-4.5 wt.%Si alloy could be a potential new diffusion barrier layer material for flip chip packaging.

Geochemical Modeling of Reactions and Partitioning of Trace Metals and Radionuclides during Titration of Contaminated Acidic Sediments

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

Zhang, Fan; Parker, Jack C.; Luo, Wensui

2008-01-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This study was undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cationmore » exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO{sub 4}{sup 2-} for contaminated sediments indicated close agreement, suggesting that the model could potentially be used to predict the acid-base behavior of the sediment-solution system under variable pH conditions.« less

Optimization of calcium phosphate fine ceramic powders preparation

NASA Astrophysics Data System (ADS)

Sezanova, K.; Tepavitcharova, S.; Rabadjieva, D.; Gergulova, R.; Ilieva, R.

2013-12-01

The effect of biomimetic synthesis method, reaction medium and further precursor treatments on the chemical and phase composition, crystal size and morphology of calcium phosphates was examined. Nanosized calcium phosphate precursors were biomimetically precipitated by the method of continuous precipitation in three types of reaction media at pH 8: (i) SBF as an inorganic electrolyte system; (ii) organic (glycerine) modified SBF (volume ratio of 1:1); (iii) polymer (10 g/l xanthan gum or 10 g/l guar gum) modified SBF (volume ratio of 1:1). After maturation (24 h) the samples were lyophilized, calcinated at 300°C for 3 hours, and washed with water, followed by new gelation, lyophilization and step-wise (200, 400, 600, 800, and 1000°C, each for 3 hours) sintering. The reaction medium influenced the chemical composition and particle size but not the morphology of the calcium phosphate powders. In all studied cases bi-phase calcium phosphate fine powders with well-shaped spherical grains, consisting of β-tricalcium phosphate (β-TCP) and hydroxyapatite (HA) with a Ca/P ratio of 1.3 - 1.6 were obtained. The SBF modifiers decreased the particle size of the product in the sequence guar gum ˜ xanthan gum < glycerin < SBF medium.

Generic HPLC platform for automated enzyme reaction monitoring: Advancing the assay toolbox for transaminases and other PLP-dependent enzymes.

PubMed

Börner, Tim; Grey, Carl; Adlercreutz, Patrick

2016-08-01

Methods for rapid and direct quantification of enzyme kinetics independent of the substrate stand in high demand for both fundamental research and bioprocess development. This study addresses the need for a generic method by developing an automated, standardizable HPLC platform monitoring reaction progress in near real-time. The method was applied to amine transaminase (ATA) catalyzed reactions intensifying process development for chiral amine synthesis. Autosampler-assisted pipetting facilitates integrated mixing and sampling under controlled temperature. Crude enzyme formulations in high and low substrate concentrations can be employed. Sequential, small (1 µL) sample injections and immediate detection after separation permits fast reaction monitoring with excellent sensitivity, accuracy and reproducibility. Due to its modular design, different chromatographic techniques, e.g. reverse phase and size exclusion chromatography (SEC) can be employed. A novel assay for pyridoxal 5'-phosphate-dependent enzymes is presented using SEC for direct monitoring of enzyme-bound and free reaction intermediates. Time-resolved changes of the different cofactor states, e.g. pyridoxal 5'-phosphate, pyridoxamine 5'-phosphate and the internal aldimine were traced in both half reactions. The combination of the automated HPLC platform with SEC offers a method for substrate-independent screening, which renders a missing piece in the assay and screening toolbox for ATAs and other PLP-dependent enzymes. Copyright © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

A novel method to measure isotopic labeled gas-phase nitrous acid (HO15NO) in biogeochemical studies

NASA Astrophysics Data System (ADS)

Wu, Dianming; Kampf, Christopher; Pöschl, Ulrich; Oswald, Robert; Cui, Junfang; Ermel, Michael; Hu, Chunsheng; Trebs, Ivonne; Sörgel, Matthias

2014-05-01

We developed a new method (gas-phase stripping-derivatization coupled to LC-MS) to measure the 15N atom percent excess (APE) of HONO in the gas-phase. Gaseous HONO is quantitatively collected and transferred to an azo dye by the well-known Griess reaction in the Long Path Absorption Photometer (LOPAP). The reaction solutions containing the dye are collected at the outflow of the LOPAP, purified by solid-phase extraction and analyzed using high performance liquid chromatography coupled to mass spectrometry (HPLC-MS). The unlabeled azo dye (C18H19O2N5S) with a monoisotopic molecular mass of 369.41 g mol-1 can be detected as its protonated molecular ion ([M+H+], M) by HPLC-MS at a retention time of 2.8 min. Due to the natural isotope distribution M + 0, M + 1, M + 2, and M + 3 ions were considered for the calculation of the 15N APE. The optimal working range was found to be between 20 and 50% for the 15N/14N ratio. The optimum pH and solvents for extraction by SPE and potential interferences are discussed. The method has been applied for the measurement of HO15NO emissions from soil in a dynamic chamber with and without spiking 15N labeled urea. Our results confirm biogenic HONO emissions from soil as HO15NO was measured after addition of 15N urea.

Review of the methods to form hydrogen peroxide in electrical discharge plasma with liquid water

NASA Astrophysics Data System (ADS)

Locke, Bruce R.; Shih, Kai-Yuan

2011-06-01

This paper presents a review of the literature dealing with the formation of hydrogen peroxide from plasma processes. Energy yields for hydrogen peroxide generation by plasma from water span approximately three orders of magnitude from 4 × 10-2 to 80 g kWh-1. A wide range of plasma processes from rf to pulsed, ac, and dc discharges directly in the liquid phase have similar energy yields and may thus be limited by radical quenching processes at the plasma-liquid interface. Reactor modification using discharges in bubbles and discharges over the liquid phase can provide modest improvements in energy yield over direct discharge in the liquid, but the interpretation is complicated by additional chemical reactions of gas phase components such as ozone and nitrogen oxides. The highest efficiency plasma process utilizes liquid water droplets that may enhance efficiency by sequestering hydrogen peroxide in the liquid and by suppressing decomposition reactions by radicals from the gas and at the interface. Kinetic simulations of water vapor reported in the literature suggest that plasma generation of hydrogen peroxide should approach 45% of the thermodynamics limit, and this fact coupled with experimental studies demonstrating improvements with the presence of the condensed liquid phase suggest that further improvements in energy yield may be possible. Plasma generation of hydrogen peroxide directly from water compares favorably with a number of other methods including electron beam, ultrasound, electrochemical and photochemical methods, and other chemical processes.

Hydrogenation at low temperatures does not always lead to saturation: the case of HNCO

NASA Astrophysics Data System (ADS)

Noble, J. A.; Theule, P.; Congiu, E.; Dulieu, F.; Bonnin, M.; Bassas, A.; Duvernay, F.; Danger, G.; Chiavassa, T.

2015-04-01

Context. It is generally agreed that hydrogenation reactions dominate chemistry on grain surfaces in cold, dense molecular cores, saturating the molecules present in ice mantles. Aims: We present a study of the low temperature reactivity of solid phase isocyanic acid (HNCO) with hydrogen atoms, with the aim of elucidating its reaction network. Methods: Fourier transform infrared spectroscopy and mass spectrometry were employed to follow the evolution of pure HNCO ice during bombardment with H atoms. Both multilayer and monolayer regimes were investigated. Results: The hydrogenation of HNCO does not produce detectable amounts of formamide (NH2CHO) as the major product. Experiments using deuterium reveal that deuteration of solid HNCO occurs rapidly, probably via cyclic reaction paths regenerating HNCO. Chemical desorption during these reaction cycles leads to loss of HNCO from the surface. Conclusions: It is unlikely that significant quantities of NH2CHO form from HNCO. In dense regions, however, deuteration of HNCO will occur. HNCO and DNCO will be introduced into the gas phase, even at low temperatures, as a result of chemical desorption.

Rate constants for reactions of ClO/x/ of atmospheric interest

NASA Technical Reports Server (NTRS)

Watson, R. T.

1977-01-01

Chemical kinetics measurements on 82 gas phase reactions of chlorine containing species are reviewed. Recommended rate constants are given. The principal species of interest are Cl, Cl2, ClO, Cl2O, ClOO, OClO, CINO, HCl and halo derivatives of methane and ethane. Absorption spectra are given for 21 species. In addition the chemical kinetics methods used to obtain these data are discussed with regard to their applicability and reliability.

RATE CONSTANTS FOR THE REACTIONS OF OH RADICALS AND CL ATOMS WITH DI-N-PROPYL ETHER AND DI-N-BUTYL ETHER AND THEIR DEUTERATED ANALOGS. (R825252)

EPA Science Inventory

Using relative rate methods, rate constants for the gas-phase reactions of OH radicals and Cl atoms with di-n-propyl ether, di-n-propyl ether-d₁₄, di-n-butyl ether and di-n-butyl ether-d₁₈ have been measured at 296 ? 2 K and atmos...

Flow injection spectrophotometric method for chloride determination in natural waters using Hg(SCN)(2) immobilized in epoxy resin.

PubMed

Silva, Claudineia R; Vieira, Heberth J; Canaes, Larissa S; Nóbrega, Joaquim A; Fatibello-Filho, Orlando

2005-02-28

A flow injection (FI) spectrophotometric method was proposed for the determination of chloride ion in natural waters. The determination of chloride was carried out by reaction with Hg(SCN)(2) immobilized in an epoxy resin bead in a solid-phase reactor (SPR) and the thiocyanate ions released were determined spectrophotometrically at 480nm after complexing reaction with Fe(III). The analytical curve for chloride was linear in the concentration range from 5.6 x 10(-5) to 2.2 x 10(-4)moll(-1) with a detection limit of 1.4 x 10(-5)moll(-1). The relative standard deviation (R.S.D.) was 2.2% for a solution containing 2.2 x 10(-4)moll(-1) (n = 10). The simple manifold allows a routine analytical frequency of 100 determinations per hour. The main advantage of the developed method is the 400% reduction of the Hg waste solution generated when compared to conventional methods for chloride determination based on the same spectrophotometric reaction.

Ferroelectric/ferrimagnetic composite ceramics with depressed interfacial reaction and low dielectric loss

NASA Astrophysics Data System (ADS)

Zheng, Hui; Weng, Wenjian; Han, Gaorong; Du, Piyi

2014-10-01

(1-x)BaTiO3/xNi0.5Zn0.5Fe2O4 (NZFO) ferroelectric/ferrimagnetic composite ceramics with restricted interfacial reaction were prepared by adopting fine NZFO precursors synthesized by combustion method. The dielectric dispersion, loss, and conductivity are significantly reduced at most compositions, particularly at concentrations below the percolation threshold. At x = 0.3, a frequency-stable permittivity of 2300 and a low loss of 0.04 at 1 kHz is realized. The recovery of the dielectric/electric properties is attributed to the interfacial amorphous phase introduced by the fine NZFO precursors, which can act as barrier for ionic inter-diffusion between the two phases and hopping conduction among ferrites.

Organic aerogel microspheres

DOEpatents

Mayer, S.T.; Kong, F.M.; Pekala, R.W.; Kaschmitter, J.L.

1999-06-01

Organic aerogel microspheres are disclosed which can be used in capacitors, batteries, thermal insulation, adsorption/filtration media, and chromatographic packings, having diameters ranging from about 1 micron to about 3 mm. The microspheres can be pyrolyzed to form carbon aerogel microspheres. This method involves stirring the aqueous organic phase in mineral oil at elevated temperature until the dispersed organic phase polymerizes and forms nonstick gel spheres. The size of the microspheres depends on the collision rate of the liquid droplets and the reaction rate of the monomers from which the aqueous solution is formed. The collision rate is governed by the volume ratio of the aqueous solution to the mineral oil and the shear rate, while the reaction rate is governed by the chemical formulation and the curing temperature.

Organic aerogel microspheres

DOEpatents

Mayer, Steven T.; Kong, Fung-Ming; Pekala, Richard W.; Kaschmitter, James L.

1999-01-01

Organic aerogel microspheres which can be used in capacitors, batteries, thermal insulation, adsorption/filtration media, and chromatographic packings, having diameters ranging from about 1 micron to about 3 mm. The microspheres can be pyrolyzed to form carbon aerogel microspheres. This method involves stirring the aqueous organic phase in mineral oil at elevated temperature until the dispersed organic phase polymerizes and forms nonsticky gel spheres. The size of the microspheres depends on the collision rate of the liquid droplets and the reaction rate of the monomers from which the aqueous solution is formed. The collision rate is governed by the volume ratio of the aqueous solution to the mineral oil and the shear rate, while the reaction rate is governed by the chemical formulation and the curing temperature.

Selective hydrogenation of phenol to cyclohexanone over Pd@CN (N-doped porous carbon): Role of catalyst reduction method

NASA Astrophysics Data System (ADS)

Hu, Shuo; Yang, Guangxin; Jiang, Hong; Liu, Yefei; Chen, Rizhi

2018-03-01

Selective phenol hydrogenation is a green and sustainable technology to produce cyclohexanone. The work focused on investigating the role of catalyst reduction method in the liquid-phase phenol hydrogenation to cyclohexanone over Pd@CN (N-doped porous carbon). A series of reduction methods including flowing hydrogen reduction, in-situ reaction reduction and liquid-phase reduction were designed and performed. The results highlighted that the reduction method significantly affected the catalytic performance of Pd@CN in the liquid-phase hydrogenation of phenol to cyclohexanone, and the liquid-phase reduction with the addition of appropriate amount of phenol was highly efficient to improve the catalytic activity of Pd@CN. The influence mechanism was explored by a series of characterizations. The results of TEM, XPS and CO chemisorption confirmed that the reduction method mainly affected the size, surface composition and dispersion of Pd in the CN material. The addition of phenol during the liquid-phase reduction could inhibit the aggregation of Pd NPs and promote the reduction of Pd (2+), and then improved the catalytic activity of Pd@CN. The work would aid the development of high-performance Pd@CN catalysts for selective phenol hydrogenation.

A proposed simulation method for directed self-assembly of nanographene

NASA Astrophysics Data System (ADS)

Geraets, J. A.; Baldwin, J. P. C.; Twarock, R.; Hancock, Y.

2017-09-01

A methodology for predictive kinetic self-assembly modeling of bottom-up chemical synthesis of nanographene is proposed. The method maintains physical transparency in using a novel array format to efficiently store molecule information and by using array operations to determine reaction possibilities. Within a minimal model approach, the parameter space for the bond activation energies (i.e. molecule functionalization) at fixed reaction temperature and initial molecule concentrations is explored. Directed self-assembly of nanographene from functionalized tetrabenzanthracene and benzene is studied with regions in the activation energy phase-space showing length-to-width ratio tunability. The degree of defects and reaction reproducibility in the simulations is also determined, with the rate of functionalized benzene addition providing additional control of the dimension and quality of the nanographene. Comparison of the reaction energetics to available density functional theory data suggests the synthesis may be experimentally tenable using aryl-halide cross-coupling and noble metal surface-assisted catalysis. With full access to the intermediate reaction network and with dynamic coupling to density functional theory-informed tight-binding simulation, the method is proposed as a computationally efficient means towards detailed simulation-driven design of new nanographene systems.

Development of a Detailed Surface Chemistry Framework in DSMC

NASA Technical Reports Server (NTRS)

Swaminathan-Gopalan, K.; Borner, A.; Stephani, K. A.

2017-01-01

Many of the current direct simulation Monte Carlo (DSMC) codes still employ only simple surface catalysis models. These include only basic mechanisms such as dissociation, recombination, and exchange reactions, without any provision for adsorption and finite rate kinetics. Incorporating finite rate chemistry at the surface is increasingly becoming a necessity for various applications such as high speed re-entry flows over thermal protection systems (TPS), micro-electro-mechanical systems (MEMS), surface catalysis, etc. In the recent years, relatively few works have examined finite-rate surface reaction modeling using the DSMC method.In this work, a generalized finite-rate surface chemistry framework incorporating a comprehensive list of reaction mechanisms is developed and implemented into the DSMC solver SPARTA. The various mechanisms include adsorption, desorption, Langmuir-Hinshelwood (LH), Eley-Rideal (ER), Collision Induced (CI), condensation, sublimation, etc. The approach is to stochastically model the various competing reactions occurring on a set of active sites. Both gas-surface (e.g., ER, CI) and pure-surface (e.g., LH, desorption) reaction mechanisms are incorporated. The reaction mechanisms could also be catalytic or surface altering based on the participation of the bulk-phase species (e.g., bulk carbon atoms). Marschall and MacLean developed a general formulation in which multiple phases and surface sites are used and we adopt a similar convention in the current work. Microscopic parameters of reaction probabilities (for gas-surface reactions) and frequencies (for pure-surface reactions) that are require for DSMC are computed from the surface properties and macroscopic parameters such as rate constants, sticking coefficients, etc. The energy and angular distributions of the products are decided based on the reaction type and input parameters. Thus, the user has the capability to model various surface reactions via user-specified reaction rate constants, surface properties and parameters.

Spectrophotometric and high performance liquid chromatographic methods for sensitive determination of bisphenol A

NASA Astrophysics Data System (ADS)

Zhuang, Yafeng; Zhou, Meng; Gu, Jia; Li, Xiangmei

2014-03-01

A new spectrophotometric method for the determination of trace amounts of bisphenol A based on a diazotization-coupling reaction was developed. In acidic solution, clenbuterol was first diazotized with sodium nitrite, then coupled with bisphenol A to from an azo-compound [I] in NH3-NH4Cl buffer, which shows a maximum absorption at 410 nm. The effects of the amount of sodium nitrite, diazo reaction time, the amount of clenbuterol, coupling reaction time and coupling reaction temperature have been examined. Under the optional conditions, the determination of the linear range of bisphenol A is 0.24-8.4 μg/mL, correlation coefficient is 0.9905 and detection limit of this method is 0.15 μg/mL. The spectrophotometric method is simple, rapid, high sensitivity with better accuracy. High performance liquid chromatography (HPLC) technique combined with this new spectrophotometric method has been also developed for the measurement of bisphenol A. The analysis was achieved on a C18 column using water and methanol as a mobile phase and the detection was done spectrophotometrically at 410 nm. These reported methods were applied to the determination of bisphenol A in hot water in contact with commercially available table-water bottle samples.

Mean grain size detection of DP590 steel plate using a corrected method with electromagnetic acoustic resonance.

PubMed

Wang, Bin; Wang, Xiaokai; Hua, Lin; Li, Juanjuan; Xiang, Qing

2017-04-01

Electromagnetic acoustic resonance (EMAR) is a considerable method to determine the mean grain size of the metal material with a high precision. The basic ultrasonic attenuation theory used for the mean grain size detection of EMAR is come from the single phase theory. In this paper, the EMAR testing was carried out based on the ultrasonic attenuation theory. The detection results show that the double peaks phenomenon occurs in the EMAR testing of DP590 steel plate. The dual phase structure of DP590 steel is the inducement of the double peaks phenomenon in the EMAR testing. In reaction to the phenomenon, a corrected method with EMAR was put forward to detect the mean grain size of dual phase steel. Compared with the traditional attenuation evaluation method and the uncorrected method with EMAR, the corrected method with EMAR shows great effectiveness and superiority for the mean grain size detection of DP590 steel plate. Copyright © 2016. Published by Elsevier B.V.

Solid-Phase Enrichment and Analysis of Azide-Labeled Natural Products: Fishing Downstream of Biochemical Pathways.

PubMed

Pérez, Alexander J; Wesche, Frank; Adihou, Hélène; Bode, Helge B

2016-01-11

Many methods have been devised over the decades to trace precursors of specific molecules in cellular environments as, for example, in biosynthesis studies. The advent of click chemistry has facilitated the powerful combination of tracing and at the same time sieving the highly complex metabolome for compounds derived from simple or complex starting materials, especially when the click reaction takes place on a solid support. While the principle of solid-phase click reactions has already been successfully applied for selective protein and peptide enrichment, the successful enrichment of much smaller primary and secondary metabolites, showing great structural diversity and undergoing many different biosynthetic steps, has seen only little development. For bacterial secondary metabolism, a far broader tolerance for "clickable" precursors was observed than in ribosomal proteinogenesis, thus making this method a surprisingly valuable tool for the tracking and discovery of compounds within the cellular biochemical network. The implementation of this method has led to the identification of several new compounds from the bacterial genera Photorhabdus and Xenorhabdus, clearly proving its power. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The role of gas phase reactions in the deflagration-to-detonation transition of high energy propellants

NASA Technical Reports Server (NTRS)

Boggs, T. L.; Price, C. F.; Atwood, A. I.; Zurn, D. E.; Eisel, J. L.; Derr, R. L.

1980-01-01

The inadequacies of the two commonly used assumptions are shown, along with the need for considering gas phase reactions. Kinetic parameters that describe the gas phase reactions for several ingredients are provided, and the first steps in convective combustion leading to deflagration to detonation transition are described.

In Situ Environmental TEM in Imaging Gas and Liquid Phase Chemical Reactions for Materials Research.

PubMed

Wu, Jianbo; Shan, Hao; Chen, Wenlong; Gu, Xin; Tao, Peng; Song, Chengyi; Shang, Wen; Deng, Tao

2016-11-01

Gas and liquid phase chemical reactions cover a broad range of research areas in materials science and engineering, including the synthesis of nanomaterials and application of nanomaterials, for example, in the areas of sensing, energy storage and conversion, catalysis, and bio-related applications. Environmental transmission electron microscopy (ETEM) provides a unique opportunity for monitoring gas and liquid phase reactions because it enables the observation of those reactions at the ultra-high spatial resolution, which is not achievable through other techniques. Here, the fundamental science and technology developments of gas and liquid phase TEM that facilitate the mechanistic study of the gas and liquid phase chemical reactions are discussed. Combined with other characterization tools integrated in TEM, unprecedented material behaviors and reaction mechanisms are observed through the use of the in situ gas and liquid phase TEM. These observations and also the recent applications in this emerging area are described. The current challenges in the imaging process are also discussed, including the imaging speed, imaging resolution, and data management. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

21 CFR 184.1005 - Acetic acid.

Code of Federal Regulations, 2011 CFR

2011-04-01

... carbohydrates or by organic synthesis. The principal synthetic methods currently employed are oxidation of acetaldehyde derived from ethylene, liquid phase oxidation of butane, and reaction of carbon monoxide with methanol derived from natural gas. (b) The ingredient meets the specifications of the Food Chemicals Codex...

The role of NH3 and hydrocarbon mixtures in GaN pseudo-halide CVD: a quantum chemical study.

PubMed

Gadzhiev, Oleg B; Sennikov, Peter G; Petrov, Alexander I; Kachel, Krzysztof; Golka, Sebastian; Gogova, Daniela; Siche, Dietmar

2014-11-01

The prospects of a control for a novel gallium nitride pseudo-halide vapor phase epitaxy (PHVPE) with HCN were thoroughly analyzed for hydrocarbons-NH3-Ga gas phase on the basis of quantum chemical investigation with DFT (B3LYP, B3LYP with D3 empirical correction on dispersion interaction) and ab-initio (CASSCF, coupled clusters, and multireference configuration interaction including MRCI+Q) methods. The computational screening of reactions for different hydrocarbons (CH4, C2H6, C3H8, C2H4, and C2H2) as readily available carbon precursors for HCN formation, potential chemical transport agents, and for controlled carbon doping of deposited GaN was carried out with the B3LYP method in conjunction with basis sets up to aug-cc-pVTZ. The gas phase intermediates for the reactions in the Ga-hydrocarbon systems were predicted at different theory levels. The located π-complexes Ga…C2H2 and Ga…C2H4 were studied to determine a probable catalytic activity in reactions with NH3. A limited influence of the carbon-containing atmosphere was exhibited for the carbon doping of GaN crystal in the conventional GaN chemical vapor deposition (CVD) process with hydrocarbons injected in the gas phase. Our results provide a basis for experimental studies of GaN crystal growth with C2H4 and C2H2 as auxiliary carbon reagents for the Ga-NH3 and Ga-C-NH3 CVD systems and prerequisites for reactor design to enhance and control the PHVPE process through the HCN synthesis.

Chrystal structure properties of Al-doped Li{sub 4}Ti{sub 5}O{sub 12} synthesized by solid state reaction method

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

Sandi, Dianisa Khoirum, E-mail: dianisa875@gmail.com; Suryana, Risa, E-mail: rsuryana@staff.uns.ac.id; Priyono, Slamet, E-mail: slam013@lipi.go.id

2016-02-08

This research aim is to analyze the effect of Aluminum (Al) doping in the structural properties of Al-doped Li{sub 4}Ti{sub 5}O{sub 12} as anode in lithium ion battery. Al-doped Li{sub 4}Ti{sub 5}O{sub 12} powders were synthesized by solid state reaction method. LiOH.H{sub 2}O, TiO{sub 2}, and Al{sub 2}O{sub 3} were raw materials. These materials were milled for 15 h, calcined at temperature of 750{sup o}C and sintered at temperature of 800{sup o}C. Mole percentage of doping Al (x) was varied at x=0; x=0.025; and x =0.05. Al-doped Li{sub 4}Ti{sub 5}O{sub 12} powders were synthesized by solid state reaction method. X-ray diffractionmore » was employed to determine the structure of Li{sub 4}Ti{sub 5}O{sub 12}. The PDXL software was performed on the x-ray diffraction data to estimate the phase percentage, the lattice parameter, the unit cell volume, and the crystal density. Al-doped Li{sub 4}Ti{sub 5}O{sub 12} has cubic crystal structure. Al-doping at x=0 and x=0.025 does not change the phase as Li{sub 4}Ti{sub 5}O{sub 12} while at x=0.050 the phase changes to the LiTiAlO{sub 4}. The diffraction patterns show that the angle shifted to the right as the increase of x which indicated that Al substitute Ti site. Percentage of Li{sub 4}Ti{sub 5}O{sub 12} phase at x=0 and x=0.025 was 97.8% and 96.8%, respectively. However, the lattice parameters, the unit cell volume, and the crystal density does not change significantly at x=0; x=0.025; and x=0.050. Based on the percentage of Li{sub 4}Ti{sub 5}O{sub 12} phase, the Al-doped Li at x=0 and x=0.025 is promising as a lithium battery anode.« less

Surface engineered nanoparticles for improved surface enhanced Raman scattering applications and method for preparing same

DOEpatents

Simmons, Blake A [San Francisco, CA; Talin, Albert Alec [Livermore, CA

2009-11-27

A method for producing metal nanoparticles that when associated with an analyte material will generate an amplified SERS spectrum when the analyte material is illuminated by a light source and a spectrum is recorded. The method for preparing the metal nanoparticles comprises the steps of (i) forming a water-in-oil microemulsion comprising a bulk oil phase, a dilute water phase, and one or more surfactants, wherein the water phase comprises a transition metal ion; (ii) adding an aqueous solution comprising a mild reducing agent to the water-in-oil microemulsion; (iii) stirring the water-in-oil microemulsion and aqueous solution to initiate a reduction reaction resulting in the formation of a fine precipitate dispersed in the water-in-oil microemulsion; and (iv) separating the precipitate from the water-in-oil microemulsion.

Surface-Activated Coupling Reactions Confined on a Surface.

PubMed

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

2015-10-20

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

Exploring the free energy surface using ab initio molecular dynamics

NASA Astrophysics Data System (ADS)

Samanta, Amit; Morales, Miguel A.; Schwegler, Eric

2016-04-01

Efficient exploration of configuration space and identification of metastable structures in condensed phase systems are challenging from both computational and algorithmic perspectives. In this regard, schemes that utilize a set of pre-defined order parameters to sample the relevant parts of the configuration space [L. Maragliano and E. Vanden-Eijnden, Chem. Phys. Lett. 426, 168 (2006); J. B. Abrams and M. E. Tuckerman, J. Phys. Chem. B 112, 15742 (2008)] have proved useful. Here, we demonstrate how these order-parameter aided temperature accelerated sampling schemes can be used within the Born-Oppenheimer and the Car-Parrinello frameworks of ab initio molecular dynamics to efficiently and systematically explore free energy surfaces, and search for metastable states and reaction pathways. We have used these methods to identify the metastable structures and reaction pathways in SiO2 and Ti. In addition, we have used the string method [W. E, W. Ren, and E. Vanden-Eijnden, Phys. Rev. B 66, 052301 (2002); L. Maragliano et al., J. Chem. Phys. 125, 024106 (2006)] within the density functional theory to study the melting pathways in the high pressure cotunnite phase of SiO2 and the hexagonal closed packed to face centered cubic phase transition in Ti.

Facile Quantification and Identification Techniques for Reducing Gases over a Wide Concentration Range Using a MOS Sensor in Temperature-Cycled Operation.

PubMed

Schultealbert, Caroline; Baur, Tobias; Schütze, Andreas; Sauerwald, Tilman

2018-03-01

Dedicated methods for quantification and identification of reducing gases based on model-based temperature-cycled operation (TCO) using a single commercial MOS gas sensor are presented. During high temperature phases the sensor surface is highly oxidized, yielding a significant sensitivity increase after switching to lower temperatures (differential surface reduction, DSR). For low concentrations, the slope of the logarithmic conductance during this low-temperature phase is evaluated and can directly be used for quantification. For higher concentrations, the time constant for reaching a stable conductance during the same low-temperature phase is evaluated. Both signals represent the reaction rate of the reducing gas on the strongly oxidized surface at this low temperature and provide a linear calibration curve, which is exceptional for MOS sensors. By determining these reaction rates on different low-temperature plateaus and applying pattern recognition, the resulting footprint can be used for identification of different gases. All methods are tested over a wide concentration range from 10 ppb to 100 ppm (4 orders of magnitude) for four different reducing gases (CO, H₂, ammonia and benzene) using randomized gas exposures.

Facile Quantification and Identification Techniques for Reducing Gases over a Wide Concentration Range Using a MOS Sensor in Temperature-Cycled Operation

PubMed Central

Schultealbert, Caroline; Baur, Tobias; Schütze, Andreas; Sauerwald, Tilman

2018-01-01

Dedicated methods for quantification and identification of reducing gases based on model-based temperature-cycled operation (TCO) using a single commercial MOS gas sensor are presented. During high temperature phases the sensor surface is highly oxidized, yielding a significant sensitivity increase after switching to lower temperatures (differential surface reduction, DSR). For low concentrations, the slope of the logarithmic conductance during this low-temperature phase is evaluated and can directly be used for quantification. For higher concentrations, the time constant for reaching a stable conductance during the same low-temperature phase is evaluated. Both signals represent the reaction rate of the reducing gas on the strongly oxidized surface at this low temperature and provide a linear calibration curve, which is exceptional for MOS sensors. By determining these reaction rates on different low-temperature plateaus and applying pattern recognition, the resulting footprint can be used for identification of different gases. All methods are tested over a wide concentration range from 10 ppb to 100 ppm (4 orders of magnitude) for four different reducing gases (CO, H2, ammonia and benzene) using randomized gas exposures. PMID:29494545

Energy-conserving impact algorithm for the heel-strike phase of gait.

PubMed

Kaplan, M L; Heegaard, J H

2000-06-01

Significant ground reaction forces exceeding body weight occur during the heel-strike phase of gait. The standard methods of analytical dynamics used to solve the impact problem do not accommodate well the heel-strike collision due to the persistent contact at the front foot and presence of contact at the back foot. These methods can cause a non-physical energy gain on the order of the total kinetic energy of the system at impact. Additionally, these standard techniques do not quantify the contact force, but the impulse over the impact. We present an energy-conserving impact algorithm based on the penalty method to solve for the ground reaction forces during gait. The rigid body assumptions are relaxed and the bodies are allowed to penetrate one another to a small degree. Associated with the deformation is a potential, from which the contact forces are derived. The empirical coefficient-of-restitution used in the standard approaches is replaced by two parameters to characterize the stiffness and the damping of the materials. We solve two simple heel-strike models to illustrate the shortcomings of a standard approach and the suitability of the proposed method for use with gait.

Potentially Reactive Forms of Silica in Volcanic Rocks Using Different Analytical Approaches

NASA Astrophysics Data System (ADS)

Esteves, Hugo; Fernandes, Isabel; Janeiro, Ana; Santos Silva, António; Pereira, Manuel; Medeiros, Sara; Nunes, João Carlos

2017-12-01

Several concrete structures show signs of deterioration resulting from internal chemical reactions, such as the alkali-silica reaction (ASR). It is well known that these swelling reactions occur in the presence of moisture, between some silica mineral phases present in the aggregates and the alkalis of the concrete, leading to the degradation of concrete structures and consequently compromising their safety. In most of the cases, rehabilitation, demolition or even rebuilding of such structures is needed and the effective costs can be very high. Volcanic rocks are commonly used as aggregates in concrete, and they are sometimes the only option due to the unavailability of other rock types. These rocks may contain different forms of silica that are deleterious to concrete, such as opal, chalcedony, cristobalite, tridymite and micro- to cryptocrystalline quartz, as well as Si-rich volcanic glass. Volcanic rocks are typically very finegrained and their constituting minerals are usually not distinguished under optical microscopy, thus leading to using complementary methods. The objective of this research is to find the more adequate analytical methods to identify silica phases that might be present in volcanic aggregates and cause ASR. The complementary methods used include X-Ray Diffraction (XRD), mineral acid digestion and Scanning Electron Microscopy with Energy Dispersive X-Ray Spectrometry (SEM/EDS), as well as Electron Probe Micro-Analysis (EPMA).

Method for solid state crystal growth

DOEpatents

Nolas, George S.; Beekman, Matthew K.

2013-04-09

A novel method for high quality crystal growth of intermetallic clathrates is presented. The synthesis of high quality pure phase crystals has been complicated by the simultaneous formation of both clathrate type-I and clathrate type-II structures. It was found that selective, phase pure, single-crystal growth of type-I and type-II clathrates can be achieved by maintaining sufficient partial pressure of a chemical constituent during slow, controlled deprivation of the chemical constituent from the primary reactant. The chemical constituent is slowly removed from the primary reactant by the reaction of the chemical constituent vapor with a secondary reactant, spatially separated from the primary reactant, in a closed volume under uniaxial pressure and heat to form the single phase pure crystals.

Effect of Reaction Period on Stoichiometry, Phase Purity, and Morphology of Hydrothermally Synthesized Cu2NiSnS4 Nanopowder

NASA Astrophysics Data System (ADS)

Babu, G. Sahaya Dennish; Shajan, X. Sahaya; Alwin, S.; Ramasubbu, V.; Balerao, Gopal M.

2018-01-01

The effect of reaction period on the phase purity, morphology, and stoichiometry of Cu2NiSnS4 (CNTS) nanopowder prepared by hydrothermal method has been investigated. Polyvinylpyrrolidone (PVP) and thioglycolic acid were used as capping agent and sulfur source, respectively. The presence of cubic stannite crystal structure and its phase purity were confirmed by powder x-ray diffraction analysis and Raman spectroscopy. Furthermore, the morphological, crystallographic, and optical features of the prepared CNTS nanopowder were characterized by field-emission scanning electron microscopy, transmission electron microscopy, and ultraviolet-visible (UV-Vis) spectrophotometry. The elemental ratios of Cu/(Ni + Sn) and Ni/Sn showed that the stoichiometry of CNTS was maintained for the compounds synthesized at 230°C with reaction period of 24 h. The occurrence of Cu+, Ni2+, Sn4+, and S2- was evaluated by x-ray photoelectron spectroscopy. The prepared material was used as counter electrode in a dye-sensitized solar cell (DSSC) as an alternative to platinum (Pt), resulting in conversion efficiency of 0.92%. These results indicate that CNTS is a prospective material to replace conventional Pt-based counter electrodes in DSSCs.

Treating electrostatics with Wolf summation in combined quantum mechanical and molecular mechanical simulations

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

Ojeda-May, Pedro; Pu, Jingzhi, E-mail: jpu@iupui.edu

The Wolf summation approach [D. Wolf et al., J. Chem. Phys. 110, 8254 (1999)], in the damped shifted force (DSF) formalism [C. J. Fennell and J. D. Gezelter, J. Chem. Phys. 124, 234104 (2006)], is extended for treating electrostatics in combined quantum mechanical and molecular mechanical (QM/MM) molecular dynamics simulations. In this development, we split the QM/MM electrostatic potential energy function into the conventional Coulomb r{sup −1} term and a term that contains the DSF contribution. The former is handled by the standard machinery of cutoff-based QM/MM simulations whereas the latter is incorporated into the QM/MM interaction Hamiltonian as amore » Fock matrix correction. We tested the resulting QM/MM-DSF method for two solution-phase reactions, i.e., the association of ammonium and chloride ions and a symmetric SN{sub 2} reaction in which a methyl group is exchanged between two chloride ions. The performance of the QM/MM-DSF method was assessed by comparing the potential of mean force (PMF) profiles with those from the QM/MM-Ewald and QM/MM-isotropic periodic sum (IPS) methods, both of which include long-range electrostatics explicitly. For ion association, the QM/MM-DSF method successfully eliminates the artificial free energy drift observed in the QM/MM-Cutoff simulations, in a remarkable agreement with the two long-range-containing methods. For the SN{sub 2} reaction, the free energy of activation obtained by the QM/MM-DSF method agrees well with both the QM/MM-Ewald and QM/MM-IPS results. The latter, however, requires a greater cutoff distance than QM/MM-DSF for a proper convergence of the PMF. Avoiding time-consuming lattice summation, the QM/MM-DSF method yields a 55% reduction in computational cost compared with the QM/MM-Ewald method. These results suggest that, in addition to QM/MM-IPS, the QM/MM-DSF method may serve as another efficient and accurate alternative to QM/MM-Ewald for treating electrostatics in condensed-phase simulations of chemical reactions.« less

Treating electrostatics with Wolf summation in combined quantum mechanical and molecular mechanical simulations.

PubMed

Ojeda-May, Pedro; Pu, Jingzhi

2015-11-07

The Wolf summation approach [D. Wolf et al., J. Chem. Phys. 110, 8254 (1999)], in the damped shifted force (DSF) formalism [C. J. Fennell and J. D. Gezelter, J. Chem. Phys. 124, 234104 (2006)], is extended for treating electrostatics in combined quantum mechanical and molecular mechanical (QM/MM) molecular dynamics simulations. In this development, we split the QM/MM electrostatic potential energy function into the conventional Coulomb r(-1) term and a term that contains the DSF contribution. The former is handled by the standard machinery of cutoff-based QM/MM simulations whereas the latter is incorporated into the QM/MM interaction Hamiltonian as a Fock matrix correction. We tested the resulting QM/MM-DSF method for two solution-phase reactions, i.e., the association of ammonium and chloride ions and a symmetric SN2 reaction in which a methyl group is exchanged between two chloride ions. The performance of the QM/MM-DSF method was assessed by comparing the potential of mean force (PMF) profiles with those from the QM/MM-Ewald and QM/MM-isotropic periodic sum (IPS) methods, both of which include long-range electrostatics explicitly. For ion association, the QM/MM-DSF method successfully eliminates the artificial free energy drift observed in the QM/MM-Cutoff simulations, in a remarkable agreement with the two long-range-containing methods. For the SN2 reaction, the free energy of activation obtained by the QM/MM-DSF method agrees well with both the QM/MM-Ewald and QM/MM-IPS results. The latter, however, requires a greater cutoff distance than QM/MM-DSF for a proper convergence of the PMF. Avoiding time-consuming lattice summation, the QM/MM-DSF method yields a 55% reduction in computational cost compared with the QM/MM-Ewald method. These results suggest that, in addition to QM/MM-IPS, the QM/MM-DSF method may serve as another efficient and accurate alternative to QM/MM-Ewald for treating electrostatics in condensed-phase simulations of chemical reactions.

Treating electrostatics with Wolf summation in combined quantum mechanical and molecular mechanical simulations

NASA Astrophysics Data System (ADS)

Ojeda-May, Pedro; Pu, Jingzhi

2015-11-01

The Wolf summation approach [D. Wolf et al., J. Chem. Phys. 110, 8254 (1999)], in the damped shifted force (DSF) formalism [C. J. Fennell and J. D. Gezelter, J. Chem. Phys. 124, 234104 (2006)], is extended for treating electrostatics in combined quantum mechanical and molecular mechanical (QM/MM) molecular dynamics simulations. In this development, we split the QM/MM electrostatic potential energy function into the conventional Coulomb r-1 term and a term that contains the DSF contribution. The former is handled by the standard machinery of cutoff-based QM/MM simulations whereas the latter is incorporated into the QM/MM interaction Hamiltonian as a Fock matrix correction. We tested the resulting QM/MM-DSF method for two solution-phase reactions, i.e., the association of ammonium and chloride ions and a symmetric SN2 reaction in which a methyl group is exchanged between two chloride ions. The performance of the QM/MM-DSF method was assessed by comparing the potential of mean force (PMF) profiles with those from the QM/MM-Ewald and QM/MM-isotropic periodic sum (IPS) methods, both of which include long-range electrostatics explicitly. For ion association, the QM/MM-DSF method successfully eliminates the artificial free energy drift observed in the QM/MM-Cutoff simulations, in a remarkable agreement with the two long-range-containing methods. For the SN2 reaction, the free energy of activation obtained by the QM/MM-DSF method agrees well with both the QM/MM-Ewald and QM/MM-IPS results. The latter, however, requires a greater cutoff distance than QM/MM-DSF for a proper convergence of the PMF. Avoiding time-consuming lattice summation, the QM/MM-DSF method yields a 55% reduction in computational cost compared with the QM/MM-Ewald method. These results suggest that, in addition to QM/MM-IPS, the QM/MM-DSF method may serve as another efficient and accurate alternative to QM/MM-Ewald for treating electrostatics in condensed-phase simulations of chemical reactions.

Ultrasonic-assisted conversion of limestone into needle-like hydroxyapatite nanoparticles.

PubMed

Klinkaewnarong, Jutharatana; Utara, Songkot

2018-09-01

Needle-like hydroxyapatite nanoparticles were successfully synthesized via a reaction between calcium oxide (CaO) that was obtained from calcined limestone and orthophosphoric acid (H 3 PO 4 ) under ultrasonic irradiation at 25 °C. The reaction systems were exposed to ultrasonic waves of 20 kHz for various times ranging from 0 to 4 h. The initial and final pH values of the mixtures of CaO and H 3 PO 4 solution were continuously observed (pH < 4.0) after ultrasonic irradiation. The powder was then dried at 60 °C and calcined at 300 °C for 3 h (3 °C/min). The products were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The results showed that the formation of needle-like hydroxyapatite (HAp) nanoparticles was substantially accelerated compared with the reaction without ultrasonic irradiation. The HAp phase was increasingly visible with longer ultrasonic irradiation time compared with the monetite phase (CaHPO 4 ). This suggests that ultrasonic waved induced a phase transition from the monetite to HAp phase. A smaller needle-like structure of HAp (diameter ∼ 7.4 nm) with a lower contamination of monetite phase was obtained following sonication for 3 h. This study shows that Thai limestone can used as a starting material for synthesizing needle-like HAp nanoparticles with the aid of ultrasonic methods. Copyright © 2018 Elsevier B.V. All rights reserved.

Aqueous nitrite ion determination by selective reduction and gas phase nitric oxide chemiluminescence

NASA Technical Reports Server (NTRS)

Dunham, A. J.; Barkley, R. M.; Sievers, R. E.; Clarkson, T. W. (Principal Investigator)

1995-01-01

An improved method of flow injection analysis for aqueous nitrite ion exploits the sensitivity and selectivity of the nitric oxide (NO) chemilluminescence detector. Trace analysis of nitrite ion in a small sample (5-160 microL) is accomplished by conversion of nitrite ion to NO by aqueous iodide in acid. The resulting NO is transported to the gas phase through a semipermeable membrane and subsequently detected by monitoring the photoemission of the reaction between NO and ozone (O3). Chemiluminescence detection is selective for measurement of NO, and, since the detection occurs in the gas-phase, neither sample coloration nor turbidity interfere. The detection limit for a 100-microL sample is 0.04 ppb of nitrite ion. The precision at the 10 ppb level is 2% relative standard deviation, and 60-180 samples can be analyzed per hour. Samples of human saliva and food extracts were analyzed; the results from a standard colorimetric measurement are compared with those from the new chemiluminescence method in order to further validate the latter method. A high degree of selectivity is obtained due to the three discriminating steps in the process: (1) the nitrite ion to NO conversion conditions are virtually specific for nitrite ion, (2) only volatile products of the conversion will be swept to the gas phase (avoiding turbidity or color in spectrophotometric methods), and (3) the NO chemiluminescence detector selectively detects the emission from the NO + O3 reaction. The method is free of interferences, offers detection limits of low parts per billion of nitrite ion, and allows the analysis of up to 180 microL-sized samples per hour, with little sample preparation and no chromatographic separation. Much smaller samples can be analyzed by this method than in previously reported batch analysis methods, which typically require 5 mL or more of sample and often need chromatographic separations as well.

Comprehensive Analysis of the Gas- and Particle-Phase Products of VOC Oxidation

NASA Astrophysics Data System (ADS)

Bakker-Arkema, J.; Ziemann, P. J.

2017-12-01

Controlled environmental chamber studies are important for determining atmospheric reaction mechanisms and gas and aerosol products formed in the oxidation of volatile organic compounds (VOCs). Such information is necessary for developing detailed chemical models for use in predicting the atmospheric fate of VOCs and also secondary organic aerosol (SOA) formation. However, complete characterization of atmospheric oxidation reactions, including gas- and particle-phase product yields, and reaction branching ratios, are difficult to achieve. In this work, we investigated the reactions of terminal and internal alkenes with OH radicals in the presence of NOx in an attempt to fully characterize the chemistry of these systems while minimizing and accounting for the inherent uncertainties associated with environmental chamber experiments. Gas-phase products (aldehydes formed by alkoxy radical decomposition) and particle-phase products (alkyl nitrates, β-hydroxynitrates, dihydroxynitrates, 1,4-hydroxynitrates, 1,4-hydroxycarbonyls, and dihydroxycarbonyls) formed through pathways involving addition of OH to the C=C double bond as well as H-atom abstraction were identified and quantified using a suite of analytical techniques. Particle-phase products were analyzed in real time with a thermal desorption particle beam mass spectrometer; and off-line by collection onto filters, extraction, and subsequent analysis of functional groups by derivatization-spectrophotometric methods developed in our lab. Derivatized products were also separated by liquid chromatography for molecular quantitation by UV absorbance and identification using chemical ionization-ion trap mass spectrometry. Gas phase aldehydes were analyzed off-line by collection onto Tenax and a 5-channel denuder with subsequent analysis by gas chromatography, or by collection onto DNPH-coated cartridges and subsequent analysis by liquid chromatography. The full product identification and quantitation, with careful minimization of uncertainties for the various components of the experiment and analyses, demonstrates our capability to comprehensively and accurately analyze the complex chemical composition of products formed in the oxidation of organic compounds in laboratory chamber studies.

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

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

A surprisingly complex aqueous chemistry of the simplest amino acid. A pulse radiolysis and theoretical study on H/D kinetic isotope effects in the reaction of glycine anions with hydroxyl radicals.

PubMed

Stefanić, I; Ljubić, I; Bonifacić, M; Sabljić, A; Asmus, K-D; Armstrong, D A

2009-04-07

A pulse radiolysis study was carried out of the reaction rate constants and kinetic isotope effects of hydroxyl-radical-induced H/D abstraction from the most-simple alpha-amino acid glycine in its anionic form in water. The rate constants and yields of three predominantly formed radical products, glycyl (NH2-*CH-CO2-), aminomethyl (NH2-*CH2), and aminyl (*NH-CH2-CO2-) radicals, as well as of their partially or fully deuterated analogs, were found to be of comparable magnitude. The primary, secondary, and primary/secondary H/D kinetic isotope effects on the rate constants were determined with respect to each of the three radicals. The unusual variety of products for such an elementary reaction between two small and simple species indicates a complex mechanism with several reactions taking place simultaneously. Thus, a theoretical modeling of the reaction mechanism and kinetics in the gas- and aqueous phase was performed by using the unrestricted density functional theory with the BB1K functional (employing the polarizable continuum model for the aqueous phase), unrestricted coupled cluster UCCSD(T) method, and improved canonical variational theory. Several hydrogen-bonded prereaction complexes and transition states were detected. In particular, the calculations pointed to a significant mechanistic role of the three-electron two-orbital (sigma/sigma* N therefore O) hemibonded prereaction complexes in the aqueous phase. A good agreement with the experimental rate constants and kinetic isotope effects was achieved by downshifting the calculated reaction barriers by 3 kcal mol(-1) and damping the NH(D) stretching frequency by a factor of 0.86.

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.

Nonenzymatic and enzymatic hydrolysis of alkyl halides: A theoretical study of the SN2 reactions of acetate and hydroxide ions with alkyl chlorides

PubMed Central

Maulitz, Andreas H.; Lightstone, Felice C.; Zheng, Ya-Jun; Bruice, Thomas C.

1997-01-01

The SN2 displacements of chloride ion from CH3Cl, C2H5Cl, and C2H4Cl2 by acetate and hydroxide ions have been investigated, using ab initio molecular orbital theory at the HF/6–31+G(d), MP2/6–31+G(d), and MP4/6–31+G(d) levels of theory. The central barriers (calculated from the initial ion–molecule complex) of the reactions, the differences of the overall reaction energies, and the geometries of the transition states are compared. Essential stereochemical changes before and after the displacement reactions are described for selected cases. The gas phase reactions of hydroxide with CH3Cl, C2H5Cl, and C2H4Cl2 have no overall barrier, but there is a small overall barrier for the reactions of acetate with CH3Cl, C2H5Cl, and C2H4Cl2. A self-consistent reaction field solvation model was used to examine the SN2 reactions between methyl chloride and hydroxide ion and between 1,2-dichloroethane and acetate in solution. As expected, the reactions in polar solvent have a large barrier. However, the transition state structures determined by ab initio calculations change only slightly in the presence of a highly polar solvent as compared with the gas phase. We also calibrated the PM3 method for future study of an enzymatic SN2 displacement of halogen. PMID:9192609

Synthesis and impurity doping of GaN powders by the two-stage vapor-phase method for phosphor applications

NASA Astrophysics Data System (ADS)

Hara, K.; Okuyama, E.; Yonemura, A.; Uchida, T.; Okamoto, N.

2006-09-01

The analysis of particle formation and the doping of luminescent impurities during the two-stage vapor-phase synthesis of GaN powder were carried. GaN particles were grown very fast during the second stage of this method, and the increment in particle size was larger for higher reaction temperature in the region between 800 and 1000 °C. The analysis on the behaviour of particle growth based on the reaction kinetics suggested that the growth almost finishes in a few seconds with an extremely high rate at the early stage at 1000 °C, whereas the growth lasts with relatively low rates for a time longer than the actual growth duration for the case of lower temperature synthesis. GaN powders doped with various impurity atoms were synthesized by supplying impurity sources with GaCl during the second stage. The samples doped with Zn, Mg and Tb showed emissions characteristic for each doped impurity.

Method for determination of some soluble atmospheric carbonyl compounds

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

Lee, Y.N.; Zhou, X.

1993-04-01

A technique was developed for the measurement of soluble atmospheric carbonyl compounds, which uses a pyrex coil gas-liquid scrubber sampler in conjunction with a high-performance liquid chromatograph equipped with a UV-visible detector for separation and identification following derivatization with 2,4-dinitrophenylhydrazine. Carbonyls exhibiting a Henry's law solubility similar to or greater than that of formaldehyde (FA) can be determined by this method; these include FA, glycolaldehyde (GA), glyoxal (GL), and methylglyoxal (MG). Based on liquid standards and field-developed chromatographic characteristics, the limits of detection are about 0.005 ppb (in the gas phase) for MG, about 0.01 ppb for GL, and aboutmore » 0.02 ppb for FA and GA. Because of the short air-liquid contact time in the coil sampler (smaller than 10 s), interferences from aqueous-phase reactions of ozone are insignificant. Also, at the low pH of the scrubbing solution, interference resulting from reactions of carbonyls with S(IV) is unimportant. 43 refs., 7 figs., 3 tabs.« less

Contact structure for use in catalytic distillation

DOEpatents

Jones, E.M. Jr.

1984-03-27

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

Contact structure for use in catalytic distillation

DOEpatents

Jones, Jr., Edward M.

1985-01-01

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

Contact structure for use in catalytic distillation

DOEpatents

Jones, E.M. Jr.

1985-08-20

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

A high-performance liquid chromatography-electronic circular dichroism online method for assessing the absolute enantiomeric excess and conversion ratio of asymmetric reactions

NASA Astrophysics Data System (ADS)

Zhang, Xiang; Wang, Mingchao; Li, Li; Yin, Dali

2017-03-01

Asymmetric reactions often need to be evaluated during the synthesis of chiral compounds. However, traditional evaluation methods require the isolation of the individual enantiomer, which is tedious and time-consuming. Thus, it is desirable to develop simple, practical online detection methods. We developed a method based on high-performance liquid chromatography-electronic circular dichroism (HPLC-ECD) that simultaneously analyzes the material conversion ratio and absolute optical purity of each enantiomer. In particular, only a reverse-phase C18 column instead of a chiral column is required in our method because the ECD measurement provides a g-factor that describes the ratio of each enantiomer in the mixtures. We used our method to analyze the asymmetric hydrosilylation of β-enamino esters, and we discussed the advantage, feasibility, and effectiveness of this new methodology.

Synthetic H sub 2 O-CO sub 2 fluid inclusions in spontaneously nucleated forsterite, enstatite, and diopside hosts: The method and applications

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

Johnson, E.L.; Jenkins, D.M.

1991-04-01

This paper describes an experimental technique for the production of primary synthetic H{sub 2}O-CO{sub 2} and H{sub 2}O-CO{sub 2}-NaCl fluid inclusions in forsterite, orthopyroxene, and clinopyroxene hosts spontaneously nucleated during the incongruent dissolution of tremolite. The host producing reactions involve the complexation and transport of Ca, Mg, and SiO{sub 2} to the growing product phases in which the inclusions are hosted. This technique, therefore, provides the opportunity to study the effects of a complex host-producing reaction on the composition of the fluids trapped as primary inclusions in the growing host phase. In addition to providing a model for the entrapmentmore » of primary fluid inclusions, the reactions provide an excellent model of the onset of granulite facies metamorphism where, in nature, fluid inclusion compositions are commonly in disequilibrium with the mineral assemblages in which they are hosted.« less

Reverse microemulsion synthesis of layered gadolinium hydroxide nanoparticles

NASA Astrophysics Data System (ADS)

Xu, Yadong; Suthar, Jugal; Egbu, Raphael; Weston, Andrew J.; Fogg, Andrew M.; Williams, Gareth R.

2018-02-01

A reverse microemulsion approach has been explored for the synthesis of layered gadolinium hydroxide (LGdH) nanoparticles in this work. This method uses oleylamine as a multifunctional agent, acting as surfactant, oil phase and base. 1-butanol is additionally used as a co-surfactant. A systematic study of the key reaction parameters was undertaken, including the volume ratio of surfactant (oleylamine) to water, the reaction time, synthesis temperature, and the amount of co-surfactant (1-butanol) added. It proved possible to obtain pristine LGdH materials at temperatures of 120 °C or below with an oleylamine: water ratio of 1:4. Using larger amounts of surfactant or higher temperatures caused the formation of Gd(OH)3, either as the sole product or as a major impurity phase. The LGdH particles produced have sizes of ca. 200 nm, with this size being largely independent of temperature or reaction time. Adjusting the amount of 1-butanol co-surfactant added permits the size to be varied between 200 and 300 nm.

A novel headspace gas chromatographic method for in situ monitoring of monomer conversion during polymerization in an emulsion environment.

PubMed

Chai, Xin-Sheng; Zhong, Jin-Feng; Hu, Hui-Chao

2012-05-18

This paper describes a novel multiple-headspace extraction/gas chromatographic (MHE-GC) technique for monitoring monomer conversion during a polymerization reaction in a water-based emulsion environment. The polymerization reaction of methyl methacrylate (MMA) in an aqueous emulsion is used as an example. The reaction was performed in a closed headspace sample vial (as a mini-reactor), with pentane as a tracer. In situ monitoring of the vapor concentration of the tracer, employing a multiple headspace extraction (sampling) scheme, coupled to a GC, makes it possible to quantitatively follow the conversion of MMA during the early stages of polymerization. Data on the integrated amount of the tracer vapor released from the monomer droplet phase during the polymerization is described by a mathematic equation from which the monomer conversion can be calculated. The present method is simple, automated and economical, and provides an efficient tool in the investigation of the reaction kinetics and effects of the reaction conditions on the early stage of polymerization. Copyright © 2012 Elsevier B.V. All rights reserved.

Theoretical Calculation of Jet Fuel Thermochemistry. 1; Tetrahydrodicylopentadiene (JP10) Thermochemistry Using the CBS-QB3 and G3(MP2)//B3LYP Methods

NASA Technical Reports Server (NTRS)

Zehe, Michael J.; Jaffe, Richard L.

2010-01-01

High-level ab initio calculations have been performed on the exo and endo isomers of gas-phase tetrahydrodicyclopentadiene (THDCPD), a principal component of the jet fuel JP10, using the Gaussian Gx and Gx(MPx) composite methods, as well as the CBS-QB3 method, and using a variety of isodesmic and homodesmotic reaction schemes. The impetus for this work is to help resolve large discrepancies existing between literature measurements of the formation enthalpy Delta (sub f)H deg (298) for exo-THDCPD. We find that use of the isodesmic bond separation reaction C10H16 + 14CH4 yields 12C2H6 yields results for the exo isomer (JP10) in between the two experimentally accepted values, for the composite methods G3(MP2), G3(MP2)//B3LYP, and CBS-QB3. Application of this same isodesmic bond separation scheme to gas-phase adamantane yields a value for Delta (sub f)H deg (298) within 5 kJ/mol of experiment. Isodesmic bond separation calculations for the endo isomer give a heat of formation in excellent agreement with the experimental measurement. Combining our calculated values for the gas-phase heat of formation with recent measurements of the heat of vaporization yields recommended values for Delta (sub f)H deg (298)liq of -126.4 and -114.7 kJ/mol for the exo and endo isomers, respectively.

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

Watson, Thomas B.

The Proton Transfer Reaction Mass Spectrometer (PTRMS) measures gas-phase compounds in ambient air and headspace samples before using chemical ionization to produce positively charged molecules, which are detected with a time-of-flight (TOF) mass spectrometer. This ionization method uses a gentle proton transfer reaction method between the molecule of interest and protonated water, or hydronium ion (H 3O +), to produce limited fragmentation of the parent molecule. The ions produced are primarily positively charged with the mass of the parent ion, plus an additional proton. Ion concentration is determined by adding the number of ions counted at the molecular ion’s mass-to-chargemore » ratio to the number of air molecules in the reaction chamber, which can be identified according to the pressure levels in the reaction chamber. The PTRMS allows many volatile organic compounds in ambient air to be detected at levels from 10–100 parts per trillion by volume (pptv). The response time is 1 to 10 seconds.« less

The effect of reaction temperature on the particle size of bismuth oxide nanoparticles synthesized via hydrothermal method

NASA Astrophysics Data System (ADS)

Zulkifli, Zulfa Aiza; Razak, Khairunisak Abdul; Rahman, Wan Nordiana Wan Abdul

2018-05-01

Bismuth oxide (Bi2O3) nanoparticles have been synthesized at different temperatures from 70 to 120˚C without any subsequent heat treatment using hydrothermal method. The particle size, and crystal structure of as-synthesized particles were investigated by X-ray diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), Energy-dispersive X-ray spectroscopy (EDX) and Fourier transform Infra-Red (FTIR). The nanoparticles are of a pure moniclinic Bi2O3 phase with rods shape. The average size of nanoparticles increases with the increase of reaction temperature. It was clear that longer reaction temperature allows precipitation completely occured and form larger nanoparticles (NPs). The crystallinity of Bi2O3 also are of high purity even at lower reaction temperature. The FTIR spectrum showed the absorption band at 845 cm-1 which is attributed to Bi-O-Bi bond, and the strong absorption band recorded at 424 cm-1 that is due to the stretching mode of Bi-O.

Laboratory Studies of Atmospheric Heterogeneous Chemistry

NASA Technical Reports Server (NTRS)

Keyser, L. F.; Leu, M-T.

1993-01-01

In the laboratory, ice films formed by freezing from the liquid or more frequently by deposition from the vapor phase have been used to simulate stratospheric cloud surfaces for measurements of reaction and uptake rates. To obtain intrinsic surface reaction probabilities that can be used in atmospheric models, the area of the film surface that actually takes part in the reaction must be known. It is important to know not only the total surface area but also the film morphology in order to determine where and how the surface is situated and, thus, what fraction of it is available for reaction. Information on the structure of these ice films has been obtained by using several experimental methods. In the sections that follow, these methods will be discussed, then the results will be used to construct a working model of the ice films, and finally the model will be applied to an experimental study of HC1 uptake by H_2O ice.

Cure kinetics, morphologies, and mechanical properties of thermoplastic/MWCNT modified multifunctional glassy epoxies prepared via continuous reaction methods

NASA Astrophysics Data System (ADS)

Cheng, Xiaole

The primary goal of this dissertation is to develop a novel continuous reactor method to prepare partially cured epoxy prepolymers for aerospace prepreg applications with the aim of replacing traditional batch reactors. Compared to batch reactors, the continuous reactor is capable of solubilizing and dispersing a broad range of additives including thermoplastic tougheners, stabilizers, nanoparticles and curatives and advancing epoxy molecular weights and viscosities while reducing energy consumption. In order to prove this concept, polyethersulfone (PES) modified 4, 4'-diaminodiphenylsulfone (44DDS)/tetraglycidyl-4, 4'-diaminodiphenylmethane (TGDDM) epoxy prepolymers were firstly prepared using both continuous reactor and batch reactor methods. Kinetic studies confirmed the chain extension reaction in the continuous reactor is similar to the batch reactor, and the molecular weights and viscosities of prepolymers were readily controlled through reaction kinetics. Atomic force microscopy (AFM) confirmed similar cured network morphologies for formulations prepared from batch and continuous reactors. Additionally tensile strength, tensile modulus and fracture toughness analyses concluded mechanical properties of cured epoxy matrices produced from both reactors were equivalent. Effects of multifunctional epoxy compositions on thermoplastics phase-separated morphologies were systematically studied using a combination of AFM with nanomechanical mapping, spectroscopic and calorimetric techniques to provide new insights to tailor cured reaction induced phase separation (CRIPS) in multifunctional epoxy blend networks. Furthermore, how resultant crosslinked glassy polymer network and phase-separated morphologies correlated with mechanical properties are discussed in detail. Multiwall carbon nanotube (MWCNT)/TGDDM epoxy prepolymers were further prepared by combining the successful strategies for advancing epoxy chemistries and dispersing nanotubes using the continuous reactor. Optical microscopy (OM) and scanning electron microscopy (SEM) were used to characterize the MWCNT dispersion states and stabilization in epoxy prepolymer matrix after continuous process and during curing cycles. Additionally, electrical conductivities and mechanical properties of final cured MWCNT/TGDDM composites were measured and discussed in view of their corresponding MWCNT dispersion states. Ternary blends of MWCNT reinforced thermoplastic/epoxy prepolymers were prepared by the continuous reactor. Influence of MWCNT on the CRIPS mechanism and the cured morphologies were systematically investigated using SEM and rheological analysis. Incorporation of MWCNT in thermoplastic/epoxy matrices can lead to a morphological transformation from phase inverted, to co-continuous, and to droplet dispersed morphology. In additional, dynamic mechanical analysis revealed the heterogeneity of MWCNT dispersion in thermoplastic/thermosets systems.

Surfactant/detergent titration analysis method and apparatus for machine working fluids, surfactant-containing wastewater and the like

DOEpatents

Smith, Douglas D.; Hiller, John M.

1998-01-01

The present invention is an improved method and related apparatus for quantitatively analyzing machine working fluids and other aqueous compositions such as wastewater which contain various mixtures of cationic, neutral, and/or anionic surfactants, soluble soaps, and the like. The method utilizes a single-phase, non-aqueous, reactive titration composition containing water insoluble bismuth nitrate dissolved in glycerol for the titration reactant. The chemical reaction of the bismuth ion and glycerol with the surfactant in the test solutions results in formation of micelles, changes in micelle size, and the formation of insoluble bismuth soaps. These soaps are quantified by physical and chemical changes in the aqueous test solution. Both classical potentiometric analysis and turbidity measurements have been used as sensing techniques to determine the quantity of surfactant present in test solutions. This method is amenable to the analysis of various types of new, in-use, dirty or decomposed surfactants and detergents. It is a quick and efficient method utilizing a single-phase reaction without needing a separate extraction from the aqueous solution. It is adaptable to automated control with simple and reliable sensing methods. The method is applicable to a variety of compositions with concentrations from about 1% to about 10% weight. It is also applicable to the analysis of waste water containing surfactants with appropriate pre-treatments for concentration.

Surfactant/detergent titration analysis method and apparatus for machine working fluids, surfactant-containing wastewater and the like

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

Smith, D.D.; Hiller, J.M.

1998-02-24

The present invention is an improved method and related apparatus for quantitatively analyzing machine working fluids and other aqueous compositions such as wastewater which contain various mixtures of cationic, neutral, and/or anionic surfactants, soluble soaps, and the like. The method utilizes a single-phase, non-aqueous, reactive titration composition containing water insoluble bismuth nitrate dissolved in glycerol for the titration reactant. The chemical reaction of the bismuth ion and glycerol with the surfactant in the test solutions results in formation of micelles, changes in micelle size, and the formation of insoluble bismuth soaps. These soaps are quantified by physical and chemical changesmore » in the aqueous test solution. Both classical potentiometric analysis and turbidity measurements have been used as sensing techniques to determine the quantity of surfactant present in test solutions. This method is amenable to the analysis of various types of new, in-use, dirty or decomposed surfactants and detergents. It is a quick and efficient method utilizing a single-phase reaction without needing a separate extraction from the aqueous solution. It is adaptable to automated control with simple and reliable sensing methods. The method is applicable to a variety of compositions with concentrations from about 1% to about 10% weight. It is also applicable to the analysis of waste water containing surfactants with appropriate pre-treatments for concentration. 1 fig.« less

Surfactant/detergent titration analysis method and apparatus for machine working fluids, surfactant-containing wastewater and the like

DOEpatents

Smith, D.D.; Hiller, J.M.

1998-02-24

The present invention is an improved method and related apparatus for quantitatively analyzing machine working fluids and other aqueous compositions such as wastewater which contain various mixtures of cationic, neutral, and/or anionic surfactants, soluble soaps, and the like. The method utilizes a single-phase, non-aqueous, reactive titration composition containing water insoluble bismuth nitrate dissolved in glycerol for the titration reactant. The chemical reaction of the bismuth ion and glycerol with the surfactant in the test solutions results in formation of micelles, changes in micelle size, and the formation of insoluble bismuth soaps. These soaps are quantified by physical and chemical changes in the aqueous test solution. Both classical potentiometric analysis and turbidity measurements have been used as sensing techniques to determine the quantity of surfactant present in test solutions. This method is amenable to the analysis of various types of new, in-use, dirty or decomposed surfactants and detergents. It is a quick and efficient method utilizing a single-phase reaction without needing a separate extraction from the aqueous solution. It is adaptable to automated control with simple and reliable sensing methods. The method is applicable to a variety of compositions with concentrations from about 1% to about 10% weight. It is also applicable to the analysis of waste water containing surfactants with appropriate pre-treatments for concentration. 1 fig.

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.

Chemical reactions in reverse micelle systems

DOEpatents

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

1993-08-24

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

Chemical compatibility between UO2 fuel and SiC cladding for LWRs. Application to ATF (Accident-Tolerant Fuels)

NASA Astrophysics Data System (ADS)

Braun, James; Guéneau, Christine; Alpettaz, Thierry; Sauder, Cédric; Brackx, Emmanuelle; Domenger, Renaud; Gossé, Stéphane; Balbaud-Célérier, Fanny

2017-04-01

Silicon carbide-silicon carbide (SiC/SiC) composites are considered to replace the current zirconium-based cladding materials thanks to their good behavior under irradiation and their resistance under oxidative environments at high temperature. In the present work, a thermodynamic analysis of the UO2±x/SiC system is performed. Moreover, using two different experimental methods, the chemical compatibility of SiC towards uranium dioxide, with various oxygen contents (UO2±x) is investigated in the 1500-1970 K temperature range. The reaction leads to the formation of mainly uranium silicides and carbides phases along with CO and SiO gas release. Knudsen Cell Mass Spectrometry is used to measure the gas release occurring during the reaction between UO2+x and SiC powders as function of time and temperature. These experimental conditions are representative of an open system. Diffusion couple experiments with pellets are also performed to study the reaction kinetics in closed system conditions. In both cases, a limited chemical reaction is observed below 1700 K, whereas the reaction is enhanced at higher temperature due to the decomposition of SiC leading to Si vaporization. The temperature of formation of the liquid phase is found to lie between 1850 < T < 1950 K.

A level set-based topology optimization method for simultaneous design of elastic structure and coupled acoustic cavity using a two-phase material model

NASA Astrophysics Data System (ADS)

Noguchi, Yuki; Yamamoto, Takashi; Yamada, Takayuki; Izui, Kazuhiro; Nishiwaki, Shinji

2017-09-01

This papers proposes a level set-based topology optimization method for the simultaneous design of acoustic and structural material distributions. In this study, we develop a two-phase material model that is a mixture of an elastic material and acoustic medium, to represent an elastic structure and an acoustic cavity by controlling a volume fraction parameter. In the proposed model, boundary conditions at the two-phase material boundaries are satisfied naturally, avoiding the need to express these boundaries explicitly. We formulate a topology optimization problem to minimize the sound pressure level using this two-phase material model and a level set-based method that obtains topologies free from grayscales. The topological derivative of the objective functional is approximately derived using a variational approach and the adjoint variable method and is utilized to update the level set function via a time evolutionary reaction-diffusion equation. Several numerical examples present optimal acoustic and structural topologies that minimize the sound pressure generated from a vibrating elastic structure.

Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

PubMed

Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

2014-12-02

Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur.

Relationship between fabrication method and chemical stability of Ni-BaZr0.8Y0.2O3-δ membrane

NASA Astrophysics Data System (ADS)

Fang, Shumin; Wang, Siwei; Brinkman, Kyle S.; Su, Qing; Wang, Haiyan; Chen, Fanglin

2015-03-01

NiO effectively promotes the sintering of highly refractory Y-doped BaZrO3 (BZY) through the formation of BaY2NiO5, providing a simple and cost-effective method for the fabrication of dense BZY electrolyte and Ni-BZY hydrogen separation membrane at ∼1400 °C. Unfortunately, insulating BaCO3 and Y2O3 phases formed on the surface of BZY and Ni-BZY prepared by solid state reaction method with NiO after annealing in wet CO2. Ni-BZY membranes prepared from different methods suffered different degree of performance loss in wet H2 at 900 °C. The chemical instability of Ni-BZY is attributed to the formation of a secondary phase (BaY2O4) generated from the reduction of BaY2NiO5 in H2 during the sintering process. Both BaY2O4 and BaY2NiO5 react with H2O, and CO2 at elevated temperatures, generating insulating Ba(OH)2 and BaCO3 phases, respectively. The less BaY2O4 is formed in the fabrication process, the better chemical stability the Ni-BZY membranes possess. Therefore, a new Ni-BZY membrane is prepared through a judicial combination of BZY powders prepared from combined EDTA-citric and solid state reaction methods, and demonstrates exceptional chemical stability in H2O and CO2, enabling stable and even improved hydrogen flux in wet 50% CO2 at 900 °C.

A multi-level quantum mechanics and molecular mechanics study of SN2 reaction at nitrogen: NH2Cl + OH(-) in aqueous solution.

PubMed

Lv, Jing; Zhang, Jingxue; Wang, Dunyou

2016-02-17

We employed a multi-level quantum mechanics and molecular mechanics approach to study the reaction NH2Cl + OH(-) in aqueous solution. The multi-level quantum method (including the DFT method with both the B3LYP and M06-2X exchange-correlation functionals and the CCSD(T) method, and both methods with the aug-cc-pVDZ basis set) was used to treat the quantum reaction region in different stages of the calculation in order to obtain an accurate potential of mean force. The obtained free energy activation barriers at the DFT/MM level of theory yielded a big difference of 21.8 kcal mol(-1) with the B3LYP functional and 27.4 kcal mol(-1) with the M06-2X functional respectively. Nonetheless, the barrier heights become very close when shifted from DFT to CCSD(T): 22.4 kcal mol(-1) and 22.9 kcal mol(-1) at CCSD(T)(B3LYP)/MM and CCSD(T)(M06-2X)/MM levels of theory, respectively. The free reaction energy obtained using CCSD(T)(M06-2X)/MM shows an excellent agreement with the one calculated using the available gas-phase data. Aqueous solution plays a significant role in shaping the reaction profile. In total, the water solution contributes 13.3 kcal mol(-1) and 14.6 kcal mol(-1) to the free energy barrier heights at CCSD(T)(B3LYP)/MM and CCSD(T)(M06-2X)/MM respectively. The title reaction at nitrogen is a faster reaction than the corresponding reaction at carbon, CH3Cl + OH(-).

Influence of malalignment on socket reaction moments during gait in amputees with transtibial prostheses.

PubMed

Boone, David A; Kobayashi, Toshiki; Chou, Teri G; Arabian, Adam K; Coleman, Kim L; Orendurff, Michael S; Zhang, Ming

2013-04-01

Alignment - the process and measured orientation of the prosthetic socket relative to the foot - is important for proper function of a transtibial prosthesis. Prosthetic alignment is performed by prosthetists using visual gait observation and amputees' feedback. The aim of this study was to investigate the effect of transtibial prosthesis malalignment on the moments measured at the base of the socket: the socket reaction moments. Eleven subjects with transtibial amputation were recruited from the community. An instrumented prosthesis alignment component was used to measure socket reaction moments during ambulation under 17 alignment conditions, including nominally aligned using conventional clinical methods, and angle perturbations of 3° and 6° (flexion, extension, abduction, and adduction) and translation perturbations of 5mm and 10mm (anterior, posterior, lateral, and medial) referenced from the nominal alignment. Coronal alignment perturbations caused systematic changes in the coronal socket reaction moments. All angle and translation perturbations revealed statistically significant differences on coronal socket reaction moments compared to the nominal alignment at 30% and 75% of stance phase (P<0.05). The effect of sagittal alignment perturbations on sagittal socket reaction moments was not as responsive as that of the coronal perturbations. The sagittal angle and translation perturbations of the socket led to statistically significant changes in minimum moment, maximum moment, and moments at 45% of stance phase in the sagittal plane. Therefore, malalignment affected the socket reaction moments in amputees with transtibial prostheses. Copyright © 2012 Elsevier B.V. All rights reserved.

Characterization of solution-phase and gas-phase reactions in on-line electrochemistry-thermospray tandem mass spectrometry.

PubMed

Volk, K J; Yost, R A; Brajter-Toth, A

1989-07-14

Electrochemistry was used on-line with high-performance liquid chromatography-thermospray tandem mass spectrometry to provide insight into the solution-phase decomposition reactions of electrochemically generated oxidation products. Products formed during electrooxidation were monitored as the electrode potential was varied. The solution reactions which follow the initial electron transfer at the electrode are affected by the vaporizer tip temperature of the thermospray probe and the composition of the thermospray buffer. Either hydrolysis or ammonolysis reactions of the initial electrochemical oxidation products can occur with pH 7 ammonium acetate buffer. Both the electrochemically generated and the synthesized disulfide of 6-thiopurine decompose under thermospray conditions to produce 6-thiopurine and purine-6-sulfinate. Solution-phase studies indicate that nucleophilic and electrophilic substitution reactions with purine-6-sulfinate result in the formation of purine, adenine, and hypoxanthine. Products were identified and characterized by tandem mass spectrometry. This work shows the first example of high-performance liquid chromatography used on-line with electrochemistry to separate stable oxidation products prior to analysis by thermospray tandem mass spectrometry. In addition, solution-phase and gas-phase studies with methylamine show that the site of the nucleophilic and electrophilic reactions is probably inside the thermospray probe. Most importantly, these results also show that the on-line combination of electrochemistry with thermospray tandem mass spectrometry provides valuable information about redox and associated chemical reactions of biological molecules such as the structures of intermediates or products as well as providing insight into reaction pathways.

Reaction Event Counting Statistics of Biopolymer Reaction Systems with Dynamic Heterogeneity.

PubMed

Lim, Yu Rim; Park, Seong Jun; Park, Bo Jung; Cao, Jianshu; Silbey, Robert J; Sung, Jaeyoung

2012-04-10

We investigate the reaction event counting statistics (RECS) of an elementary biopolymer reaction in which the rate coefficient is dependent on states of the biopolymer and the surrounding environment and discover a universal kinetic phase transition in the RECS of the reaction system with dynamic heterogeneity. From an exact analysis for a general model of elementary biopolymer reactions, we find that the variance in the number of reaction events is dependent on the square of the mean number of the reaction events when the size of measurement time is small on the relaxation time scale of rate coefficient fluctuations, which does not conform to renewal statistics. On the other hand, when the size of the measurement time interval is much greater than the relaxation time of rate coefficient fluctuations, the variance becomes linearly proportional to the mean reaction number in accordance with renewal statistics. Gillespie's stochastic simulation method is generalized for the reaction system with a rate coefficient fluctuation. The simulation results confirm the correctness of the analytic results for the time dependent mean and variance of the reaction event number distribution. On the basis of the obtained results, we propose a method of quantitative analysis for the reaction event counting statistics of reaction systems with rate coefficient fluctuations, which enables one to extract information about the magnitude and the relaxation times of the fluctuating reaction rate coefficient, without a bias that can be introduced by assuming a particular kinetic model of conformational dynamics and the conformation dependent reactivity. An exact relationship is established between a higher moment of the reaction event number distribution and the multitime correlation of the reaction rate for the reaction system with a nonequilibrium initial state distribution as well as for the system with the equilibrium initial state distribution.

Investigation of Reaction Mechanism on the Lime-Free Roasting of Chromium-Containing Slag

NASA Astrophysics Data System (ADS)

Yu, Kai-ping; Zhang, Hong-ling; Chen, Bo; Xu, Hong-bin; Zhang, Yi

2015-12-01

The lime-free roasting process of trivalent chromium-containing slag was investigated. The effect of Fe and liquid phase on the conversion reaction of chromium was discussed. The oxidation of trivalent chromium depends greatly on the diffusion of Na+ and O2. Both the raw material Na2CO3 and the intermediate product NaFeO2 serve as the carriers of Na+. The Na+ diffusion is improved by the binary liquid phase of Na2CrO4-Na2CO3, whereas excess liquid phase results in a low conversion rate of chromium by hindering the diffusion of oxygen towards the reaction interface. With the increasing of liquid volume, the controlled step of chromium oxidation changes from Na+ diffusion to oxygen diffusion. The mechanism study showed that the volume of liquid phase increased while raising the reaction temperature or prolonging the reaction time. Based on the role of both liquid phase and Fe, the oxidation process of chromium was summarized as a three-stage model: the Na+ diffusion-controlled stage, the O2 diffusion-controlled stage, and the oxidation reaction halted stage.

Efficient Conservative Reformulation Schemes for Lithium Intercalation

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

Urisanga, PC; Rife, D; De, S

Porous electrode theory coupled with transport and reaction mechanisms is a widely used technique to model Li-ion batteries employing an appropriate discretization or approximation for solid phase diffusion with electrode particles. One of the major difficulties in simulating Li-ion battery models is the need to account for solid phase diffusion in a second radial dimension r, which increases the computation time/cost to a great extent. Various methods that reduce the computational cost have been introduced to treat this phenomenon, but most of them do not guarantee mass conservation. The aim of this paper is to introduce an inherently mass conservingmore » yet computationally efficient method for solid phase diffusion based on Lobatto III A quadrature. This paper also presents coupling of the new solid phase reformulation scheme with a macro-homogeneous porous electrode theory based pseudo 20 model for Li-ion battery. (C) The Author(s) 2015. Published by ECS. All rights reserved.« less

Phase equilibria and crystal structure of the complex oxides in the Sr Fe Co O system

NASA Astrophysics Data System (ADS)

Aksenova, T. V.; Gavrilova, L. Ya.; Cherepanov, V. A.

2008-06-01

Phase relations in the Sr-Fe-Co-O system have been investigated at 1100 °C in air by X-ray powder diffraction on quenched samples. Solid solutions of the form SrFe 1-xCo xO 3-δ (0⩽ x⩽0.7), Sr 3Fe 2-yCo yO 7-δ (0⩽ y⩽0.4) and Sr 4Fe 6-zCo zO 13±δ (0⩽ z⩽1.6) were prepared by solid-state reaction and by the sol-gel method. The structural parameters of single-phase samples were refined by the Rietveld profile method. The variation of the lattice parameters with composition has been determined for each solid solution and a cross-section of the phase diagram at 1100 °C in air for the entire Sr-Fe-Co-O system has been constructed.

Direct measurement of nuclear cross-section of astrophysical interest: Results and perspectives

NASA Astrophysics Data System (ADS)

Cavanna, Francesca; Prati, Paolo

2018-03-01

Stellar evolution and nucleosynthesis are interconnected by a wide network of nuclear reactions: the study of such connection is usually known as nuclear astrophysics. The main task of this discipline is the determination of nuclear cross-section and hence of the reaction rate in different scenarios, i.e. from the synthesis of a few very light isotopes just after the Big Bang to the heavy element production in the violent explosive end of massive stars. The experimental determination of reaction cross-section at the astrophysical relevant energies is extremely difficult, sometime impossible, due to the Coulomb repulsion between the interacting nuclei which turns out in cross-section values down to the fbar level. To overcome these obstacles, several experimental approaches have been developed and the adopted techniques can be roughly divided into two categories, i.e. direct and indirect methods. In this review paper, the general problem of nuclear astrophysics is introduced and discussed from the point of view of experimental approach. We focus on direct methods and in particular on the features of low-background experiments performed at underground laboratory facilities. The present knowledge of reactions involved in the Big Bang and stellar hydrogen-burning scenarios is discussed as well as the ongoing projects aiming to investigate mainly the helium- and carbon-burning phases. Worldwide, a new generation of experiment in the MeV range is in the design phase or at the very first steps and decisive progresses are expected to come in the next years.

Analysis of reaction products formed in the gas phase reaction of E,E-2,4-hexadienal with atmospheric oxidants: Reaction mechanisms and atmospheric implications

NASA Astrophysics Data System (ADS)

Colmenar, I.; Martin, P.; Cabañas, B.; Salgado, S.; Martinez, E.

2018-03-01

An analysis of reaction products for the reaction of E,E-2,4-hexadienal with chlorine atoms (Cl) and OH and NO3 radicals has been carried out at the first time with the aim of obtaining a better understanding of the tropospheric reactivity of α,β-unsaturated carbonyl compounds. Fourier Transform Infrared (FTIR) spectroscopy and Gas Chromatography-Mass Spectrometry with a Time of Flight detector (GC-TOFMS) were used to carry out the qualitative and/or quantitative analyses. Reaction products in gas and particulate phase were observed from the reactions of E,E-2,4- hexadienal with all oxidants. E/Z-Butenedial and maleic anhydride were the main products identified in gas phase. E-butenedial calculated molar yield ranging from 4 to 10%. A significant amount of multifunctional compounds (chloro and hydroxy carbonyls) was identified. These compounds could be formed in particulate phase explaining the ∼90% of unaccounted carbon in gas phase. The reaction with Cl atoms in the presence of NOx with a long reaction time gave Peroxy Acetyl Nitrate (PAN) as an additional product, which is known for being an important specie in the generation of the photochemical smog. Nitrated compounds were the major organic products from the reaction with the NO3 radical. Based on the identified products, the reaction mechanisms have been proposed. In these mechanisms a double bond addition of the atmospheric oxidant at C4/C5 of E,E-2,4-hexadienal is the first step for tropospheric degradation.

Effect of reaction atmosphere on structural and optical properties of hexagonal molybdenum oxide (h-MoO{sub 3})

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

Doss, V. Arumai; Chithambararaj, A.; Bose, A. Chandra, E-mail: acbose@nitt.edu

2016-05-23

The present work aims to synthesize single phase h-MoO{sub 3} nanocrytals by chemical precipitation method exposed under different reaction atmospheres. The reaction atmosphere have been successfully tuned as air, nitrogen and argon and studied its effects on structural, functional, morphology and optical properties by using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy and diffuse reflectance spectroscopy (DRS) measurements. The XRD result indicates that the sample exhibits characteristic hexagonal phase of MoO{sub 3}. The crystallite size is estimated by well known Scherrer’s method. The crystallite size is relative small in the case of sample prepared atmore » argon atmosphere. The functional groups such as Mo-O, N-H and O-H are identified from FT-IR spectroscopy. The particle exhibits rod like morphology with perfect hexagonal cross-section. The optical absorption observed at 420-450 nm corresponds to fundamental optical absorption by h-MoO{sub 3}. The band gap values are estimated using Kublka-Munk (K-M) function and found to be 2. 87 eV, 2.93 eV and 2.97 eV for samples synthesized under air, nitrogen and argon, respectively.« less

CO2 valorization by means of Dielectric Barrier Discharge

NASA Astrophysics Data System (ADS)

Machrafi, H.; Cavadias, S.; Amouroux, J.

2011-01-01

As atmospheric pollution is causing several environmental problems it is incumbent to reduce the impact of pollution on the environment. One particular problem is the production of CO2 by many transport and industrial applications. Instead of stocking CO2 and instead of being a product, it can be used as a source. The case considered is the CO2 reformation of methane producing hydrogen and CO. It is an endothermic reaction, for which the activation barrier needs to be surpassed. This can be done efficiently by the method of Dielectric Barrier Discharge. The process relies on the collision of electrons, which are accelerated under an electrical field that is created in the discharge area. This leads to the formation of reactive species, which facilitate the abovementioned reaction. This study is performed using a Matlab program with the Reaction Engineering module in COMSOL (with an incorporated kinetic mechanism) in order to model the discharge phase. Then COMSOL (continuity and Navier-Stokes equations) is used to model the flow in the post-discharge phase. The results showed that both a 2D and 3D model can be used to model the chemical-plasma process. These methods need strongly reduced kinetic mechanism, which in some cases can cause loss of precision.

Construction and application of a new dual-hybrid random phase approximation.

PubMed

Mezei, Pál D; Csonka, Gábor I; Ruzsinszky, Adrienn; Kállay, Mihály

2015-10-13

The direct random phase approximation (dRPA) combined with Kohn-Sham reference orbitals is among the most promising tools in computational chemistry and applicable in many areas of chemistry and physics. The reason for this is that it scales as N(4) with the system size, which is a considerable advantage over the accurate ab initio wave function methods like standard coupled-cluster. dRPA also yields a considerably more accurate description of thermodynamic and electronic properties than standard density-functional theory methods. It is also able to describe strong static electron correlation effects even in large systems with a small or vanishing band gap missed by common single-reference methods. However, dRPA has several flaws due to its self-correlation error. In order to obtain accurate and precise reaction energies, barriers and noncovalent intra- and intermolecular interactions, we construct a new dual-hybrid dRPA (hybridization of exact and semilocal exchange in both the energy and the orbitals) and test the performance of this new functional on isogyric, isodesmic, hypohomodesmotic, homodesmotic, and hyperhomodesmotic reaction classes. We also use a test set of 14 Diels-Alder reactions, six atomization energies (AE6), 38 hydrocarbon atomization energies, and 100 reaction barrier heights (DBH24, HT-BH38, and NHT-BH38). For noncovalent complexes, we use the NCCE31 and S22 test sets. To test the intramolecular interactions, we use a set of alkane, cysteine, phenylalanine-glycine-glycine tripeptide, and monosaccharide conformers. We also discuss the delocalization and static correlation errors. We show that a universally accurate description of chemical properties can be provided by a large, 75% exact exchange mixing both in the calculation of the reference orbitals and the final energy.

Toward Determining ATPase Mechanism in ABC Transporters: Development of the Reaction Path–Force Matching QM/MM Method

PubMed Central

Zhou, Y.; Ojeda-May, P.; Nagaraju, M.; Pu, J.

2016-01-01

Adenosine triphosphate (ATP)-binding cassette (ABC) transporters are ubiquitous ATP-dependent membrane proteins involved in translocations of a wide variety of substrates across cellular membranes. To understand the chemomechanical coupling mechanism as well as functional asymmetry in these systems, a quantitative description of how ABC transporters hydrolyze ATP is needed. Complementary to experimental approaches, computer simulations based on combined quantum mechanical and molecular mechanical (QM/MM) potentials have provided new insights into the catalytic mechanism in ABC transporters. Quantitatively reliable determination of the free energy requirement for enzymatic ATP hydrolysis, however, requires substantial statistical sampling on QM/MM potential. A case study shows that brute force sampling of ab initio QM/MM (AI/MM) potential energy surfaces is computationally impractical for enzyme simulations of ABC transporters. On the other hand, existing semiempirical QM/MM (SE/MM) methods, although affordable for free energy sampling, are unreliable for studying ATP hydrolysis. To close this gap, a multiscale QM/MM approach named reaction path–force matching (RP–FM) has been developed. In RP–FM, specific reaction parameters for a selected SE method are optimized against AI reference data along reaction paths by employing the force matching technique. The feasibility of the method is demonstrated for a proton transfer reaction in the gas phase and in solution. The RP–FM method may offer a general tool for simulating complex enzyme systems such as ABC transporters. PMID:27498639

Study the Formation of H2, HD and D2 under Various Interstellar Conditions

NASA Astrophysics Data System (ADS)

Sahu, Dipen; Chakrabarti, Sandip Kumar; Das, Ankan

2016-07-01

Hydrogen is the most abundant molecule in the Interstellar medium (ISM). Formation of gas phase hydrogen molecule is inefficient; perhaps grain surface acts as a necessary ingredients for the formation of H_2 molecule. H atoms accrete on the grain surface, recombine there and desorb in the gas phase. Similarly, deuterium accretion on grain surfaces can produce simple dueterated molecules (HD and D_2) on the ISM. Unlike gas phase reactions, rate equations can not yield accurate result for grain surface reactions due to inherent randomness of surface species. We use Monte-Carlo method to follow this surface chemistry which effectively take care of this randomness. We use square grids and impose periodic boundary condition on them to mimic the spherical nature of grains. Various types of rough surfaces are considered to study the impact on effective production rates. We found that these simple but most important molecules are produced in low temperature (physisorption sites) as well as in high temperature (chemisorption sites) regions.

Investigation of Synthesis and Magnetic Properties of Rod-Shaped CoFe2O4 via Precipitation-Topotactic Reaction Employing α-FeOOH and γ-FeOOH As Templates

NASA Astrophysics Data System (ADS)

Cao, Xiaohui; Dong, Hongfei; Tan, Yuzhuo; Meng, Jinhong

2018-03-01

Rod-shaped CoFe2O4 was prepared by chemical precipitation-topotactic reaction method, and in this preparation needle-like γ-FeOOH and α-FeOOH were synthesized to use as template materials. The evolution of phase and morphology in the process of calcination exhibits that α-FeOOH and γ-FeOOH experienced different routes to form the α-Fe2O3 middle phase with different crystallinity and morphology. The synthesis process of CoFe2O4 revealed that the crystallinity, purity and morphology of CoFe2O4 depend on the α-Fe2O3 middle phase. The magnetic measurement showed that the CoFe2O4 prepared from α-FeOOH has higher saturation magnetization and coercivity, and the crystallinity and morphology may play important roles in achieving a better magnetic performance.

Application of a hybrid Electrocoagulation-Fenton process in yarn dye wastewater: Kinetic study

NASA Astrophysics Data System (ADS)

Riadi, L.; Sapei, L.; Lidiawati, T.; Agustin, Y. E.

2016-11-01

Reactive dyes contain a significant portion of colorants used in yarn dying process and also in textile industry. Since the COD content is usually high in such wastewater,we conducted a hybrid electrocoagulation-fenton method to treat the wastewater. This work describes the application of the hybrid system to the removal of chemical oxygen demand and color from the wastewater in a batch reactor. Having worked with initial pH of 3,0; temperature at 30°C, molar ratio of Fe2+/H2O2 =1/10 and the mol ratio H2O2/COD = 4, we got 88.3% COD conversion and 88.5% color removal. The COD degradation process can be explained in two phases, the first phase is instantaneous reaction and the second phase is first order reaction. The kinetic constant was 0.0053 minute-1 and the rate of COD degradation was 0.0053[COD] mg/L minute.

Optimization of the β-Elimination/Michael Addition Chemistry on Reversed-Phase Supports for Mass Spectrometry Analysis of O-Linked Protein Modifications

PubMed Central

Nika, Heinz; Nieves, Edward; Hawke, David H.; Angeletti, Ruth Hogue

2013-01-01

We previously adapted the β-elimination/Michael addition chemistry to solid-phase derivatization on reversed-phase supports, and demonstrated the utility of this reaction format to prepare phosphoseryl peptides in unfractionated protein digests for mass spectrometric identification and facile phosphorylation-site determination. Here, we have expanded the use of this technique to β-N-acetylglucosamine peptides, modified at serine/threonine, phosphothreonyl peptides, and phosphoseryl/phosphothreonyl peptides, followed in sequence by proline. The consecutive β-elimination with Michael addition was adapted to optimize the solid-phase reaction conditions for throughput and completeness of derivatization. The analyte remained intact during derivatization and was recovered efficiently from the silica-based, reversed-phase support with minimal sample loss. The general use of the solid-phase approach for enzymatic dephosphorylation was demonstrated with phosphoseryl and phosphothreonyl peptides and was used as an orthogonal method to confirm the identity of phosphopeptides in proteolytic mixtures. The solid-phase approach proved highly suitable to prepare substrates from low-level amounts of protein digests for phosphorylation-site determination by chemical-targeted proteolysis. The solid-phase protocol provides for a simple, robust, and efficient tool to prepare samples for phosphopeptide identification in MALDI mass maps of unfractionated protein digests, using standard equipment available in most biological laboratories. The use of a solid-phase analytical platform is expected to be readily expanded to prepare digest from O-glycosylated- and O-sulfonated proteins for mass spectrometry-based structural characterization. PMID:23997661

Phase locking route behind complex periodic windows in a forced oscillator

NASA Astrophysics Data System (ADS)

Jan, Hengtai; Tsai, Kuo-Ting; Kuo, Li-wei

2013-09-01

Chaotic systems have complex reactions against an external driving force; even in cases with low-dimension oscillators, the routes to synchronization are diverse. We proposed a stroboscope-based method for analyzing driven chaotic systems in their phase space. According to two statistic quantities generated from time series, we could realize the system state and the driving behavior simultaneously. We demonstrated our method in a driven bi-stable system, which showed complex period windows under a proper driving force. With increasing periodic driving force, a route from interior periodic oscillation to phase synchronization through the chaos state could be found. Periodic windows could also be identified and the circumstances under which they occurred distinguished. Statistical results were supported by conditional Lyapunov exponent analysis to show the power in analyzing the unknown time series.

Identification of volatile organic compounds emitted by a naturally aged book using solid-phase microextraction/gas chromatography/mass spectrometry.

PubMed

Lattuati-Derieux, Agnès; Bonnassies-Termes, Sylvette; Lavédrine, Bertrand

2004-02-13

Solid-phase microextraction (SPME) coupled to gas chromatography/mass spectrometry (GC/MS) has been applied to the analysis of volatile organic compounds emitted from a naturally aged groundwood pulp paper originating from an old book in order to access the products produced through the decomposition reactions occurring in paper upon ageing. Two different extraction methods were developed and compared: headspace SPME and contact SPME. The influence of few extraction parameters were tested in order to define the best extraction conditions. An optimised non-destructive contact SPME method was elaborated and allowed the characterisation of more than 50 individual constituents.

TiO2 synthesized by microwave assisted solvothermal method: Experimental and theoretical evaluation

NASA Astrophysics Data System (ADS)

Moura, K. F.; Maul, J.; Albuquerque, A. R.; Casali, G. P.; Longo, E.; Keyson, D.; Souza, A. G.; Sambrano, J. R.; Santos, I. M. G.

2014-02-01

In this study, a microwave assisted solvothermal method was used to synthesize TiO2 with anatase structure. The synthesis was done using Ti (IV) isopropoxide and ethanol without templates or alkalinizing agents. Changes in structural features were observed with increasing time of synthesis and evaluated using periodic quantum chemical calculations. The anatase phase was obtained after only 1 min of reaction besides a small amount of brookite phase. Experimental Raman spectra are in accordance with the theoretical one. Micrometric spheres constituted by nanometric particles were obtained for synthesis from 1 to 30 min, while spheres and sticks were observed after 60 min.

The formation of urea in space. I. Ion-molecule, neutral-neutral, and radical gas-phase reactions

NASA Astrophysics Data System (ADS)

Brigiano, Flavio Siro; Jeanvoine, Yannick; Largo, Antonio; Spezia, Riccardo

2018-02-01

Context. Many organic molecules have been observed in the interstellar medium thanks to advances in radioastronomy, and very recently the presence of urea was also suggested. While those molecules were observed, it is not clear what the mechanisms responsible to their formation are. In fact, if gas-phase reactions are responsible, they should occur through barrierless mechanisms (or with very low barriers). In the past, mechanisms for the formation of different organic molecules were studied, providing only in a few cases energetic conditions favorable to a synthesis at very low temperature. A particularly intriguing class of such molecules are those containing one N-C-O peptide bond, which could be a building block for the formation of biological molecules. Urea is a particular case because two nitrogen atoms are linked to the C-O moiety. Thus, motivated also by the recent tentative observation of urea, we have considered the synthetic pathways responsible to its formation. Aims: We have studied the possibility of forming urea in the gas phase via different kinds of bi-molecular reactions: ion-molecule, neutral, and radical. In particular we have focused on the activation energy of these reactions in order to find possible reactants that could be responsible for to barrierless (or very low energy) pathways. Methods: We have used very accurate, highly correlated quantum chemistry calculations to locate and characterize the reaction pathways in terms of minima and transition states connecting reactants to products. Results: Most of the reactions considered have an activation energy that is too high; but the ion-molecule reaction between NH2OHNH2OH2+ and formamide is not too high. These reactants could be responsible not only for the formation of urea but also of isocyanic acid, which is an organic molecule also observed in the interstellar medium.

Kinetics and mechanism of electron transfer reaction of single and double chain surfactant cobalt(III) complex by Fe2+ ions in liposome (dipalmitoylphosphotidylcholine) vesicles: effects of phase transition

NASA Astrophysics Data System (ADS)

Nagaraj, Karuppiah; Senthil Murugan, Krishnan; Thangamuniyandi, Pilavadi

2015-05-01

In this study, we report the kinetics of reduction reactions of single and double chain surfactant cobalt(III) complexes of octahedral geometry, cis-[Co(en)2(4AMP)(DA)](ClO4)3 and cis-[Co(dmp)2(C12H25NH2)2](ClO4)3 (en = ethylenediamine, dmp = 1,3-diaminopropane, 4AMP = 4-aminopropane, C12H25NH2 = dodecylamine) by Fe2+ ion in dipalmitoylphosphotidylcholine (DPPC) vesicles at different temperatures under pseudo first-order conditions. The kinetics of these reactions is followed by spectrophotometry method. The reactions are found to be second order and the electron transfer is postulated as outer sphere. The remarkable findings in the present investigation are that, below the phase transition temperature of DPPC, the rate decreases with an increase in the concentration of DPPC, while above the phase transition temperature the rate increases with an increase in the concentration of DPPC. The main driving force for this phenomenon is considered to be the intervesicular hydrophobic interaction between vesicles surface and hydrophobic part of the surfactant complexes. Besides, comparing the values of rate constants of these outer-sphere electron transfer reactions in the absence and in the presence of DPPC, the rate constant values in the presence of DPPC are always found to be greater than in the absence of DPPC. This is ascribed to the double hydrophobic fatty acid chain in the DPPC that gives the molecule an overall tubular shape due to the intervesicular hydrophobic interaction between vesicles surface and hydrophobic part of the surfactant complexes more suitable for vesicle aggregation which facilitates lower activation energy, and consequently higher rate is observed in the presence of DPPC. The activation parameters (ΔS# and ΔH#) of the reactions at different temperatures have been calculated which corroborate the kinetics of the reaction.

Reaction pathways towards the formation of dolomite-analogues at ambient conditions

NASA Astrophysics Data System (ADS)

Pimentel, Carlos; Pina, Carlos M.

2016-04-01

In this paper we present results of a study of the crystallisation behaviour of the dolomite-analogues norsethite and PbMg(CO3)2 at room temperature and atmospheric pressure. Whereas precipitation of norsethite was previously obtained by mixing solutions (Hood et al., 1974; Pimentel and Pina, 2014a,b), we report, for the first time, the synthesis of PbMg(CO3)2 by using the same method. The formation of both phases was promoted by ageing slurries for periods of time ranging from a few days (norsethite) up to 6 months (PbMg(CO3)2). The crystallisation of both norsethite and PbMg(CO3)2 occurs by sequences of dissolution-precipitation reactions involving several amorphous and crystalline precursor phases, which were identified and characterised by X-ray diffraction and scanning electron microscopy. Depending on the initial composition and Ba:Mg and Pb:Mg ratios in the slurries, different precursors and reaction kinetics were observed. This demonstrates the existence of different reaction pathways towards the formation of the investigated dolomite-analogues. Our experimental results provide new insights into the possible mechanisms of formation of dolomite and other double carbonates in nature.

Atmospheric chemistry of cyc-CF2CF2CF2CH=CH-: Kinetics, products, and mechanism of gas-phase reaction with OH radicals, and atmospheric implications

NASA Astrophysics Data System (ADS)

Guo, Qin; Zhang, Ni; Uchimaru, Tadafumi; Chen, Liang; Quan, Hengdao; Mizukado, Junji

2018-04-01

The rate constants for the gas-phase reactions of cyc-CF2CF2CF2CH=CH- with OH radicals were determined by a relative rate method between 253 and 328 K. The rate constant k1 at 298 K was measured to be (1.08 ± 0.04) × 10-13 cm3 molecule-1 s-1, and the Arrhenius expression was k1 = (3.72 ± 0.14) × 10-13 exp [(-370 ± 12)/T]. The atmospheric lifetime of cyc-CF2CF2CF2CH=CH- was calculated to be 107 d. The products and mechanism for the reaction of cyc-CF2CF2CF2CH=CH- with OH radicals were also investigated. CO, CO2, and COF2 were identified as the main carbon-containing products following the OH-initiated reaction. Moreover, the radiative efficiency (RE) was determined to be 0.143 W m-2 ppb-1, and the global warming potentials (GWPs) for 20, 100, and 500 yr were 54, 15, and 4, respectively. The photochemical ozone creation potential of the title compound was estimated to be 1.3.

Developing a New Sampling And Analysis Method For Hydrazine And Monomethyl Hydrazine: Using a Derivatizing Agent With Solid Phase Microextraction

NASA Technical Reports Server (NTRS)

Allen, John

2001-01-01

Solid phase microextraction (SPME) will be used to develop a method for detecting monomethyl hydrazine (MMH) and hydrazine (Hz). A derivatizing agent, pentafluorobenzoyl chloride (PFBCI), is known to react readily with MMH and Hz. The SPME fiber can either be coated with PFBCl and introduced into a gaseous stream containing MMH, or PFBCl and MMH can react first in a syringe barrel and after a short equilibration period a SPME is used to sample the resulting solution. These methods were optimized and compared. Because Hz and MMH can degrade the SPME, letting the reaction occur first gave better results. Only MMH could be detected using either of these methods. Future research will concentrate on constructing calibration curves and determining the detection limit.

A Fully-automated One-pot Synthesis of [18F]Fluoromethylcholine with Reduced Dimethylaminoethanol Contamination via [18F]Fluoromethyl Tosylate

PubMed Central

Rodnick, Melissa E.; Brooks, Allen F.; Hockley, Brian G.; Henderson, Bradford D.; Scott, Peter J. H.

2013-01-01

Introduction A novel one-pot method for preparing [18F]fluoromethylcholine ([18F]FCH) via in situ generation of [18F]fluoromethyl tosylate ([18F]FCH2OTs), and subsequent [18F]fluoromethylation of dimethylaminoethanol (DMAE), has been developed. Methods [18F]FCH was prepared using a GE TRACERlab FXFN, although the method should be readily adaptable to any other fluorine-18 synthesis module. Initially ditosylmethane was fluorinated to generate [18F]FCH2OTs. DMAE was then added and the reaction was heated at 120°C for 10 min to generate [18F]FCH. After this time, reaction solvent was evaporated, and the crude reaction mixture was purified by solid-phase extraction using C18-Plus and CM-Light Sep-Pak cartridges to provide [18F]FCH formulated in USP saline. The formulated product was passed through a 0.22 μm filter into a sterile dose vial, and submitted for quality control testing. Total synthesis time was 1.25 hours from end-of-bombardment. Results Typical non-decay-corrected yields of [18F]FCH prepared using this method were 91 mCi (7% non-decay corrected based upon ~1.3 Ci [18F]fluoride), and doses passed all other quality control (QC) tests. Conclusion A one-pot liquid-phase synthesis of [18F]FCH has been developed. Doses contain extremely low levels of residual DMAE (31.6 μg / 10 mL dose or ~3 ppm) and passed all other requisite QC testing, confirming their suitability for use in clinical imaging studies. PMID:23665261

The Goldilocks Principle in Phase Labeling. Minimalist and Orthogonal Phase Tagging for Chromatography-Free Mitsunobu Reaction.

PubMed

Szigeti, Mariann; Dobi, Zoltán; Soós, Tibor

2018-03-02

An inexpensive and chromatography-free Mitsunobu methodology has been developed using low molecular weight and orthogonally phase-tagged reagents, a tert-butyl-tagged highly apolar phosphine, and a water-soluble DIAD analogue. The byproduct of the Mitsunobu reactions can be removed by sequential liquid-liquid extractions using traditional solvents such as hexanes, MeOH, water, and EtOAc. Owing to the orthogonal phase labeling, the spent reagents can be regenerated. This new variant of the Mitsunobu reaction promises to provide an alternative and complementary solution for the well-known separation problem of the Mitsunobu reaction without having to resort to expensive, large molecular weight reagents and chromatography.

A Chemiluminescence Detector for Ozone Measurement.

ERIC Educational Resources Information Center

Carroll, H.; And Others

An ozone detector was built and evaluated for its applicability in smog chamber studies. The detection method is based on reaction of ozone with ethylene and measurement of resultant chemiluminescence. In the first phase of evaluation, the detector's response to ozone was studied as a function of several instrument parameters, and optimum…

Enzymatic oxidation of ethanol in the gaseous phase.

PubMed

Barzana, E; Karel, M; Klibanov, A M

1989-11-01

The enzymatic conversion of gaseous substrates represents a novel concept in bioprocessing. A critical parameter in such systems is the water activity, A(w) The present article reports the effect of A(w) on the catalytic performance of alcohol oxidase acting on ethanol vapors. Enzyme activity in the gas-phase reaction increases several orders of magnitude, whereas the thermostability decreases drastically when A(w) is increased from 0.11 to 0.97. The enzyme is active on gaseous substrates even at hydration levels below the monolayer coverage. Enhanced thermostability at lower hydrations results in an increase in the optimum temperature of the gas-phase reaction catalyzed by alcohol oxidase. The apparent activation energy decreases as A(w) increases, approaching the value obtained for the enzyme in aqueous solution. The formation of a pread-sorbed ethanol phase on the surface of the support is not a prerequisite for the reaction, suggesting that the reaction occurs by direct interaction of the gaseous substrate with the enzyme. The gas-phase reaction follows Michaelis-Menten kinetics, with a K(m) value almost 100 times lower than that in aqueous solution. Based on vapor-liquid equilibrium data and observed K(m) values, it is postulated that during the gas-phase reaction the ethanol on the enzyme establishes an equilibrium with the ethanol vapor similar to that between ethanol in water and ethanol in the gas phase.

Enhanced Multiferroic Properties of YMnO3 Ceramics Fabricated by Spark Plasma Sintering Along with Low-Temperature Solid-State Reaction

PubMed Central

Wang, Meng; Wang, Ting; Song, Shenhua; Ravi, Muchakayala; Liu, Renchen; Ji, Shishan

2017-01-01

Based on precursor powders with a size of 200–300 nm prepared by the low-temperature solid-state reaction method, phase-pure YMnO3 ceramics are fabricated using spark plasma sintering (SPS). X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal that the high-purity YMnO3 ceramics can be prepared by SPS at 1000 °C for 5 minutes with annealing at 800 °C for 2 h. The relative density of the sample is as high as 97%, which is much higher than those of the samples sintered by other methods. The present dielectric and magnetic properties are much better than those of the samples fabricated by conventional methods and SPS with ball-milling precursors, and the ferroelectric loops at room temperature can be detected. These findings indicate that the YMnO3 ceramics prepared by the low temperature solid reaction method and SPS possess excellent dielectric lossy ferroelectric properties at room temperature, and magnetic properties at low temperature (10 K), making them suitable for potential multiferroic applications. PMID:28772832

Ratioed scatter diagrams - An erotetic method for phase identification on complex surfaces using scanning Auger microscopy

NASA Technical Reports Server (NTRS)

Browning, R.

1984-01-01

By ratioing multiple Auger intensities and plotting a two-dimensional occupational scatter diagram while digitally scanning across an area, the number and elemental association of surface phases can be determined. This can prove a useful tool in scanning Auger microscopic analysis of complex materials. The technique is illustrated by results from an anomalous region on the reaction zone of a SiC/Ti-6Al-4V metal matrix composite material. The anomalous region is shown to be a single phase associated with sulphur and phosphorus impurities. Imaging of a selected phase from the ratioed scatter diagram is possible and may be a useful technique for presenting multiple scanning Auger images.

Effect of the Gouy phase on the coherent phase control of chemical reactions.

PubMed

Gordon, Robert J; Barge, Vishal J

2007-11-28

We show how the spatial phase of a focused laser beam may be used as a tool for controlling the branching ratio of a chemical reaction. Guoy discovered [Acad. Sci., Paris, C. R. 110, 1250 (1890)] that when an electromagnetic wave passes through a focus its phase increases by pi. In a coherent control scheme involving the absorption of n photons of frequency omega(m) and m photons of frequency omega(n), the overall phase shift produced by the Gouy phase is (n-m)pi. At any given point in space, this phase shift is identical for all reaction products. Nevertheless, if the yields for different reaction channels have different intensity dependencies, the Gouy phase produces a net phase lag between the products that varies with the axial coordinate of the laser focus. We obtain here analytical and numerical values of this phase as the laser focus is scanned across the diameter of the molecular beam, taking into account the Rayleigh range and astigmatism of the laser beam and saturation of the transition. We also show that the modulation depth of the interference pattern may be increased by optimizing the relative intensities of the two fields.

Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes.

PubMed

Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

2016-12-01

The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (U VI O 2 2+ ) coordinated by formate or acetate ligands. Anionic complexes containing U VI O 2 2+ and formate ligands fragment by decarboxylation and elimination of CH 2 =O, ultimately to produce an oxo-hydride species [U VI O 2 (O)(H)] - . Cationic species ultimately dissociate to make [U VI O 2 (OH)] + . Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH 3 CO 2 •, with associated reduction of uranyl to U V O 2 + . Subsequent CID steps cause elimination of CO 2 and CH 4 , ultimately to produce [U V O 2 (O)] - . Loss of CH 4 occurs by an intra-complex H + transfer process that leaves U V O 2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH 2 =C=O to leave [U V O 2 (O)] - . Elimination of CH 4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H 2 O. The reactions of other anionic species with gas-phase H 2 O create hydroxyl products, presumably through the elimination of H 2 . Graphical Abstract ᅟ.

Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes

NASA Astrophysics Data System (ADS)

Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

2016-12-01

The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (UVIO2 2+) coordinated by formate or acetate ligands. Anionic complexes containing UVIO2 2+ and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [UVIO2(O)(H)]-. Cationic species ultimately dissociate to make [UVIO2(OH)]+. Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to UVO2 +. Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [UVO2(O)]-. Loss of CH4 occurs by an intra-complex H+ transfer process that leaves UVO2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [UVO2(O)]-. Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2.

Rapid-mix and chemical quench studies of ferredoxin-reduced stearoyl-acyl carrier protein desaturase.

PubMed

Lyle, Karen S; Haas, Jeffrey A; Fox, Brian G

2003-05-20

Stearoyl-ACP Delta9 desaturase (Delta9D) catalyzes the NADPH- and O(2)-dependent insertion of a cis double bond between the C9 and C10 positions of stearoyl-ACP (18:0-ACP) to produce oleoyl-ACP (18:1-ACP). This work revealed the ability of reduced [2Fe-2S] ferredoxin (Fd) to act as a catalytically competent electron donor during the rapid conversion of 18:0-ACP into 18:1-ACP. Experiments on the order of addition for substrate and reduced Fd showed high conversion of 18:0-ACP to 18:1-ACP (approximately 95% per Delta9D active site in a single turnover) when 18:0-ACP was added prior to reduced Fd. Reactions of the prereduced enzyme-substrate complex with O(2) and the oxidized enzyme-substrate complex with reduced Fd were studied by rapid-mix and chemical quench methods. For reaction of the prereduced enzyme-substrate complex, an exponential burst phase (k(burst) = 95 s(-1)) of product formation accounted for approximately 90% of the turnover expected for one subunit in the dimeric protein. This rapid phase was followed by a slower phase (k(linear) = 4.0 s(-1)) of product formation corresponding to the turnover expected from the second subunit. For reaction of the oxidized enzyme-substrate complex with excess reduced Fd, a slower, linear rate (k(obsd) = 3.4 s(-1)) of product formation was observed over approximately 1.5 turnovers per Delta9D active site potentially corresponding to a third phase of reaction. An analysis of the deuterium isotope effect on the two rapid-mix reaction sequences revealed only a modest effect on k(burst) ((D)k(burst) approximately 1.5) and k(linear) (D)k(linear) approximately 1.4), indicating C-H bond cleavage does not contribute significantly to the rate-limiting steps of pre-steady-state catalysis. These results were used to assemble and evaluate a minimal kinetic model for Delta9D catalysis.

Effect of the synthesis conditions on the electrochemical properties of LiFePO{sub 4} obtained from NH{sub 4}FePO{sub 4}

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

Prosini, Pier Paolo, E-mail: pierpaolo.prosini@enea.it; Gislon, Paola; Cento, Cinzia

Graphical abstract: - Highlights: • Four different samples of FAP were synthesized by precipitation techniques. • The samples were used as precursors to synthesize electrochemical active LiFePO{sub 4}. • Their morphology, composition, structure and electrochemical performance were studied. • The LiFePO{sub 4} electrochemical performance resulted affected by the preparation method - Abstract: In this paper the morphological, structural and electrochemical properties of crystalline lithium iron phosphate (LiFePO{sub 4}) obtained from ferrous ammonium phosphate (FAP) have been studied. The FAP was obtained following four different processes, namely: (1) homogeneous phase precipitation, (2) heterogeneous phase precipitation from stoichiometric sodium phosphate, (3) heterogeneousmore » phase precipitation from stoichiometric ammonium phosphate, and (4) heterogeneous phase precipitation from over stoichiometric ammonium phosphate. Lithium iron phosphate was prepared by solid state reaction of FAP with lithium hydroxide. In order to evaluate the effect of reaction time and synthesis temperature the LiFePO{sub 4} was prepared varying the heating temperatures (550, 600 and 700 °C) and the reaction times (1 or 2 h). The morphology of the materials was evaluated by scanning electron microscopy while the chemical composition was determined by electron energy loss spectroscopy. X-ray diffraction was used to evaluate phase composition, crystal structure and crystallite size. The so obtained LiFePO{sub 4}'s were fully electrochemical characterized and a correlation was found between the crystal size and the electrochemical performance.« less

Determination of free and deconjugated testosterone and epitestosterone in urine using SPME and LC-MS/MS.

PubMed

Zhan, Yanwei; Musteata, Florin M; Basset, Fabien A; Pawliszyn, Janusz

2011-01-01

A thin sheet of polydimethylsilosane membrane was used as an extraction phase for solid-phase microextraction. Compared with fiber or rod solid-phase microextraction geometries, the thin film exhibited much higher extraction capacity without sacrificing extraction time due to its higher area-to-volume ratio. The analytical method involved direct extraction of unconjugated testosterone (T) and epitestosterone (ET) followed by separation on a C18 column and detection by selected reaction monitoring in positive ionization mode. The limit of detection was 1 ng/l for both T and ET. After method validation, free (unconjugated) T and ET were extracted and quantified in real samples. Since T and ET are extensively metabolized, the proposed method was also applied to extract the steroids after enzymatic deconjugation of urinary-excreted steroid glucuronides. The proposed method allows quantification of both conjugated and unconjugated steroids, and revealed that there was a change in the ratio of T to ET after enzymatic deconjugation, indicating different rates of metabolism.

Massively parallel haplotyping on microscopic beads for the high-throughput phase analysis of single molecules.

PubMed

Boulanger, Jérôme; Muresan, Leila; Tiemann-Boege, Irene

2012-01-01

In spite of the many advances in haplotyping methods, it is still very difficult to characterize rare haplotypes in tissues and different environmental samples or to accurately assess the haplotype diversity in large mixtures. This would require a haplotyping method capable of analyzing the phase of single molecules with an unprecedented throughput. Here we describe such a haplotyping method capable of analyzing in parallel hundreds of thousands single molecules in one experiment. In this method, multiple PCR reactions amplify different polymorphic regions of a single DNA molecule on a magnetic bead compartmentalized in an emulsion drop. The allelic states of the amplified polymorphisms are identified with fluorescently labeled probes that are then decoded from images taken of the arrayed beads by a microscope. This method can evaluate the phase of up to 3 polymorphisms separated by up to 5 kilobases in hundreds of thousands single molecules. We tested the sensitivity of the method by measuring the number of mutant haplotypes synthesized by four different commercially available enzymes: Phusion, Platinum Taq, Titanium Taq, and Phire. The digital nature of the method makes it highly sensitive to detecting haplotype ratios of less than 1:10,000. We also accurately quantified chimera formation during the exponential phase of PCR by different DNA polymerases.

Impact of In-Cloud Aqueous Processes on the Chemistry and Transport of Biogenic Volatile Organic Compounds

NASA Astrophysics Data System (ADS)

Li, Yang; Barth, Mary C.; Patton, Edward G.; Steiner, Allison L.

2017-10-01

We investigate the impacts of cloud aqueous processes on the chemistry and transport of biogenic volatile organic compounds (BVOC) using the National Center for Atmospheric Research's large-eddy simulation code with an updated chemical mechanism that includes both gas- and aqueous-phase reactions. We simulate transport and chemistry for a meteorological case with a diurnal pattern of nonprecipitating cumulus clouds from the Baltimore-Washington area DISCOVER-AQ campaign. We evaluate two scenarios with and without aqueous-phase chemical reactions. In the cloud layer (2-3 km), the addition of aqueous phase reactions decreases HCHO by 18% over the domain due to its solubility and the fast depletion from aqueous reactions, resulting in a corresponding decrease in radical oxidants (e.g., 18% decrease in OH). The decrease of OH increases the mixing ratios of isoprene and methacrolein (MACR) (100% and 15%, respectively) in the cloud layer because the reaction rate is lower. Aqueous-phase reactions can modify the segregation between OH and BVOC by changing the sign of the segregation intensity, causing up to 55% reduction in the isoprene-OH reaction rate and 40% reduction for the MACR-OH reaction when clouds are present. Analysis of the isoprene-OH covariance budget shows the chemistry term is the primary driver of the strong segregation in clouds, triggered by the decrease in OH. All organic acids except acetic acid are formed only through aqueous-phase reactions. For acids formed in the aqueous phase, turbulence mixes these compounds on short time scales, with the near-surface mixing ratios of these acids reaching 20% of the mixing ratios in the cloud layer within 1 h of cloud formation.

On-the-Fly Kinetic Monte Carlo Simulation of Aqueous Phase Advanced Oxidation Processes.

PubMed

Guo, Xin; Minakata, Daisuke; Crittenden, John

2015-08-04

We have developed an on-the-fly kinetic Monte Carlo (KMC) model to predict the degradation mechanisms and fates of intermediates and byproducts that are produced during aqueous-phase advanced oxidation processes (AOPs). The on-the-fly KMC model is composed of a reaction pathway generator, a reaction rate constant estimator, a mechanistic reduction module, and a KMC solver. The novelty of this work is that we develop the pathway as we march forward in time rather than developing the pathway before we use the KMC method to solve the equations. As a result, we have fewer reactions to consider, and we have greater computational efficiency. We have verified this on-the-fly KMC model for the degradation of polyacrylamide (PAM) using UV light and titanium dioxide (i.e., UV/TiO2). Using the on-the-fly KMC model, we were able to predict the time-dependent profiles of the average molecular weight for PAM. The model provided detailed and quantitative insights into the time evolution of the molecular weight distribution and reaction mechanism. We also verified our on-the-fly KMC model for the destruction of (1) acetone, (2) trichloroethylene (TCE), and (3) polyethylene glycol (PEG) for the ultraviolet light and hydrogen peroxide AOP. We demonstrated that the on-the-fly KMC model can achieve the same accuracy as the computer-based first-principles KMC (CF-KMC) model, which has already been validated in our earlier work. The on-the-fly KMC is particularly suitable for molecules with large molecular weights (e.g., polymers) because the degradation mechanisms for large molecules can result in hundreds of thousands to even millions of reactions. The ordinary differential equations (ODEs) that describe the degradation pathways cannot be solved using traditional numerical methods, but the KMC can solve these equations.

Novel approach to quantitative polymerase chain reaction using real-time detection: application to the detection of gene amplification in breast cancer.

PubMed

Bièche, I; Olivi, M; Champème, M H; Vidaud, D; Lidereau, R; Vidaud, M

1998-11-23

Gene amplification is a common event in the progression of human cancers, and amplified oncogenes have been shown to have diagnostic, prognostic and therapeutic relevance. A kinetic quantitative polymerase-chain-reaction (PCR) method, based on fluorescent TaqMan methodology and a new instrument (ABI Prism 7700 Sequence Detection System) capable of measuring fluorescence in real-time, was used to quantify gene amplification in tumor DNA. Reactions are characterized by the point during cycling when PCR amplification is still in the exponential phase, rather than the amount of PCR product accumulated after a fixed number of cycles. None of the reaction components is limited during the exponential phase, meaning that values are highly reproducible in reactions starting with the same copy number. This greatly improves the precision of DNA quantification. Moreover, real-time PCR does not require post-PCR sample handling, thereby preventing potential PCR-product carry-over contamination; it possesses a wide dynamic range of quantification and results in much faster and higher sample throughput. The real-time PCR method, was used to develop and validate a simple and rapid assay for the detection and quantification of the 3 most frequently amplified genes (myc, ccndl and erbB2) in breast tumors. Extra copies of myc, ccndl and erbB2 were observed in 10, 23 and 15%, respectively, of 108 breast-tumor DNA; the largest observed numbers of gene copies were 4.6, 18.6 and 15.1, respectively. These results correlated well with those of Southern blotting. The use of this new semi-automated technique will make molecular analysis of human cancers simpler and more reliable, and should find broad applications in clinical and research settings.

Characterization of the reaction products and precipitates at the interface of carbon fiber reinforced magnesium–gadolinium composite

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

Wang, Yaping; Jiang, Longtao, E-mail: longtaojiang@163.com; Chen, Guoqin

2016-03-15

In the present work, carbon fiber reinforced magnesium-gadolinium composite was fabricated by pressure infiltration method. The phase composition, micro-morphology, and crystal structure of reaction products and precipitates at the interface of the composite were investigated. Scanning electron microscopy and energy dispersive spectroscopy analysis revealed the segregation of gadolinium element at the interface between carbon fiber and matrix alloy. It was shown that block-shaped Gd4C5, GdC2 and nano-sized Gd2O3 were formed at the interface during the fabrication process due to the interfacial reaction. Furthermore, magnesium-gadolinium precipitates including needle-like Mg5Gd (or Mg24Gd5) and thin plate-shaped long period stacking-ordered phase, were also observedmore » at the interface and in the matrix near the interface. The interfacial microstructure and bonding mode were influenced by these interfacial products, which were beneficial for the improvement of the interfacial bonding strength. - Highlights: • Gadolinium element segregated on the surface of carbon fibers. • Block-shaped Gd{sub 4}C{sub 5} and GdC{sub 2} were formed at the interface via chemical reaction. • Gadolinium and oxygen reacted at the interface and formed nano-scaled Gd{sub 2}O{sub 3}. • The precipitates formed in the interface were identified to be Mg{sub 5}Gd (or Mg{sub 24}Gd{sub 5}) and plate-shaped long period stacking-ordered phase.« less

Detonation Initiation of Heterogeneous Melt-Cast High Explosives

NASA Astrophysics Data System (ADS)

Chuzeville, Vincent; Baudin, Gerard; Lefrancois, Alexandre; Boulanger, Remi; Catoire, Laurent

2015-06-01

The melt-cast explosives' shock initiation mechanisms are less investigated than pressed and cast-cured ones. If the existence of hot-spots is widely recognized, their formation mechanism is not yet established. We study here two melt-cast explosives, NTO-TNT 60:40 and RDX-TNT 60:40 in order to establish a relation between the microstructure and the reaction rate using a two-phase model based on a ZND approach. Such a model requires the reaction rate, the equations of state of the unreacted phase and of the detonation products and an interaction model between the two phases to describe the reaction zone thermodynamics. The reaction rate law can be written in a factorized form including the number of initiation sites, the explosive's deflagration velocity around hot spots and a function depending on gas volume fraction produced by the deflagration front propagation. The deflagration velocity mainly depends on pressure and is determined from pop-plot tests using the hypothesis of the single curve build-up. This hypothesis has been verified for our two melt-cast explosives. The function depending on gas volume fraction is deduced from microstructural observations and from an analogy with the solid nucleation and growth theory. It has been established for deflagration fronts growing from grain's surface and a given initial grain size distribution. The model requires only a few parameters, calibrated thanks to an inversion method. A good agreement is obtained between experiments and numerical simulations.

Increased Depth and Breadth of Plasma Protein Quantitation via Two-Dimensional Liquid Chromatography/Multiple Reaction Monitoring-Mass Spectrometry with Labeled Peptide Standards.

PubMed

Percy, Andrew J; Yang, Juncong; Chambers, Andrew G; Borchers, Christoph H

2016-01-01

Absolute quantitative strategies are emerging as a powerful and preferable means of deriving concentrations in biological samples for systems biology applications. Method development is driven by the need to establish new-and validate current-protein biomarkers of high-to-low abundance for clinical utility. In this chapter, we describe a methodology involving two-dimensional (2D) reversed-phase liquid chromatography (RPLC), operated under alkaline and acidic pH conditions, combined with multiple reaction monitoring (MRM)-mass spectrometry (MS) (also called selected reaction monitoring (SRM)-MS) and a complex mixture of stable isotope-labeled standard (SIS) peptides, to quantify a broad and diverse panel of 253 proteins in human blood plasma. The quantitation range spans 8 orders of magnitude-from 15 mg/mL (for vitamin D-binding protein) to 450 pg/mL (for protein S100-B)-and includes 31 low-abundance proteins (defined as being <10 ng/mL) of potential disease relevance. The method is designed to assess candidates at the discovery and/or verification phases of the biomarker pipeline and can be adapted to examine smaller or alternate panels of proteins for higher sample throughput. Also detailed here is the application of our recently developed software tool-Qualis-SIS-for protein quantitation (via regression analysis of standard curves) and quality assessment of the resulting data. Overall, this chapter provides the blueprint for the replication of this quantitative proteomic method by proteomic scientists of all skill levels.

Hydrogen production via reforming of biogas over nanostructured Ni/Y catalyst: Effect of ultrasound irradiation and Ni-content on catalyst properties and performance

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

Sharifi, Mahdi; Reactor and Catalysis Research Center; Haghighi, Mohammad, E-mail: haghighi@sut.ac.ir

2014-12-15

Highlights: • Synthesis of nanostructured Ni/Y catalyst by sonochemical and impregnation methods. • Enhancement of size distribution and active phase dispersion by employing sonochemical method. • Evaluation of biogas reforming over Ni/Y catalyst with different Ni-loadings. • Preparation of highly active and stable catalyst with low Ni content for biogas reforming. • Getting H{sub 2}/CO very close to equilibrium ratio by employing sonochemical method. - Abstract: The effect of ultrasound irradiation and various Ni-loadings on dispersion of active phase over zeolite Y were evaluated in biogas reforming for hydrogen production. X-ray diffraction, field emission scanning electron microscopy, energy dispersive X-ray,more » Brunauer–Emmett–Teller, Fourier transform infrared analysis and TEM analysis were employed to observe the characteristics of nanostructured catalysts. The characterizations implied that utilization of ultrasound irradiation enhanced catalyst physicochemical properties including high dispersion of Ni on support, smallest particles size and high catalyst surface area. The reforming reactions were carried out at GHSV = 24 l/g.h, P = 1 atm, CH{sub 4}/CO{sub 2} = 1 and temperature range of 550–850 °C. Activity test displayed that ultrasound irradiated Ni(5 wt.%)/Y had the best performance and the activity remained stable during 600 min. Furthermore, the proposed reaction mechanism showed that there are three major reaction channels in biogas reforming.« less

Chalcogen Polymers for Completely Solution-Processed Inorganic Photovoltaics

NASA Astrophysics Data System (ADS)

Martin, Trevor R.

Chalcopyrite materials such as CuInSxSe2-x (CISSe), the gallium alloy variant CuInxGa1-xSySe2-y (CIGSSe), and the earth-abundant kesterite material Cu2ZnSnS xSe4-x (CZTSSe) possess a range of properties that are ideally suited for thin-film photovoltaics (PV) applications. Although these materials are beginning to see some commercial success, they are manufactured using complicated and expensive techniques such as high temperature processing, vacuum deposition methods, and vapor-phase reactions. These production methods require an exorbitantly large capital investment to create new manufacturing facilities, which severely hampers the widespread and rapid deployment of these emerging solar energy technologies. This work has focused on developing novel chalcogen polymers to synthesize nanoparticles and produce thin-films for printed photovoltaics applications. This new method provides a pathway towards using chalcogen copolymers to produce these materials via a completely solution-processed, low-temperature fabrication procedure. This technique constitutes one of the first viable means to produce low-bandgap chalcogenides without additional vapor-phase or high-temperature reactions. Therefore, this process can potentially be implemented to rapidly and cheaply manufacture printed chalcopyrite and kesterite photovoltaics.

Deuterium Substitution used as a Tool for Investigating Mechanisms of Gas-Phase Free-Radical Reactions

NASA Technical Reports Server (NTRS)

Wine, P. H.; Hynes, A. J.; Nicovich, J. M.

1997-01-01

Results are presented and discussed for a number of gas phase free radical reactions where H/D isotope effects provide valuable mechanistic insights. The cases considered are (1) the reactions of OH, NO3, and Cl with atmospheric reduced sulfur compounds, (2) the reactions of OH and OD with CH3CN and CD3CN, and (3) the reactions of alkyl radicals with HBr and DBr.

Derivatization reaction-based surface-enhanced Raman scattering (SERS) for detection of trace acetone.

PubMed

Zheng, Ying; Chen, Zhuo; Zheng, Chengbin; Lee, Yong-Ill; Hou, Xiandeng; Wu, Li; Tian, Yunfei

2016-08-01

A facile method was developed for determination of trace volatile acetone by coupling a derivatization reaction to surface-enhanced Raman scattering (SERS). With iodide modified Ag nanoparticles (Ag IMNPs) as the SERS substrate, acetone without obvious Raman signal could be converted to SERS-sensitive species via a chemical derivatization reaction with 2,4-dinitrophenylhydrazine (2,4-DNPH). In addition, acetone can be effectively separated from liquid phase with a purge-sampling device and then any serious interference from sample matrices can be significantly reduced. The optimal conditions for the derivatization reaction and the SERS analysis were investigated in detail, and the selectivity and reproducibility of this method were also evaluated. Under the optimal conditions, the limit of detection (LOD) for acetone was 5mgL(-1) or 0.09mM (3σ). The relative standard deviation (RSD) for 80mgL(-1) acetone (n=9) was 1.7%. This method was successfully used for the determination of acetone in artificial urine and human urine samples with spiked recoveries ranging from 92% to 110%. The present method is convenient, sensitive, selective, reliable and suitable for analysis of trace acetone, and it could have a promising clinical application in early diabetes diagnosis. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of three-dimensional reduced graphene oxide layer supported cobalt nanocrystals and their high catalytic activity in F-T CO2 hydrogenation

NASA Astrophysics Data System (ADS)

He, Fei; Niu, Na; Qu, Fengyu; Wei, Shuquan; Chen, Yujin; Gai, Shili; Gao, Peng; Wang, Yan; Yang, Piaoping

2013-08-01

The reduced graphene oxide (rGO) supported cobalt nanocrystals have been synthesized through an in situ crystal growth method using Co(acac)2 under solvothermal conditions by using DMF as the solvent. By carefully controlling the reaction temperature, the phase transition of the cobalt nanocrystals from the cubic phase to the hexagonal phase has been achieved. Moreover, the microscopic structure and morphology as well as the reduction process of the composite have been investigated in detail. It is found that oxygen-containing functional groups on the graphene oxide (GO) can greatly influence the formation process of the Co nanocrystals by binding the Co2+ cations dissociated from the Co(acac)2 in the initial reaction solution at 220 °C, leading to the 3D reticular structure of the composite. Furthermore, this is the first attempt to use a Co/rGO composite as the catalyst in the F-T CO2 hydrogenation process. The catalysis testing results reveal that the as-synthesized 3D structured composite exhibits ideal catalytic activity and good stability, which may greatly extend the scope of applications for this kind of graphene-based metal hybrid material.The reduced graphene oxide (rGO) supported cobalt nanocrystals have been synthesized through an in situ crystal growth method using Co(acac)2 under solvothermal conditions by using DMF as the solvent. By carefully controlling the reaction temperature, the phase transition of the cobalt nanocrystals from the cubic phase to the hexagonal phase has been achieved. Moreover, the microscopic structure and morphology as well as the reduction process of the composite have been investigated in detail. It is found that oxygen-containing functional groups on the graphene oxide (GO) can greatly influence the formation process of the Co nanocrystals by binding the Co2+ cations dissociated from the Co(acac)2 in the initial reaction solution at 220 °C, leading to the 3D reticular structure of the composite. Furthermore, this is the first attempt to use a Co/rGO composite as the catalyst in the F-T CO2 hydrogenation process. The catalysis testing results reveal that the as-synthesized 3D structured composite exhibits ideal catalytic activity and good stability, which may greatly extend the scope of applications for this kind of graphene-based metal hybrid material. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr03038e

Encapsulated nano-heat-sinks for thermal management of heterogeneous chemical reactions.

PubMed

Zhang, Minghui; Hong, Yan; Ding, Shujiang; Hu, Jianjun; Fan, Yunxiao; Voevodin, Andrey A; Su, Ming

2010-12-01

This paper describes a new way to control temperatures of heterogeneous exothermic reactions such as heterogeneous catalytic reaction and polymerization by using encapsulated nanoparticles of phase change materials as thermally functional additives. Silica-encapsulated indium nanoparticles and silica encapsulated paraffin nanoparticles are used to absorb heat released in catalytic reaction and to mitigate gel effect of polymerization, respectively. The local hot spots that are induced by non-homogenous catalyst packing, reactant concentration fluctuation, and abrupt change of polymerization rate lead to solid to liquid phase change of nanoparticle cores so as to avoid thermal runaway by converting energies from exothermic reactions to latent heat of fusion. By quenching local hot spots at initial stage, reaction rates do not rise significantly because the thermal energy produced in reaction is isothermally removed. Nanoparticles of phase change materials will open a new dimension for thermal management of exothermic reactions to quench local hot spots, prevent thermal runaway of reaction, and change product distribution.

Dynamics and control of gold-encapped gallium arsenide nanowires imaged by 4D electron microscopy

PubMed Central

Chen, Bin; Fu, Xuewen; Tang, Jau; Lysevych, Mykhaylo; Tan, Hark Hoe; Jagadish, Chennupati; Zewail, Ahmed H.

2017-01-01

Eutectic-related reaction is a special chemical/physical reaction involving multiple phases, solid and liquid. Visualization of a phase reaction of composite nanomaterials with high spatial and temporal resolution provides a key understanding of alloy growth with important industrial applications. However, it has been a rather challenging task. Here, we report the direct imaging and control of the phase reaction dynamics of a single, as-grown free-standing gallium arsenide nanowire encapped with a gold nanoparticle, free from environmental confinement or disturbance, using four-dimensional (4D) electron microscopy. The nondestructive preparation of as-grown free-standing nanowires without supporting films allows us to study their anisotropic properties in their native environment with better statistical character. A laser heating pulse initiates the eutectic-related reaction at a temperature much lower than the melting points of the composite materials, followed by a precisely time-delayed electron pulse to visualize the irreversible transient states of nucleation, growth, and solidification of the complex. Combined with theoretical modeling, useful thermodynamic parameters of the newly formed alloy phases and their crystal structures could be determined. This technique of dynamical control aided by 4D imaging of phase reaction processes on the nanometer-ultrafast time scale opens new venues for engineering various reactions in a wide variety of other systems. PMID:29158393

Equilibration in the time-dependent Hartree-Fock approach probed with the Wigner distribution function

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

Loebl, N.; Maruhn, J. A.; Reinhard, P.-G.

2011-09-15

By calculating the Wigner distribution function in the reaction plane, we are able to probe the phase-space behavior in the time-dependent Hartree-Fock scheme during a heavy-ion collision in a consistent framework. Various expectation values of operators are calculated by evaluating the corresponding integrals over the Wigner function. In this approach, it is straightforward to define and analyze quantities even locally. We compare the Wigner distribution function with the smoothed Husimi distribution function. Different reaction scenarios are presented by analyzing central and noncentral {sup 16}O +{sup 16}O and {sup 96}Zr +{sup 132}Sn collisions. Although we observe strong dissipation in the timemore » evolution of global observables, there is no evidence for complete equilibration in the local analysis of the Wigner function. Because the initial phase-space volumes of the fragments barely merge and mean values of the observables are conserved in fusion reactions over thousands of fm/c, we conclude that the time-dependent Hartree-Fock method provides a good description of the early stage of a heavy-ion collision but does not provide a mechanism to change the phase-space structure in a dramatic way necessary to obtain complete equilibration.« less

Atmospheric H2O2 measurement: comparison of cold trap method with impinger bubbling method

NASA Technical Reports Server (NTRS)

Sakugawa, H.; Kaplan, I. R.

1987-01-01

Collection of atmospheric H2O2 was performed by a cold trap method using dry ice-acetone as the refrigerant. The air was drawn by a pump into a glass gas trap immersed in the dry ice-acetone slush in a dewar flask at a flow rate of 2.5 l min-1 for approximately 2 h. Collection efficiency was > 99% and negligible interferences by O3, SO2 or organic matter with the collected H2O2 in the trap were observed. This method was compared with the air impinger bubbling method which has been previously described (Kok et al., 1978a, b, Envir. Sci. Technol. 12, 1072-1080). The measured total peroxide (H2O2 + organic peroxide) values in a series of aim samples collected by the impinger bubbling method (0.06-3.7 ppb) were always higher than those obtained by the cold trap method (0.02-1.2 ppb). Laboratory experiments suggest that the difference in values between the two methods probably results from the aqueous phase generation of H2O2 and organic peroxide in the impinger solution by a reaction of atmospheric O3 with olefinic and aromatic compounds. If these O3-organic compound reactions which occur in the impinger also occur in aqueous droplets in the atmosphere, the process could be very important for aqueous phase generation of H2O2 in clouds and rainwater.

Novel duplex vapor-electrochemical method for silicon solar cells. [reaction of fluorine and silicon compounds with sodium

NASA Technical Reports Server (NTRS)

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

1979-01-01

The dependence of the SiF4 Na reaction initiation time and of the efficiency of the reaction on Na particle size and reaction temperature were studied. Close to 100 percent utilization of Na was obtained, and formation of byproduct fluoro-silicate was decreased to below 10 percent. A SiF4 Na reactor was built to scale up the reaction by a factor of about four and is now being tested. A scaled up melting system was built and successfully used to separate Si from kilogram quantities of SiF4 NaF mixtures. Support studies of the volatilization of NaF performed in a smaller melting system indicated minimal loss of NaF as vapor at 1410 C. The wetting of graphite was also investigated to determine the constituents of the NaF phase which promote good wetting.

Environmentally friendly chemical recycling of poly(bisphenol-A carbonate) through phase transfer-catalysed alkaline hydrolysis under microwave irradiation.

PubMed

Tsintzou, Georgia P; Antonakou, Eleni V; Achilias, Dimitris S

2012-11-30

The various and widespread uses of polycarbonate (PC) polymers require a meaningful and environmentally friendly disposal method. In this study, depolymerisation of polycarbonate with water in a microwave reactor is suggested as a recycling method. Hydrolysis was investigated in an alkaline (NaOH) solution using a phase-transfer catalyst. All of the experiments were carried out in a sealed microwave reactor, in which the reaction pressure, temperature and microwave power were continuously controlled and recorded. In the hydrolysis products, bisphenol-A monomer was obtained and identified by FTIR measurements. PC degradation higher than 80% can be obtained at 160°C after a microwave irradiation time of either 40 min or 10 min using either a 5 or 10% (w/v) NaOH solution, respectively. GPC, TGA and DSC measurements of the PC residues revealed that surface erosion is the degradation mechanism. First-order reaction kinetics were estimated by implementing a simple kinetic model. Finally, greater than 85% degradation was achieved when waste CDs were treated with the same method. The results confirm the importance of the microwave power technique as a promising recycling method for PC-based waste plastics, resulting in monomer recovery in addition to substantial energy savings. Copyright © 2012 Elsevier B.V. All rights reserved.

Geometrical Optimization Approach to Isomerization: Models and Limitations.

PubMed

Chang, Bo Y; Shin, Seokmin; Engel, Volker; Sola, Ignacio R

2017-11-02

We study laser-driven isomerization reactions through an excited electronic state using the recently developed Geometrical Optimization procedure. Our goal is to analyze whether an initial wave packet in the ground state, with optimized amplitudes and phases, can be used to enhance the yield of the reaction at faster rates, driven by a single picosecond pulse or a pair of femtosecond pulses resonant with the electronic transition. We show that the symmetry of the system imposes limitations in the optimization procedure, such that the method rediscovers the pump-dump mechanism.

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.

Determination of the diffusion coefficient and phase-transfer rate parameter in LaNi{sub 5} and MmNi{sub 3.6}Co{sub 0.8}Mn{sub 0.4}Al{sub 0.3} using microelectrodes

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

Lundqvist, A.; Lindbergh, G.

1998-11-01

A potential-step method for determining the diffusion coefficient and phase-transfer parameter in metal hydrides by using microelectrodes was investigated. It was shown that a large potential step is not enough to ensure a completely diffusion-limited mass transfer if a surface-phase transfer reaction takes place at a finite rate. It was shown, using a kinetic expression for the surface phase-transfer reaction, that the slope of the logarithm of the current vs. time curve will be constant both in the case of the mass-transfer limited by diffusion or by diffusion and a surface-phase transfer. The diffusion coefficient and phase-transfer rate parameter weremore » accurately determined for MmNi{sub 3.6}Co{sub 0.8}Mn{sub 0.4}Al{sub 0.3} using a fit to the whole transient. The diffusion coefficient was found to be (1.3 {+-} 0.3) {times} 10{sup {minus}13} m{sup 2}/s. The fit was good and showed that a pure diffusion model was not enough to explain the observed transient. The diffusion coefficient and phase-transfer rate parameter were also estimated for pure LaNi{sub 5}. A fit of the whole curve showed that neither a pure diffusion model nor a model including phase transfer could explain the whole transient.« less

An internally consistent set of thermodynamic data for twentyone CaO-Al2O3-SiO2- H2O phases by linear parametric programming

NASA Astrophysics Data System (ADS)

Halbach, Heiner; Chatterjee, Niranjan D.

1984-11-01

The technique of linear parametric programming has been applied to derive sets of internally consistent thermodynamic data for 21 condensed phases of the quaternary system CaO-Al2O3-SiO2-H2O (CASH) (Table 4). This was achieved by simultaneously processing: a) calorimetric data for 16 of these phases (Table 1), and b) experimental phase equilibria reversal brackets for 27 reactions (Table 3) involving these phases. Calculation of equilibrium P-T curves of several arbitrarily picked reactions employing the preferred set of internally consistent thermodynamic data from Table 4 shows that the input brackets are invariably satisfied by the calculations (Fig. 2a). By contrast, the same equilibria calculated on the basis of a set of thermodynamic data derived by applying statistical methods to a large body of comparable input data (Haas et al. 1981; Hemingway et al. 1982) do not necessarily agree with the experimental reversal brackets. Prediction of some experimentally investigated phase relations not included into the linear programming input database also appears to be remarkably successful. Indications are, therefore, that the thermodynamic data listed in Table 4 may be used with confidence to predict geologic phase relations in the CASH system with considerable accuracy. For such calculated phase diagrams and their petrological implications, the reader's attention is drawn to the paper by Chatterjee et al. (1984).

Cation Exchange Reactions for Improved Quality and Diversity of Semiconductor Nanocrystals

NASA Astrophysics Data System (ADS)

Beberwyck, Brandon James

Observing the size and shape dependent physical properties of semiconductor nanocrystals requires synthetic methods capable of not only composition and crystalline phase control but also molecular scale uniformity for a particle consisting of tens to hundreds of thousands of atoms. The desire for synthetic methods that produce uniform nanocrystals of complex morphologies continues to increase as nanocrystals find roles in commercial applications, such as biolabeling and display technologies, that are simultaneously restricting material compositions. With these constraints, new synthetic strategies that decouple the nanocrystal's chemical composition from its morphology are necessary. This dissertation explores the cation exchange reaction of colloidal semiconductor nanocrystals, a template-based chemical transformation that enables the interconversion of nanocrystals between a variety of compositions while maintaining their size dispersity and morphology. Chapter 1 provides an introduction to the versatility of this replacement reaction as a synthetic method for semiconductor nanocrystals. An overview of the fundamentals of the cation exchange reaction and the diversity of products that are achievable is presented. Chapter 2 examines the optical properties of nanocrystal heterostructures produced through cation exchange reactions. The deleterious impact of exchange on the photoluminescence is correlated to residual impurities and a simple annealing protocol is demonstrated to achieve photoluminescence yields comparable to samples produced by conventional methods. Chapter 3 investigates the extension of the cation exchange reaction beyond ionic nanocrystals. Covalent III-V nanocrystal of high crystallinity and low size dispersity are synthesized by the cation exchange of cadmium pnictide nanocrystals with group 13 ions. Lastly, Chapter 4 highlights future studies to probe cation exchange reactions in colloidal semiconductor nanocrystals and progress that needs to be made for its adoption as a routine synthetic approach.

Operando characterization of catalysts through use of a portable microreactor

DOE PAGES

Zhao, Shen; Li, Yuanyuan; Stavitski, Eli; ...

2015-10-09

To provide new understandings of the mechanisms of catalytic reactions, improved methods are needed than can monitor changes in the electronic, structural and chemical properties of catalysts, doing so in the operando conditions in which catalysts work. We describe here a microreactor-based approach that integrates the capabilities of advanced x-ray, electron, optical and gas-phase compositional analysis techniques in operando conditions. For several exemplary catalytic systems, we demonstrate how this approach enables characterization of three major factors contributing to structure-property correlations evidenced in heterogeneously catalyzed reactions, namely: the atomic structure and elemental compositions of nanocatalysts; the physiochemical properties of the supportmore » and catalyst-support interfaces; and the gas and surface-phase chemistry occurring under operando conditions. We highlight the generality of the approach as well as outline opportunities for future developments.« less

High pressure cosmochemistry of major planetary interiors: Laboratory studies of the water-rich region of the system ammonia-water

NASA Technical Reports Server (NTRS)

Nicol, Malcolm; Johnson, Mary; Boone, Steven; Cynn, Hyunchee

1987-01-01

Several studies relative to high pressure cosmochemistry of major planetary interiors are summarized. The behavior of gas-ice mixtures at very high pressures, studies of the phase diagram of (NH3) sub x (H2O) sub 1-x at pressures to 5GPa and temperatures from 240 to 370 K, single crystal growth of ammonia dihydrate at room temperature in order to determine their structures by x-ray diffraction, spectroscopy of chemical reactions during shock compression in order to evaluate how the reactions affect the interpretation of equation of state data obtained by shock methods, and temperature and x-ray diffraction measurements made on resistively heated wire in diamond anvil cells in order to obtain phase and structural data relevant to the interiors of terrestrial planets are among the studies discussed.

Real-time high-resolution X-ray imaging and nuclear magnetic resonance study of the hydration of pure and Na-doped C3A in the presence of sulfates

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

Kirchheim,, A. P.; Dal Molin, D.C.; Emwas, Abdul-Hamid

2010-12-01

This study details the differences in real-time hydration between pure tricalcium aluminate (cubic C{sub 3}A or 3CaO {center_dot} Al{sub 2}O{sub 3}) and Na-doped tricalcium aluminate (orthorhombic C{sub 3}A or Na{sub 2}Ca{sub 8}Al{sub 6}O{sub 18}), in aqueous solutions containing sulfate ions. Pure phases were synthesized in the laboratory to develop an independent benchmark for the reactions, meaning that their reactions during hydration in a simulated early age cement pore solution (saturated with respect to gypsum and lime) were able to be isolated. Because the rate of this reaction is extremely rapid, most microscopy methods are not adequate to study the earlymore » phases of the reactions in the early stages. Here, a high-resolution full-field soft X-ray imaging technique operating in the X-ray water window, combined with solution analysis by {sup 27}Al nuclear magnetic resonance (NMR) spectroscopy, was used to capture information regarding the mechanism of C{sub 3}A hydration during the early stages. There are differences in the hydration mechanism between the two types of C{sub 3}A, which are also dependent on the concentration of sulfate ions in the solution. The reactions with cubic C{sub 3}A (pure) seem to be more influenced by higher concentrations of sulfate ions, forming smaller ettringite needles at a slower pace than the orthorhombic C{sub 3}A (Na-doped) sample. The rate of release of aluminate species into the solution phase is also accelerated by Na doping.« less

GAS-PHASE OXIDATION PRODUCTS OF BIPHENYL AND POLYCHLORINATED BIPHENYLS (R825377)

EPA Science Inventory

Our laboratory recently measured the gas-phase reaction rate constants of
polychlorinated biphenyls (PCBs) with the hydroxyl radical (OH) and concluded
that OH reactions are the primary removal pathway of PCBs from the atmosphere.
With the reaction system previousl...

Determination of atomic positions from time resolved high resolution transmission electron microscopy images.

PubMed

Hussaini, Zahra; Lin, Pin Ann; Natarajan, Bharath; Zhu, Wenhui; Sharma, Renu

2018-03-01

For many reaction processes, such as catalysis, phase transformations, nanomaterial synthesis etc., nanoscale observations at high spatial (sub-nanometer) and temporal (millisecond) resolution are required to characterize and comprehend the underlying factors that favor one reaction over another. The combination of such spatial and temporal resolution (up to 600 µs), while rich in information, produces a large number of snapshots, each of which must be analyzed to obtain the structural (and thereby chemical) information. Here we present a methodology for automated quantitative measurement of real-time atomic position fluctuations in a nanoparticle. We leverage a combination of several image processing algorithms to precisely identify the positions of the atomic columns in each image. A geometric model is then used to measure the time-evolution of distances and angles between neighboring atomic columns to identify different phases and quantify local structural fluctuations. We apply this technique to determine the atomic-level fluctuations in the relative fractions of metal and metal-carbide phases in a cobalt catalyst nanoparticle during single-walled carbon nanotube (SWCNT) growth. These measurements provided a means to obtain the number of carbon atoms incorporated into and released from the catalyst particle, thereby helping resolve carbon reaction pathways during SWCNT growth. Further we demonstrate the use of this technique to measure the reaction kinetics of iron oxide reduction. Apart from reducing the data analysis time, the statistical approach allows us to measure atomic distances with sub-pixel resolution. We show that this method can be applied universally to measure atomic positions with a precision of 0.01 nm from any set of atomic-resolution video images. With the advent of high time-resolution direct detection cameras, we anticipate such methods will be essential in addressing the metrology problem of quantifying large datasets of time-resolved images in future. Published by Elsevier B.V.

Anti-allergic activity of the Morinda citrifolia extract and its constituents

PubMed Central

Murata, Kazuya; Abe, Yumi; Shinohara, Kaito; Futamura-Masuda, Megumi; Uwaya, Akemi; Isami, Fumiyuki; Matsuda, Hideaki

2014-01-01

Background: Morinda citrifolia (Rubiaceae), commonly known as noni is distributed throughout tropical and sub-tropical regions of the world. Anti-allergic effects of noni have not been reported despite the clinical usage as an anti-allergic agent. Materials and Methods: To investigate the anti-allergic effects of the 50% ethanolic extract of M. citrifolia fruits and leaves (MCF-ext and MCL-ext), dinitrofluorobenzene (DNFB)-induced triphasic cutaneous reaction and picryl chloride-induced contact dermatitis (PC-CD) tests were performed. Results: In DNFB-induced triphasic cutaneous reaction, oral administration of MCF-ext and MCL-ext exhibited dose-dependent inhibition of cutaneous reaction at 1 h (immediate phase response) after the DNFB challenge. MCF-ext also inhibited ear swelling at 24 h (late phase response) and 8 days (very late phase response) after the DNFB challenge. The effect of MCL-ext on the immediate phase response was attributed to the anti-degranulation from RBL-2H3 cells, while MCF-ext had no significant effect on degranulation. The active components of anti-degranulation activity in MCL-ext were determined to be ursolic acid, rutin and kaempferol-3-O-α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranoside. In the PC-CD test, both MCF-ext and MCL-ext showed an anti-swelling effect but the potency of MCF-ext was stronger than MCL-ext. Conclusion: These data suggest that noni fruits and leaves can be a daily consumable material for the prevention of allergic symptoms. PMID:25002809

SOLID-LIQUID PHASE TRANSFER CATALYZED SYNTHESIS OF CINNAMYL ACETATE-KINETICS AND ANALYSIS OF FACTORS AFFECTING THE REACTION IN A BATCH REACTOR

EPA Science Inventory

The use of solid-liquid phase transfer catalysis has an advantage of carrying out reaction between two immiscible substrates, one in solid phase and the other in liquid phase, with high selectivity and at relatively low temperatures. In this study we investigated the synthesis ci...

Hydrogen sulfide measurement using sulfide dibimane: critical evaluation with electrospray ion trap mass spectrometry

PubMed Central

Shen, Xinggui; Chakraborty, Sourav; Dugas, Tammy R; Kevil, Christopher G

2015-01-01

Accurate measurement of hydrogen sulfide bioavailability remains a technical challenge due to numerous issues involving sample processing, detection methods used, and actual biochemical products measured. Our group and others have reported that reverse phase HPLC detection of sulfide dibimane (SDB) product from the reaction of H2S/HS− with monobromobimane allows for analytical detection of hydrogen sulfide bioavailability in free and other biochemical forms. However, it remains unclear whether possible interfering contaminants may contribute to HPLC SDB peak readings that may result in inaccurate measurements of bioavailable sulfide. In this study, we critically compared hydrogen sulfide dependent SDB detection using reverse phase HPLC (RP-HPLC) versus quantitative SRM electrospray ionization mass spectrometry (ESI/MS) to obtain greater clarity into the validity of the reverse phase HPLC method for analytical measurement of hydrogen sulfide. Using an LCQ-deca ion-trap mass spectrometer, SDB was identified by ESI/MS positive ion mode, and quantified by selected reaction monitoring (SRM) using hydrocortisone as an internal standard. Collision induced dissociation (CID) parameters were optimized at MS2 level for SDB and hydrocortisone. ESI/MS detection of SDB standard was found to be a log order more sensitive than RP-HPLC with a lower limit of 0.25 nM. Direct comparison of tissue and plasma SDB levels using RP-HPLC and ESI/MS methods revealed comparable sulfide levels in plasma, aorta, heart, lung and brain. Together, these data confirm the use of SDB as valid indicator of H2S bioavailability and highlights differences between analytical detection methods. PMID:24932544

A sensitive method for the determination of Sulfonamides in seawater samples by Solid Phase Extraction and UV-Visible spectrophotometry

NASA Astrophysics Data System (ADS)

Errayess, Sophia Ait; Lahcen, Abdellatif Ait; Idrissi, Laila; Marcoaldi, Caterina; Chiavarini, Salvatore; Amine, Aziz

2017-06-01

The authors have developed a sensitive spectrophotometric method for determination of sulfonamide derivatives such as sulfanilamide (SAA), sulfadiazine (SDZ), sulfacetamide (SCT) sulfamethoxazole (SMX), sulfamerazine (SMR), sulfadimethoxine (SDX), sulfamethiazole (SMT) and Sulfathiazole (STZ). This method is based on the Bratton-Marshall reaction, which involves the diazotization of sulfonamides with sodium nitrite under acidic conditions, followed by coupling with N-(1-naphtyl) ethylenediamine dihydrochloride (NED) to form a pink colored compound. Therefore, the Bratton-Marshall method was modified by optimizing the reaction conditions, which allows us to determine a low concentration range of sulfonamides compared to the reported methods. The limits of detection and quantification obtained were 0.019-0.05 and 0.06-0.16 μg mL- 1, respectively. In comparison with other reported methods using different coupling agents, the proposed method was found to be the most simple and sensitive for sulfonamides determination. In this paper, the modified method was successfully employed for the determination of sulfonamides in drinking water, seawater and pharmaceutical and veterinary formulations. The purpose of this work is to optimize and develop a simple method for extraction and concentration of sulfonamides present as residues in seawater and their quantification with the recommended spectrophotometric method. Solid phase extraction (SPE) of sulfonamides from seawater samples was evaluated using Oasis HLB cartridges (3 mL, 540 mg). The recovery efficiency was investigated in the sulfonamides concentration range comprised between 0.19 and 126 ng mL- 1. The ease of use of this extraction method makes it very useful for routine laboratory work.

Nanoscale Properties of Rocks and Subduction Zone Rheology: Inferences for the Mechanisms of Deep Earthquakes

NASA Astrophysics Data System (ADS)

Riedel, M. R.

2007-12-01

Grain boundaries are the key for the understanding of mineral reaction kinetics. More generally, nanometer scale processes involved in breaking and establishing bonds at reaction sites determine how and at which rate bulk rock properties change in response to external tectonic forcing and possibly feed back into various geodynamic processes. A particular problem is the effects of grain-boundary energy on the kinetics of the olivine-spinel phase transformation in subducting slabs. Slab rheology is affected in many ways by this (metastable) mineral phase change. Sluggish kinetics due to metastable hindrance is likely to cause particular difficulties, because of possible strong non-linear feedback loops between strain-rate and change of creep properties during transformation. In order to get these nanoscale properties included into thermo-mechanical models, reliable kinetic data is required. The measurement of grain-boundary energies is, however, a rather difficult problem. Conventional methods of grain boundary surface tension measurement include (a) equilibrium angles at triple junction (b) rotating ball method (c) thermal groove method, and others (Gottstein & Shvindlerman, 1999). Here I suggest a new method that allows for the derivation of grain-boundary energies for an isochemical phase transformation based on experimental (in-situ) kinetic data in combination with a corresponding dynamic scaling law (Riedel and Karato, 1997). The application of this method to the olivine-spinel phase transformation in subducting slabs provides a solution to the extrapolation problem of measured kinetic data: Any kinetic phase boundary measured at the laboratory time scale can be "scaled" to the correct critical isotherm at subduction zones, under experimentelly "forbidden" conditions (Liou et al., 2000). Consequences for the metastability hypothesis that relates deep seismicity with olivine metastability are derived and discussed. References: Gottstein G, Shvindlerman LS (1999) Grain Boundary Migration in Metals, CRC Press, 385 pp., New York. Riedel MR, Karato S (1997) Grain-Size Evolution in Subducted Oceanic Lithosphere Associated with the Olivine- Spinel Transformation and Its Effects on Rheology. EPSL 148: 27-43. Liou JG, Hacker BR, Zhang RY (2000) Into the forbidden zone. Science 287, 1215-1216.

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

NASA Astrophysics Data System (ADS)

Nourry, Sendres; Krim, Lahouari

2015-07-01

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

End-Member Formulation of Solid Solutions and Reactive Transport

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

Lichtner, Peter C.

2015-09-01

A model for incorporating solid solutions into reactive transport equations is presented based on an end-member representation. Reactive transport equations are solved directly for the composition and bulk concentration of the solid solution. Reactions of a solid solution with an aqueous solution are formulated in terms of an overall stoichiometric reaction corresponding to a time-varying composition and exchange reactions, equivalent to reaction end-members. Reaction rates are treated kinetically using a transition state rate law for the overall reaction and a pseudo-kinetic rate law for exchange reactions. The composition of the solid solution at the onset of precipitation is assumed tomore » correspond to the least soluble composition, equivalent to the composition at equilibrium. The stoichiometric saturation determines if the solid solution is super-saturated with respect to the aqueous solution. The method is implemented for a simple prototype batch reactor using Mathematica for a binary solid solution. Finally, the sensitivity of the results on the kinetic rate constant for a binary solid solution is investigated for reaction of an initially stoichiometric solid phase with an undersaturated aqueous solution.« less

Study on Kinetic Mechanism of Bastnaesite Concentrates Decomposition Using Calcium Hydroxide

NASA Astrophysics Data System (ADS)

Cen, Peng; Wu, Wenyuan; Bian, Xue

2018-06-01

The thermal decomposition of bastnaesite concentrates using calcium hydroxide was studied. Calcium hydroxide can effectively inhibit the emission of fluorine during roasting by transforming it to calcium fluoride. The decomposition rate increased with increasing reaction temperature and amount of calcium hydroxide. The decomposition kinetics were investigated. The decomposition reaction was determined to be a heterogeneous gas-solid reaction, and it followed an unreacted shrinking core model. By means of the integrated rate equation method, the reaction was proven to be kinetically first order. Different reaction models were fit to the experimental data to determine the reaction control process. The chemical reaction at the phase interface controlled the reaction rate in the temperatures ranging from 673 K to 773 K (400 °C to 500 °C) with an apparent activation energy of 82.044 kJ·mol-1. From 773 K to 973 K (500 °C to 700 °C), diffusion through the solid product's layer became the determining step, with a lower activation energy of 15.841 kJ·mol-1.

An Unusual Salt Effect in an Interfacial Nucleophilic Substitution Reaction.

PubMed

Li, Shuheng; Mrksich, Milan

2018-06-12

This paper reports a kinetic characterization of the interfacial reaction of N-methylpyrrolidine with a self-assembled monolayer presenting an iodoalkyl group. SAMDI (self-assembled monolayers for matrix-assisted laser desorption/ionization) mass spectrometry was used to determine the extent of reaction for monolayers that were treated with a range of concentrations of the nucleophile for a range of times. These data revealed a second-order rate constant for the reaction that was approximately 100-fold greater than that for the analogous solution-phase reaction. However, addition of sodium iodide to the reaction mixture resulted in a 7-fold decrease in the reaction rate. Addition of bromide and chloride salts also gave slower rate constants for the reaction, but only at 100- and 1000-fold higher concentrations than was observed with iodide, respectively. The corresponding solution-phase reactions, by contrast, had rate constants that were unaffected by the concentration of halide salts. This work provides a well-characterized example illustrating the extent to which the kinetics and properties of an interfacial reaction can depart substantially from their better-understood solution-phase counterparts.

Evolution of Secondary Phases Formed upon Solidification of a Ni-Based Alloy

NASA Astrophysics Data System (ADS)

Zuo, Qiang; Liu, Feng; Wang, Lei; Chen, Changfeng

2013-07-01

The solidification of UNS N08028 alloy subjected to different cooling rates was studied, where primary austenite dendrites occur predominantly and different amounts of sigma phase form in the interdendritic regions. The solidification path and elemental segregation upon solidification were simulated using the CALPHAD method, where THERMO-CALC software packages and two classical segregation models were employed to predict the real process. It is thus revealed that the interdendritic sigma phase is formed via eutectic reaction at the last stage of solidification. On this basis, an analytical model was developed to predict the evolution of nonequilibrium eutectic phase, while the isolated morphology of sigma phase can be described using divorced eutectic theory. Size, fraction, and morphology of the sigma phase were quantitatively studied by a series of experiments; the results are in good agreement with the model prediction.

Probability and Cumulative Density Function Methods for the Stochastic Advection-Reaction Equation

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

Barajas-Solano, David A.; Tartakovsky, Alexandre M.

We present a cumulative density function (CDF) method for the probabilistic analysis of $d$-dimensional advection-dominated reactive transport in heterogeneous media. We employ a probabilistic approach in which epistemic uncertainty on the spatial heterogeneity of Darcy-scale transport coefficients is modeled in terms of random fields with given correlation structures. Our proposed CDF method employs a modified Large-Eddy-Diffusivity (LED) approach to close and localize the nonlocal equations governing the one-point PDF and CDF of the concentration field, resulting in a $(d + 1)$ dimensional PDE. Compared to the classsical LED localization, the proposed modified LED localization explicitly accounts for the mean-field advectivemore » dynamics over the phase space of the PDF and CDF. To illustrate the accuracy of the proposed closure, we apply our CDF method to one-dimensional single-species reactive transport with uncertain, heterogeneous advection velocities and reaction rates modeled as random fields.« less

Processing of CuInSe{sub 2}-based solar cells: Characterization of deposition processes in terms of chemical reaction analyses. Phase 2 Annual Report, 6 May 1996--5 May 1997

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

Anderson, T.

This report describes research performed by the University of Florida during Phase 2 of this subcontract. First, to study CIGS, researchers adapted a contactless, nondestructive technique previously developed for measuring photogenerated excess carrier lifetimes in SOI wafers. This dual-beam optical modulation (DBOM) technique was used to investigate the differences between three alternative methods of depositing CdS (conventional chemical-bath deposition [CBD], metal-organic chemical vapor deposition [MOCVD], and sputtering). Second, a critical assessment of the Cu-In-Se thermochemical and phase diagram data using standard CALPHAD procedures is being performed. The outcome of this research will produce useful information on equilibrium vapor compositions (requiredmore » annealing ambients, Sex fluxes from effusion cells), phase diagrams (conditions for melt-assisted growth), chemical potentials (driving forces for diffusion and chemical reactions), and consistent solution models (extents of solid solutions and extending phase diagrams). Third, an integrated facility to fabricate CIS PV devices was established that includes migration-enhanced epitaxy (MEE) for deposition of CIS, a rapid thermal processing furnace for absorber film formation, sputtering of ZnO, CBD or MOCVD of CdS, metallization, and pattern definition.« less

Crystal Phase and Architecture Engineering of Lotus-Thalamus-Shaped Pt-Ni Anisotropic Superstructures for Highly Efficient Electrochemical Hydrogen Evolution.

PubMed

Zhang, Zhicheng; Liu, Guigao; Cui, Xiaoya; Chen, Bo; Zhu, Yihan; Gong, Yue; Saleem, Faisal; Xi, Shibo; Du, Yonghua; Borgna, Armando; Lai, Zhuangchai; Zhang, Qinghua; Li, Bing; Zong, Yun; Han, Yu; Gu, Lin; Zhang, Hua

2018-06-07

The rational design and synthesis of anisotropic 3D nanostructures with specific composition, morphology, surface structure, and crystal phase is of significant importance for their diverse applications. Here, the synthesis of well-crystalline lotus-thalamus-shaped Pt-Ni anisotropic superstructures (ASs) via a facile one-pot solvothermal method is reported. The Pt-Ni ASs with Pt-rich surface are composed of one Ni-rich "core" with face-centered cubic (fcc) phase, Ni-rich "arms" with hexagonal close-packed phase protruding from the core, and facet-selectively grown Pt-rich "lotus seeds" with fcc phase on the end surfaces of the "arms." Impressively, these unique Pt-Ni ASs exhibit superior electrocatalytic activity and stability toward the hydrogen evolution reaction under alkaline conditions compared to commercial Pt/C and previously reported electrocatalysts. The obtained overpotential is as low as 27.7 mV at current density of 10 mA cm -2 , and the turnover frequency reaches 18.63 H 2 s -1 at the overpotential of 50 mV. This work provides a new strategy for the synthesis of highly anisotropic superstructures with a spatial heterogeneity to boost their promising application in catalytic reactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CHEMKIN2. General Gas-Phase Chemical Kinetics

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

Rupley, F.M.

1992-01-24

CHEMKIN is a high-level tool for chemists to use to describe arbitrary gas-phase chemical reaction mechanisms and systems of governing equations. It remains, however, for the user to select and implement a solution method; this is not provided. It consists of two major components: the Interpreter and the Gas-phase Subroutine Library. The Interpreter reads a symbolic description of an arbitrary, user-specified chemical reaction mechanism. A data file is generated which forms a link to the Gas-phase Subroutine Library, a collection of about 200 modular subroutines which may be called to return thermodynamic properties, chemical production rates, derivatives of thermodynamic properties,more » derivatives of chemical production rates, or sensitivity parameters. Both single and double precision versions of CHEMKIN are included. Also provided is a set of FORTRAN subroutines for evaluating gas-phase transport properties such as thermal conductivities, viscosities, and diffusion coefficients. These properties are an important part of any computational simulation of a chemically reacting flow. The transport properties subroutines are designed to be used in conjunction with the CHEMKIN Subroutine Library. The transport properties depend on the state of the gas and on certain molecular parameters. The parameters considered are the Lennard-Jones potential well depth and collision diameter, the dipole moment, the polarizability, and the rotational relaxation collision number.« less

Salting-out assisted liquid-liquid extraction for the determination of biogenic amines in fruit juices and alcoholic beverages after derivatization with 1-naphthylisothiocyanate and high performance liquid chromatography.

PubMed

Jain, Archana; Gupta, Manju; Verma, Krishna K

2015-11-27

A new method for determining biogenic amines in fruit juices and alcoholic beverages is described involving reaction of biogenic amines with 1-naphthylisothiocyanate followed by extraction of 1-naphthylthiourea derivatives with water-miscible organic solvent acetonitrile when solvents phase separation occurred using ammonium sulphate, a process called salting-out assisted liquid-liquid extraction. The extract was analyzed by high-performance liquid chromatography with UV detection at 254nm. The new reagent avoided many of the inconveniences as observed with existing derivatizing agents, such as dansyl chloride and benzoyl chloride, in regard to their inselectivity, instability, adverse effect of excess reagent, and necessity to remove excess reagent. The procedure has been optimized with respect to reaction time and temperature, water-miscible extraction solvent, and salt for solvents phase separation. Use of reagent as dispersed phase in aqueous medium produced derivatives in high yield. A linear calibration was obtained between the amount of biogenic amines in range 1-1000μgL(-1) and peak areas of corresponding thioureas formed; the correlation coefficient was 0.9965, and the limit of detection and limit of quantification found were 1.1μgL(-1) and 3.2μgL(-1), respectively. The pre-concentration method gave an average enrichment factor of 94. The application of the method has been demonstrated in the determination of biogenic amines in commercial samples of fruit juices and alcoholic beverages. In spiking experiments to real samples, the average recovery found by the present method was 94.5% that agreed well with 95.8% obtained by established comparison methods. Copyright © 2015 Elsevier B.V. All rights reserved.

Antioxidant effect of aqueous extract of four plants with therapeutic potential on gynecological diseases; Semen persicae, Leonurus cardiaca, Hedyotis diffusa, and Curcuma zedoaria.

PubMed

Ji, Shaojian; Fattahi, Amir; Raffel, Nathalie; Hoffmann, Inge; Beckmann, Matthias W; Dittrich, Ralf; Schrauder, Michael

2017-11-25

Little information is available concerning antioxidant effects of plant teas (water boiled) which are used more commonly in traditional Chinese medicine than other extracts. Thus, we addressed this issue by evaluating the ability of teas from four different plants with therapeutic potential on gynecological diseases. The aqueous extracts of Semen persicae, Leonurus cardiaca, Hedyotis diffusa, and Curcuma zedoaria rhizome were prepared and then their effects on copper-induced low-density lipoprotein cholesterol (LDL-C) oxidation were evaluated by spectrophotometric method. Density gradient ultracentrifugation method was recruited to isolate LDL-C from healthy individuals. Our results showed that adding 10, 20, and 30 µl S. persicae could increase the lag phase duration of LDL-C oxidation compared with control reaction 12, 21, and 33%, respectively. The most effective delay (87%) was observed when 30 µl H. diffusa was added to the reaction. In cases of L. cardiaca and C. zedoaria, we found no significant influence on the lag phase duration (p > 0.05). Moreover, our findings about starting point of the decomposition phase were almost in parallel with the lag phase results, as 30 µl of S. persicae or H. diffusa teas could significantly increase the initiation time of decomposition (p < 0.05). In conclusion our results showed that both S. persicae and H. diffusa teas and not L. cardiaca and C. zedoaria could have medicinal therapeutic effects partly through direct oxidation prevention.

Nano powders, components and coatings by plasma technique

DOEpatents

McKechnie, Timothy N [Brownsboro, AL; Antony, Leo V. M. [Huntsville, AL; O'Dell, Scott [Arab, AL; Power, Chris [Guntersville, AL; Tabor, Terry [Huntsville, AL

2009-11-10

Ultra fine and nanometer powders and a method of producing same are provided, preferably refractory metal and ceramic nanopowders. When certain precursors are injected into the plasma flame in a reactor chamber, the materials are heated, melted and vaporized and the chemical reaction is induced in the vapor phase. The vapor phase is quenched rapidly to solid phase to yield the ultra pure, ultra fine and nano product. With this technique, powders have been made 20 nanometers in size in a system capable of a bulk production rate of more than 10 lbs/hr. The process is particularly applicable to tungsten, molybdenum, rhenium, tungsten carbide, molybdenum carbide and other related materials.

Nano powders, components and coatings by plasma technique

NASA Technical Reports Server (NTRS)

McKechnie, Timothy N. (Inventor); Antony, Leo V. M. (Inventor); O'Dell, Scott (Inventor); Power, Chris (Inventor); Tabor, Terry (Inventor)

2009-01-01

Ultra fine and nanometer powders and a method of producing same are provided, preferably refractory metal and ceramic nanopowders. When certain precursors are injected into the plasma flame in a reactor chamber, the materials are heated, melted and vaporized and the chemical reaction is induced in the vapor phase. The vapor phase is quenched rapidly to solid phase to yield the ultra pure, ultra fine and nano product. With this technique, powders have been made 20 nanometers in size in a system capable of a bulk production rate of more than 10 lbs/hr. The process is particularly applicable to tungsten, molybdenum, rhenium, tungsten carbide, molybdenum carbide and other related materials.

Pulsed laser photolysis study of the reaction between O(3P) and HO2

NASA Technical Reports Server (NTRS)

Ravishankara, A. R.; Wine, P. H.; Nicovich, J. M.

1983-01-01

It is pointed out that bimolecular reactions involving two free radicals are of great interest because both reactants have unpaired electrons and hence could interact at distances longer than those typical of radical-molecule encounters. A method based on laser photolysis is being developed to produce selectively free radicals in the homogeneous gas phase. This is to be done in such a way as to isolate the reaction of interest and subsequently follow the course of the reaction using spectroscopic techniques. The present investigation is concerned with a study in which the rate coefficient for the reaction of O(3P) with HO2, has been measured at N2 pressures ranging from 10 to 500 torr, taking into account the reaction O(3P)+HO2 yields OH-O2. In the described study, O(3P) and HO2 were produced by cophotolysis of O3 and H2O2 in N2 at 248.5 nm using a KrF excimer laser.

Use of virtual reality intervention to improve reaction time in children with cerebral palsy: A randomized controlled trial.

PubMed

Pourazar, Morteza; Mirakhori, Fatemeh; Hemayattalab, Rasool; Bagherzadeh, Fazlolah

2017-09-21

The purpose of this study was to investigate the training effects of Virtual Reality (VR) intervention program on reaction time in children with cerebral palsy. Thirty boys ranging from 7 to 12 years (mean = 11.20; SD = .76) were selected by available sampling method and randomly divided into the experimental and control groups. Simple Reaction Time (SRT) and Discriminative Reaction Time (DRT) were measured at baseline and 1 day after completion of VR intervention. Multivariate analysis of variance (MANOVA) and paired sample t-test were performed to analyze the results. MANOVA test revealed significant effects for group in posttest phase, with lower reaction time in both measures for the experimental group. Based on paired sample t-test results, both RT measures significantly improved in experimental group following the VR intervention program. This paper proposes VR as a promising tool into the rehabilitation process for improving reaction time in children with cerebral palsy.

The UMIST database for astrochemistry 2006

NASA Astrophysics Data System (ADS)

Woodall, J.; Agúndez, M.; Markwick-Kemper, A. J.; Millar, T. J.

2007-05-01

Aims:We present a new version of the UMIST Database for Astrochemistry, the fourth such version to be released to the public. The current version contains some 4573 binary gas-phase reactions, an increase of 10% from the previous (1999) version, among 420 species, of which 23 are new to the database. Methods: Major updates have been made to ion-neutral reactions, neutral-neutral reactions, particularly at low temperature, and dissociative recombination reactions. We have included for the first time the interstellar chemistry of fluorine. In addition to the usual database, we have also released a reaction set in which the effects of dipole-enhanced ion-neutral rate coefficients are included. Results: These two reactions sets have been used in a dark cloud model and the results of these models are presented and discussed briefly. The database and associated software are available on the World Wide Web at www.udfa.net. Tables 1, 2, 4 and 9 are only available in electronic form at http://www.aanda.org

Phase transitions between lower and higher level management learning in times of crisis: an experimental study based on synergetics.

PubMed

Liening, Andreas; Strunk, Guido; Mittelstadt, Ewald

2013-10-01

Much has been written about the differences between single- and double-loop learning, or more general between lower level and higher level learning. Especially in times of a fundamental crisis, a transition between lower and higher level learning would be an appropriate reaction to a challenge coming entirely out of the dark. However, so far there is no quantitative method to monitor such a transition. Therefore we introduce theory and methods of synergetics and present results from an experimental study based on the simulation of a crisis within a business simulation game. Hypothesized critical fluctuations - as a marker for so-called phase transitions - have been assessed with permutation entropy. Results show evidence for a phase transition during the crisis, which can be interpreted as a transition between lower and higher level learning.

Integrating Crystallography into Early Metabolism Studies

NASA Astrophysics Data System (ADS)

Cruciani, Gabriele; Aristei, Yasmin; Goracci, Laura; Carosati, Emanuele

Since bioavailability, activity, toxicity, distribution, and final elimination all depend on metabolic biotransformations, it would be extremely advantageous if this information to be produced early in the discovery phase. Once obtained, researchers can judge whether or not a potential candidate should be eliminated from the pipeline, or modified to improve chemical stability or safety. The use of in silico methods to predict the site of metabolism in Phase I cytochrome-mediated reactions is a starting point in any metabolic pathway prediction. This paper presents a new method, which provides the site of metabolism for any CYP-mediated reaction acting on unknown substrates. The methodology can be applied automatically to all the cytochromes whose Xray 3D structure is known, but can be also applied to homology model 3D structures. The fully automated procedure can be used to detect positions that should be protected in order to avoid metabolic degradation, or to check the suitability of a new scaffold or pro-drug. Therefore the procedure is also a valuable new tool in early ADME-Tox, where drug-safety and metabolic profile patterns must be evaluated as soon, and as early, as possible.

Solid phase monofunctionalization of gold nanoparticles using ionic exchange resin as polymer support.

PubMed

Zou, Jianhua; Dai, Qiu; Wang, Jinhai; Liu, Xiong; Huo, Qun

2007-07-01

A solid phase modification method using anionic exchange resin as polymer support was developed for the synthesis of monofunctional gold nanoparticles. Based on a "catch and release" mechanism to control the number of functional groups attached to the nanoparticle surface, bifunctional thiol ligands with a carboxylic acid end group were first immobilized at a controlled density on anionic exchange resin through electrostatic interactions. Gold nanoparticles were then immobilized to the anionic exchange resin by a one-to-one place exchange reaction between resin-bound thiol ligands and butanethiol-protected gold nanoparticles in solution. After cleaving off from the resin under mild conditions, gold nanoparticles with a single carboxyl group attached to the surface were obtained as the major product. Experimental conditions such as the solvents used for ligand loading and solid phase place exchange reaction, and the loading density of the ligands, were found to play a critical role towards the successful synthesis of monofunctional nanoparticles. Overall, the noncovalent bond-based ligand immobilization technique reported here greatly simplified the process of solid phase monofunctionalization of nanoparticles compared to a previously reported covalent bond-based ligand immobilization technique.

Evaluation and reporting of enzyme immunoassay determinations of antibody to herpes simplex virus in sera and cerebrospinal fluid.

PubMed Central

Cremer, N E; Cossen, C K; Hanson, C V; Shell, G R

1982-01-01

Several methods for evaluating and reporting enzyme immunoassay (EIA) determinations of antibody to herpes simplex virus derived from one dilution of single serum samples were studied. An EIA ratio method for serological evidence of current infection from paired serum samples was also evaluated. Optical density (OD) of the reaction at a 1:100 serum dilution and estimated titers obtained by reference of the OD of the serum dilution to a standard curve were compared to the corresponding plotted EIA titer obtained by titration to endpoint. Neither the OD per se nor the estimated titer was completely predictive of the plotted titer (correlation coefficient [r] of 0.824 and 0.817, respectively), and they provided only a semiquantitative measurement of antibody concentration. For an antibody status report, however, OD would be sufficient if related to the cutoff value as an EIA index (OD of sample divided by cutoff OD for positive specimens). The OD of the EIA reaction at a single dilution (1:5) of cerebrospinal fluid, on the other hand, correlated quite well with the titer obtained by titration (r = 0.950). For serological diagnosis of current infection, the OD ratio of convalescence-phase/acute-phase sera was determined at several dilutions. A ratio of greater than or equal to 1.54 was calculated as a reliable index for a significant rise in antibody concentration and compatible with current infection. By determining the convalescent-phase/acute-phase serum ratio at two dilutions, 1:100 and 1:1,000, the EIA ratio method appeared to be a sensitive as or more sensitive than, complement fixation in diagnosing current infection. PMID:6284791

One pot synthesis of exchange coupled Nd2Fe14B/alpha-Fe by pechini type sol-gel method.

PubMed

Hussain, Abid; Jadhav, Abhijit P; Baek, Yeon Kyung; Choi, Hul Jin; Lee, Jaeho; Kang, Young Soo

2013-11-01

In this work, a combination of nanoparticles of Nd2Fe14B hard magnetic phase and alpha-Fe soft magnetic phase were synthesized by one pot chemical synthesis technique using sol-gel method. A gel of Nd-Fe-B was prepared using NdCl3 x 6H2O, FeCl3 x 6H2O, H3BO3, citric acid, and ethylene glycol by pechini type sol-gel method. The gel was subsequently calcined and annealed to obtain the mixed oxide powders. The produced metal oxide particles were identified with XRD, SEM, TEM to obtain the crystal structure, shape and domain structure of them. The nanoparticles of mixed phase of Nd2Fe14B/alpha-Fe were obtained from these oxides by a process of reduction-diffusion in vacuum by employing CaH2 as reducing agent. During this process it was optimized by controlling temperature, reaction time and concentration of the reducing agent (CaH2). The phase formation of Nd2Fe14B was resulted by the direct diffusion of NdH2, Fe and B. The magnetic property of produced hard and soft phases was successfully identified with vibrating sample magnetometer (VSM). The mixed domains of the hard and soft phases were identified with selected area electron diffraction method (SAED) patterns.

Group Contribution Methods for Phase Equilibrium Calculations.

PubMed

Gmehling, Jürgen; Constantinescu, Dana; Schmid, Bastian

2015-01-01

The development and design of chemical processes are carried out by solving the balance equations of a mathematical model for sections of or the whole chemical plant with the help of process simulators. For process simulation, besides kinetic data for the chemical reaction, various pure component and mixture properties are required. Because of the great importance of separation processes for a chemical plant in particular, a reliable knowledge of the phase equilibrium behavior is required. The phase equilibrium behavior can be calculated with the help of modern equations of state or g(E)-models using only binary parameters. But unfortunately, only a very small part of the experimental data for fitting the required binary model parameters is available, so very often these models cannot be applied directly. To solve this problem, powerful predictive thermodynamic models have been developed. Group contribution methods allow the prediction of the required phase equilibrium data using only a limited number of group interaction parameters. A prerequisite for fitting the required group interaction parameters is a comprehensive database. That is why for the development of powerful group contribution methods almost all published pure component properties, phase equilibrium data, excess properties, etc., were stored in computerized form in the Dortmund Data Bank. In this review, the present status, weaknesses, advantages and disadvantages, possible applications, and typical results of the different group contribution methods for the calculation of phase equilibria are presented.

Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

NASA Astrophysics Data System (ADS)

Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

2015-04-01

Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

SOME PROTECTION METHODS FOR CUTANEOUS IRRADIATION WITH FAST ELECTRONS (in Italian)

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

Trucchi, O.

1962-09-01

The influence exerted by some substances, particularly by fatty substances and cortisone derivatives, on the skin reaction to fast electrons is examined. The means employed were applied on the skin immediately before the irradiation; their effectiveness varies in relation with the dose fractionation; this decreases in general the capacity of the various substances tested of modifying the skin reaction. The changes induced by these means are both quantitative and relative to the course (anticipation of the appearance of the erythema); they may occur uniformly in all phases of the reaction or only in one (a change of the first phasemore » of the erythema is usually observed). The quality of the excipient, the action of which is often responsible for the aggravation of the skin reaction, is to be taken into account in the evaluation of the typical effect of the medications. Within the limits of the doses employed (1000 rad in only a sitting, 5000 rad in case of fractionation) the influence of fatty substances on the skin reactions due to irradiation with quick electrons proved not to be marked but only scarcely appreciable. The mineral fats may increase the reaction due to quick electrons in some cases: they do not have, however, either a protective or therapeutic effect during the acute phase of the reaction. The cortisone derivatives are uneffective when they are directly and exclusively applied on the irradiated skin, while they are successfully used by general route, especially in the reactions of the mucous membranes produced by quick electrons; in any way, the topical use of cortisone derivatives with excipients deprived from mineral fats proved to be preferable. Among the physical means employed, the compression gave the best results, in the cases where it could be applied. (auth)« less

Propensity approach to nonequilibrium thermodynamics of a chemical reaction network: Controlling single E-coli β-galactosidase enzyme catalysis through the elementary reaction stepsa)

NASA Astrophysics Data System (ADS)

Das, Biswajit; Banerjee, Kinshuk; Gangopadhyay, Gautam

2013-12-01

In this work, we develop an approach to nonequilibrium thermodynamics of an open chemical reaction network in terms of the elementary reaction propensities. The method is akin to the microscopic formulation of the dissipation function in terms of the Kullback-Leibler distance of phase space trajectories in Hamiltonian system. The formalism is applied to a single oligomeric enzyme kinetics at chemiostatic condition that leads the reaction system to a nonequilibrium steady state, characterized by a positive total entropy production rate. Analytical expressions are derived, relating the individual reaction contributions towards the total entropy production rate with experimentally measurable reaction velocity. Taking a real case of Escherichia coli β-galactosidase enzyme obeying Michaelis-Menten kinetics, we thoroughly analyze the temporal as well as the steady state behavior of various thermodynamic quantities for each elementary reaction. This gives a useful insight in the relative magnitudes of various energy terms and the dissipated heat to sustain a steady state of the reaction system operating far-from-equilibrium. It is also observed that, the reaction is entropy-driven at low substrate concentration and becomes energy-driven as the substrate concentration rises.

Kinetics and products of the OH radical-initiated reaction of 3-methyl-2-butenal.

PubMed

Tuazon, Ernesto C; Aschmann, Sara M; Nishino, Noriko; Arey, Janet; Atkinson, Roger

2005-06-07

Kinetics and products of the gas-phase reaction of OH radicals with 3-methyl-2-butenal [(CH3)2C=CHCHO] have been investigated at room temperature and atmospheric pressure of air. Using a relative rate method with methacrolein as the reference compound, a rate constant for the reaction of OH radicals with 3-methyl-2-butenal of (6.21 +/- 0.18) x 10(-11) cm3 molecule(-1) s(-1) at 296 +/- 2 K was measured, where the indicated error does not include the uncertainty in the rate constant for the methacrolein reference compound. Products of this reaction were investigated using in situ Fourier transform infrared (FT-IR) spectroscopy and solid phase microextraction (SPME) fibers coated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine for on-fiber derivatization of carbonyl compounds, with subsequent thermal desorption and analysis by gas chromatography. The products observed and the molar formation yields were: glyoxal, 40 +/- 3%; acetone, 74 +/- 6%; 2-hydroxy-2-methylpropanal, 4.6 +/- 0.7%; CO2, 39% initially, decreasing to 30% at greater extents of reaction; peroxyacyl nitrate(s) [RC(O)OONO2], 5-8%, increasing with the extent of reaction and with the sum of the CO2 and RC(O)OONO2 yields being 38 +/- 6%; and organic nitrates [RONO2], 8.5 +/- 2.3%. The formation of these products is readily explained by a reaction mechanism based on those previously formulated for the corresponding reactions of the alpha,beta-unsaturated aldehydes acrolein, crotonaldehyde and methacrolein. Based on the mechanism proposed, at room temperature H-atom abstraction from the CHO group accounts for 40 +/- 6% of the overall reaction, and OH radical addition to the carbon atoms of the C=C bond accounts for 53 +/- 4% of the overall reaction. Hence 93 +/- 8% of the reaction products and pathways are accounted for.

CuO/CeO2 catalysts for glycerol selective conversion to lactic acid.

PubMed

Palacio, Ruben; Torres, Sebastian; Royer, Sébastien; Mamede, Anne Sophie; López, Diana; Hernández, Diana

2018-03-26

Ceria supported copper oxide catalysts were produced by a deposition-precipitation method, at a high copper loading (up to >25 wt%). These materials demonstrated excellent properties for glycerol selective conversion to lactic acid, with a conversion reaching up to 87% with a selectivity to lactic acid of 74% (8 h reaction, 220 °C, under N2 pressure). These catalysts also exhibited high stability upon 5 successive reaction cycles. The formation of a crystalline CuO phase was demonstrated in the nanocomposites at a high Cu loading, with elongated shaped particles formed on the cerium oxide surface. Such particles were however, not observed at low Cu loadings. XPS analysis revealed that Cu(ii) was the main Cu species on the fresh catalyst, and that this species was reduced to Cu(i) during the reaction. Complementary characterization over the spent catalyst clearly showed the morphological modifications of the CuO phase, however, did not impact significantly either glycerol conversion or selectivity to lactic acid upon recycling. For instance, apparently, the catalytic activity of CuO largely depends on the Cu(ii) species.

Effect of alkaline earth metals on the liquid-phase hydrogenation of hydroquinone over Ru-based catalysts

NASA Astrophysics Data System (ADS)

Li, Hongwei; Ji, Dong; Li, Yu; Liang, Yalan; Li, Gui Xian

2015-12-01

A series of Ru-based catalysts modified by alkaline earth metals were prepared by the impregnation-precipitation method and characterized using transmission electron microscopy, X-ray diffraction, ICP optical emission spectroscopy, Infrared Spectroscopy of adsorbed pyridine analysis and surface area analysis. The performance of the catalysts was measured via liquid-phase hydroquinone hydrogenation reaction. Results show that the Ru-Sr/NaY catalyst has the best activity and selectivity among those Ru-based catalysts. The conversion of hydroquinone and the selectivity to 1,4-cyclohexanediol reached up to 99.6% and 89.6% at optimum reaction condition (700 r/min, 423 K and 5 MPa pressure of H2 in 3 h). This may be attributed to the fact that the right amount of Strontium is beneficial to the good dispersion of the ruthenium nanoclusters on the surface of NaY and modify the acidic properties of the catalyst. Moreover, IR of adsorbed pyridine analysis suggested the proper ratio of L/B acid of the catalysts played an important role in the performance of the hydroquinone hydrogenation reaction.

The Cu-Li-Sn Phase Diagram: Isopleths, Liquidus Projection and Reaction Scheme

PubMed Central

Flandorfer, Hans

2016-01-01

The Cu-Li-Sn phase diagram was constructed based on XRD and DTA data of 60 different alloy compositions. Eight ternary phases and 14 binary solid phases form 44 invariant ternary reactions, which are illustrated by a Scheil-Schulz reaction scheme and a liquidus projection. Phase equilibria as a function of concentration and temperature are shown along nine isopleths. This report together with an earlier publication of our group provides for the first time comprehensive investigations of phase equilibria and respective phase diagrams. Most of the phase equilibria could be established based on our experimental results. Only in the Li-rich part where many binary and ternary compounds are present estimations had to be done which are all indicated by dashed lines. A stable ternary miscibility gap could be found which was predicted by modelling the liquid ternary phase in a recent work. The phase diagrams are a crucial input for material databases and thermodynamic optimizations regarding new anode materials for high-power Li-ion batteries. PMID:27788175

Radiation reaction in fusion plasmas.

PubMed

Hazeltine, R D; Mahajan, S M

2004-10-01

The effects of a radiation reaction on thermal electrons in a magnetically confined plasma, with parameters typical of planned burning plasma experiments, are studied. A fully relativistic kinetic equation that includes the radiation reaction is derived. The associated rate of phase-space contraction is computed and the relative importance of the radiation reaction in phase space is estimated. A consideration of the moments of the radiation reaction force show that its effects are typically small in reactor-grade confined plasmas, but not necessarily insignificant.

The value of automated gel column agglutination technology in the identification of true inherited D blood types in massively transfused patients.

PubMed

Summers, Thomas; Johnson, Viviana V; Stephan, John P; Johnson, Gloria J; Leonard, George

2009-08-01

Massive transfusion of D- trauma patients in the combat setting involves the use of D+ red blood cells (RBCs) or whole blood along with suboptimal pretransfusion test result documentation. This presents challenges to the transfusion service of tertiary care military hospitals who ultimately receive these casualties because initial D typing results may only reflect the transfused RBCs. After patients are stabilized, mixed-field reaction results on D typing indicate the patient's true inherited D phenotype. This case series illustrates the utility of automated gel column agglutination in detecting mixed-field reactions in these patients. The transfusion service test results, including the automated gel column agglutination D typing results, of four massively transfused D- patients transfused D+ RBCs is presented. To test the sensitivity of the automated gel column agglutination method in detecting mixed-field agglutination reactions, a comparative analysis of three automated technologies using predetermined mixtures of D+ and D- RBCs is also presented. The automated gel column agglutination method detected mixed-field agglutination in D typing in all four patients and in the three prepared control specimens. The automated microwell tube method identified one of the three prepared control specimens as indeterminate, which was subsequently manually confirmed as a mixed-field reaction. The automated solid-phase method was unable to detect any mixed fields. The automated gel column agglutination method provides a sensitive means for detecting mixed-field agglutination reactions in the determination of the true inherited D phenotype of combat casualties transfused massive amounts of D+ RBCs.

Geometric phase effects in ultracold chemistry

NASA Astrophysics Data System (ADS)

Hazra, Jisha; Naduvalath, Balakrishnan; Kendrick, Brian K.

2016-05-01

In molecules, the geometric phase, also known as Berry's phase, originates from the adiabatic transport of the electronic wavefunction when the nuclei follow a closed path encircling a conical intersection between two electronic potential energy surfaces. It is demonstrated that the inclusion of the geometric phase has an important effect on ultracold chemical reaction rates. The effect appears in rotationally and vibrationally resolved integral cross sections as well as cross sections summed over all product quantum states. It arises from interference between scattering amplitudes of two reaction pathways: a direct path and a looping path that encircle the conical intersection between the two lowest adiabatic electronic potential energy surfaces. Illustrative results are presented for the O+ OH --> H+ O2 reaction and for hydrogen exchange in H+ H2 and D+HD reactions. It is also qualitatively demonstrated that the geometric phase effect can be modulated by applying an external electric field allowing the possibility of quantum control of chemical reactions in the ultracold regime. This work was supported in part by NSF Grant PHY-1505557 (N.B.) and ARO MURI Grant No. W911NF-12-1-0476 (N.B.).

Characterization of Sodium Ion Electrochemical Reaction with Tin Anodes: Experiment and Theory

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

Baggetto, Loic; Meisner, Roberta A; Ganesh, Panchapakesan

2013-01-01

Tin anodes show a rich structure and reaction chemistry which we have investigated in detail. Upon discharge five plateaus are observed corresponding to -Sn, an unidentified phase (Na/Sn = 0.6), an amorphous phase (Na/Sn = 1.2), a hexagonal R-3m Na5Sn2, and fully sodiated Na15Sn 4. With charging there are six plateaus, which are related to the formation of Na5Sn2 followed by the formation of amorphous phases and -Sn. Upon cycling the formation of metastable Na5Sn2 seems to be suppressed, leading to a single charge plateau at 0.2 V. Theoretical voltages calculated from existing crystal structures using DFT provide a goodmore » match with constant current measurements, however, the voltage is more negative compared to quasi-equilibrium measurements (GITT). Search for additional (meta)stable phases using cluster-expansion method predicts many phases lower in energy than the convex hull, including the R-3m Na5Sn2 phase characterized experimentally. The presence of multiple phases in varying lattices with very similar formation energy suggests why the reaction mechanism is non-reversible. Interpretation of M ssbauer spectroscopy data is not yet elucidated due to the very low recoil-free fraction of the materials. The electrode surface is terminated with a SEI layer rich in carbonates such as Na2CO3 and Na alkyl carbonates as evidenced by XPS. After a full charge at 2V, strong evidence for the formation of oxidized Sn4+ is obtained. Subjecting the electrode to a rest after a full charge at 2 V reveals that aging in the electrolyte reduces the oxidized Sn4+ into Sn2+ and Sn0, and concomitantly suppresses the electrolyte decomposition represented by an anomalous discharge plateau at 1.2 V. Thereby, the catalytic decomposition of the electrolyte during discharge is caused by nanosized Sn particles covered by oxidized Sn4+ and not by pure metallic Sn.« less

Nonlinear Analysis of Two-phase Circumferential Motion in the Ablation Circumstance

NASA Astrophysics Data System (ADS)

Xiao-liang, Xu; Hai-ming, Huang; Zi-mao, Zhang

2010-05-01

In aerospace craft reentry and solid rocket propellant nozzle, thermal chemistry ablation is a complex process coupling with convection, heat transfer, mass transfer and chemical reaction. Based on discrete vortex method (DVM), thermal chemical ablation model and particle kinetic model, a computational module dealing with the two-phase circumferential motion in ablation circumstance is designed, the ablation velocity and circumferential field can be thus calculated. The calculated nonlinear time series are analyzed in chaotic identification method: relative chaotic characters such as correlation dimension and the maximum Lyapunov exponent are calculated, fractal dimension of vortex bulbs and particles distributions are also obtained, thus the nonlinear ablation process can be judged as a spatiotemporal chaotic process.

Time-resolved broadband cavity-enhanced absorption spectroscopy for chemical kinetics.

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

Sheps, Leonid; Chandler, David W.

Experimental measurements of elementary reaction rate coefficients and product branching ratios are essential to our understanding of many fundamentally important processes in Combustion Chemistry. However, such measurements are often impossible because of a lack of adequate detection techniques. Some of the largest gaps in our knowledge concern some of the most important radical species, because their short lifetimes and low steady-state concentrations make them particularly difficult to detect. To address this challenge, we propose a novel general detection method for gas-phase chemical kinetics: time-resolved broadband cavity-enhanced absorption spectroscopy (TR-BB-CEAS). This all-optical, non-intrusive, multiplexed method enables sensitive direct probing of transientmore » reaction intermediates in a simple, inexpensive, and robust experimental package.« less

High performance liquid chromatography method for the determination of cinnamyl alcohol dehydrogenase activity in soybean roots.

PubMed

dos Santos, W D; Ferrarese, Maria de Lourdes Lucio; Ferrarese-Filho, O

2006-01-01

This study proposes a simple, quick and reliable method for determining the cinnamyl alcohol dehydrogenase (CAD; EC 1.1.1.195) activity in soybean (Glycine max L. Merr.) roots using reversed-phase high performance liquid chromatography (RP-HPLC). The method includes a single extraction of the tissue and conduction of the enzymatic reaction at 30 degrees C with cinnamaldehydes (coniferyl or sinapyl), substrates of CAD. Disappearance of the substrates in the reaction mixture is monitored at 340 nm (for coniferaldehyde) or 345 nm (for sinapaldehyde) by isocratic elution with methanol/acetic acid through a GLC-ODS (M) column. This HPLC technique furnishes a rapid and reliable measure of cinnamaldehyde substrates, and may be used as an alternative tool to analyze CAD activity in enzyme preparation without previous purification.

Theoretical and experimental studies on silica-coated carbon spheres composites

NASA Astrophysics Data System (ADS)

Guo, Xingmei; Liu, Haixing; Shen, Yinghua; Niu, Mei; Yang, Yongzhen; Liu, Xuguang

2013-10-01

In order to prepare carbon-based photonic crystals, first of all, theoretical modeling calculation was used to predict the bandgap characteristics of silica-coated carbon spheres. Then, silica-coated carbon spheres composites were synthesized using tetraethyl orthosilicate as precursor of silica by a sol-gel method combined with Stöber method. Effect of reaction conditions on surface coating of carbon spheres with silica, including the pH, the amount of precursor and reaction time, was emphasized. The morphology and structure of the composites and the effect coating of carbon spheres with silica were characterized by field-emission scanning electron microscopy, high resolution transmission electron microscopy and Fourier-transform infrared spectrometry. The coating ratio of silica was investigated by thermogravimetry. The results show that pH value played an important role in coating reaction, the dosage of the precursor and reaction time had significant effect on coating layer thickness, that is, coating ratio. Carbon spheres coated with silica had good dispersibility and dispersion stability in water and ethanol, which is preconditions of reactivity of carbon spheres in liquid phase and lays the basis for the application of carbon spheres.

Reaction-time-resolved measurements of laser-induced fluorescence in a shock tube with a single laser pulse

NASA Astrophysics Data System (ADS)

Zabeti, S.; Fikri, M.; Schulz, C.

2017-11-01

Shock tubes allow for the study of ultra-fast gas-phase reactions on the microsecond time scale. Because the repetition rate of the experiments is low, it is crucial to gain as much information as possible from each individual measurement. While reaction-time-resolved species concentration and temperature measurements with fast absorption methods are established, conventional laser-induced fluorescence (LIF) measurements with pulsed lasers provide data only at a single reaction time. Therefore, fluorescence methods have rarely been used in shock-tube diagnostics. In this paper, a novel experimental concept is presented that allows reaction-time-resolved LIF measurements with one single laser pulse using a test section that is equipped with several optical ports. After the passage of the shock wave, the reactive mixture is excited along the center of the tube with a 266-nm laser beam directed through a window in the end wall of the shock tube. The emitted LIF signal is collected through elongated sidewall windows and focused onto the entrance slit of an imaging spectrometer coupled to an intensified CCD camera. The one-dimensional spatial resolution of the measurement translates into a reaction-time-resolved measurement while the species information can be gained from the spectral axis of the detected two-dimensional image. Anisole pyrolysis was selected as the benchmark reaction to demonstrate the new apparatus.

The Heterogeneous Oxidation of Organic Droplets -Temperature and Physical Phase Effects

NASA Astrophysics Data System (ADS)

Hung, H.; Tang, C.; Lin, L.

2008-12-01

The heterogeneous reactions of oleic acid droplets with ozone are studied at different temperatures to imitating the atmospheric condition. The reactions are monitored concomitantly by using attenuated total reflectance Fourier Transform infrared spectroscopy (ATR-FT-IR) for the organic species and UV-VIS spectrometry for the ozone concentration, in order to investigate reaction rate discrepancies reported in literature as well as the oxidation mechanism, temperature and physical phase effects. The less and semi- volatile products are identified and resolved by a liquid chromatography and a gas chromatography mass spectrometer, respectively. The identified products are predominantly composed by nananoic acid and azelaic acid and might be due to propagation reactions possibly initiated by a secondary reaction such as the stabilized Criegee intermediates reacting with oleic acid. For temperature effect, the oxidation rate decreases with temperature when the oleic acid droplets are in the same physical phases. As oleic acid turns into the solid phase, the oxidation mechanism is observed to be different from the liquid phase. Furthermore, the concentration of ozone was monitored to examine the kinetics of the oxidation reaction. The integrated ozone profile recorded by UV-VIS spectrometry shows that the consumed ozone represents only approximately 12% of total oleic acid for the solid cases at 4°C in contrast to 30% for the liquid cases at 25°C, and hence confirmed the existence of secondary reactions.

The pH-controlled synthesis of a gold nanoparticle/polymer matrix via electrodeposition at a liquid liquid interface

NASA Astrophysics Data System (ADS)

Lepková, K.; Clohessy, J.; Cunnane, V. J.

2007-09-01

A controlled synthesis of metal nanoparticles co-deposited in a polymer matrix at various pH conditions has been investigated at the interface between two immiscible phases. The pH value of the aqueous phase is modified, resulting in various types of reaction between the gold compound and the monomer. The types of electrochemical processes and their kinetic parameters are determined using both the method of Nicholson and a method based on the Butler-Volmer equation. Cyclic voltammetry is the experimental method used. A material analysis via transmission electron microscopy and particle size distribution calculations confirm that nanoparticles of different sizes can be synthesized by modification of the system pH. The stability of the generated nanocomposite is also discussed.

The α-Effect and Competing Mechanisms: The Gas-Phase Reactions of Microsolvated Anions with Methyl Formate

NASA Astrophysics Data System (ADS)

Thomsen, Ditte L.; Nichols, Charles M.; Reece, Jennifer N.; Hammerum, Steen; Bierbaum, Veronica M.

2014-02-01

The enhanced reactivity of α-nucleophiles, which contain an electron lone pair adjacent to the reactive site, has been demonstrated in solution and in the gas phase and, recently, for the gas-phase SN2 reactions of the microsolvated HOO-(H2O) ion with methyl chloride. In the present work, we continue to explore the significance of microsolvation on the α-effect as we compare the gas-phase reactivity of the microsolvated α-nucleophile HOO-(H2O) with that of microsolvated normal alkoxy nucleophiles, RO-(H2O), in reactions with methyl formate, where three competing reactions are possible. The results reveal enhanced reactivity of HOO-(H2O) towards methyl formate, and clearly demonstrate the presence of an overall α-effect for the reactions of the microsolvated α-nucleophile. The association of the nucleophiles with a single water molecule significantly lowers the degree of proton abstraction and increases the SN2 and BAC2 reactivity compared with the unsolvated analogs. HOO-(H2O) reacts with methyl formate exclusively via the BAC2 channel. While microsolvation lowers the overall reaction efficiency, it enhances the BAC2 reaction efficiency for all anions compared with the unsolvated analogs. This may be explained by participation of the solvent water molecule in the BAC2 reaction in a way that continuously stabilizes the negative charge throughout the reaction.

Effective Permeability Change in Wellbore Cement with Carbon Dioxide Reaction

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

Um, Wooyong; Jung, Hun Bok; Martin, Paul F.

2011-11-01

Portland cement, a common sealing material for wellbores for geological carbon sequestration was reacted with CO{sub 2} in supercritical, gaseous, and aqueous phases at various pressure and temperature conditions to simulate cement-CO{sub 2} reaction along the wellbore from carbon injection depth to the near-surface. Hydrated Portland cement columns (14 mm diameter x 90 mm length; water-to-cement ratio = 0.33) including additives such as steel coupons and Wallula basalt fragments were reacted with CO{sub 2} in the wet supercritical (the top half) and dissolved (the bottom half) phases under carbon sequestration condition with high pressure (10 MPa) and temperature (50 C)more » for 5 months, while small-sized hydrated Portland cement columns (7 mm diameter x 20 mm length; water-to-cement ratio = 0.38) were reacted with CO{sub 2} in dissolved phase at high pressure (10 MPa) and temperature (50 C) for 1 month or with wet CO{sub 2} in gaseous phase at low pressure (0.2 MPa) and temperature (20 C) for 3 months. XMT images reveal that the cement reacted with CO{sub 2} saturated groundwater had degradation depth of {approx}1 mm for 1 month and {approx}3.5 mm for 5 month, whereas the degradation was minor with cement exposure to supercritical CO{sub 2}. SEM-EDS analysis showed that the carbonated cement was comprised of three distinct zones; the innermost less degraded zone with Ca atom % > C atom %, the inner degraded zone with Ca atom % {approx} C atom % due to precipitation of calcite, the outer degraded zone with C atom % > Ca atom % due to dissolution of calcite and C-S-H, as well as adsorption of carbon to cement matrix. The outer degraded zone of carbonated cement was porous and fractured because of dissolution-dominated reaction by carbonic acid exposure, which resulted in the increase in BJH pore volume and BET surface area. In contrast, cement-wet CO{sub 2}(g) reaction at low P (0.2 MPa)-T (20 C) conditions for 1 to 3 months was dominated by precipitation of micron-sized calcite on the outside surface of cement, which resulted in the decrease in BJH pore volume and BET surface area. Cement carbonation and pore structure change are significantly dependent on pressure and temperature conditions as well as the phase of CO{sub 2}, which controls the balance between precipitation and dissolution in cement matrix. Geochemical modeling result suggests that ratio of solid (cement)-to-solution (carbonated water) has a significant effect on cement carbonation, thus the cement-CO{sub 2} reaction experiment needs to be conducted under realistic conditions representing the in-situ wellbore environment of carbon sequestration field site. Total porosity and air permeability for a duplicate cement column with water-to-cement ratio of 0.38 measured after oven-drying by Core Laboratories using Boyle's Law technique and steady-state method were 31% and 0.576 mD. A novel method to measure the effective liquid permeability of a cement column using X-ray micro-tomography images after injection of pressurized KI (potassium iodide) is under development by PNNL. Preliminary results indicate the permeability of a cement column with water-to-cement ratio of 0.38 is 4-8 mD. PNNL will apply the method to understand the effective permeability change of Portland cement by CO{sub 2}(g) reaction under a variety of pressure and temperature conditions to develop a more reliable well-bore leakage risk model.« less

Synthesis of TiCr2 intermetallic compound from mechanically activated starting powders via calcio-thermic co-reduction

NASA Astrophysics Data System (ADS)

Bayat, O.; Khavandi, A. R.; Ghasemzadeh, R.

2017-05-01

Effect of mechanical activation of TiO2 and Cr2O3 oxides as starting materials was investigated for direct synthesis of TiCr2. Differential thermal analysis (DTA) indicated that increasing the ball milling time resulted in lower exothermic reaction temperatures between molten Ca-Cr2O3 and molten Ca-TiO2. A model-free Kissinger type method was applied to DTA data to evaluate the reaction kinetics. The results reveal that the activation energy of the exothermic reactions decreased with increasing the milling time. The structure, oxygen content, and average particle sizes of the obtained TiCr2 product were affected by the ball milling time of the starting materials. Increasing the milling time from 10 to 40 h decreased the average particle size and oxygen content of the obtained TiCr2 from 10 to 2 μm and from 1690 to 1290 ppm, respectively. The X-ray diffraction (XRD) results showed that TiCr2 compounds with metastable bcc phase can be produced using nano-sized starting materials, while only a slight amount of bcc phase can be obtained in the TiCr2 compounds, using micron-sized starting materials. The TiCr2 obtained by this method had a hydrogen absorption capability of 0.63 wt % and the kinetics of the hydrogen absorption increased for the 40 h milled sample.

Correlation between product purity and process parameters for the synthesis of Cu2ZnSnS4 nanoparticles using microwave irradiation

NASA Astrophysics Data System (ADS)

Ahmad, R.; Nicholson, K. S.; Nawaz, Q.; Peukert, W.; Distaso, M.

2017-07-01

Kesterites (CZT(S,Se)4) emerged as a favourable photovoltaic material, leading to solar cell efficiencies as high as 12.7%. The development of sustainable roll-to-roll printing processes that make use of Cu2ZnSnS4 (CZTS) nanoparticle inks requires the proper design of synthetic approaches and the understanding of the relation between process parameters and product purity. In the current paper, we developed this relationship by calculating a specific energy factor. A microwave-assisted synthetic method that operates at atmospheric pressure and makes use of eco-friendly solvents is established. Four solvents, i.e. ethylene glycol (EG), diethylene glycol (di-EG), triethylene glycol (tri-EG) and tetraethylene glycol (tet-EG) are compared and the temperature during the reaction is assessed by two different methods. In particular, two by-products have been identified, i.e. Cu2 - x S and a hexagonal phase. We show that the variation of reaction parameters such as power irradiation, type of solvent and precursor concentration influences the nanoparticles' sizes (from 12 to 6 nm) and also the temperature-time profile of reaction which, in turn, can be related to phase purity of CZTS nanoparticles. The results suggest that the product purity scales with the specific energy factor providing a useful tool to a rational design of high-quality CZTS nanoparticles.

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

PubMed Central

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

2017-01-01

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

Effect of calcination temperature of a copper ferrite synthesized by a sol-gel method on its structural characteristics and performance as Fenton catalyst to remove gallic acid from water.

PubMed

López-Ramón, María V; Álvarez, Miguel A; Moreno-Castilla, Carlos; Fontecha-Cámara, María A; Yebra-Rodríguez, África; Bailón-García, Esther

2018-02-01

A copper ferrite synthesized by a sol-gel combustion method was calcined at different temperatures up to 800°C, determining changes in its structural characteristics and magnetic measurements and studying its catalytic performance in gallic acid removal by Fenton reaction. The main objective was to study the effect of the calcination temperature of copper ferrite on its crystalline phase formation and transformation, activity and metal ion leaching. The cubic-to-tetragonal transformation of the spinel occurred via its reaction with the CuO phase, displacing Fe 3+ ions in B (octahedral) sites out of the spinel structure by the following reaction: 2Fe 3+ B +3CuO→Fe 2 O 3 +3Cu 2+ B . The catalysts showed superparamagnetic or substantial superparamagnetic behaviour. At higher calcination temperatures, catalyst activity was lower, and Cu ion leaching was markedly decreased. There was no Fe ion leaching with any catalyst. The as-prepared catalyst showed better catalytic performance than a commercial copper ferrite. Leached Cu ions acted as homogeneous catalysts, and their contribution to the overall removal mechanism was examined. Cu 2 O present in the as-prepared catalysts made only a small contribution to their activity. Finally, the reutilization of various catalysts was studied by performing different catalytic cycles. Copyright © 2017 Elsevier Inc. All rights reserved.

Metabolites identification of Huo Luo Xiao Ling Dan in rat urine by UPLC coupled with electrospray ionization time-of-flight mass spectrometry.

PubMed

Wang, Fenrong; Wu, Yun; Ai, Yu; Bian, Qiaoxia; Ma, Wen; Lee, David Y-W; Dai, Ronghua

2016-03-01

Huo Luo Xiao Ling Dan (HLXLD), a Chinese herbal formula, is used in folk medicine for the treatment of arthritis and other chronic inflammatory diseases. However, the in vivo integrated metabolism of its multiple components remains unknown. In this paper, an ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (UPLC-Q-TOF-MS) method was developed for detection and identification of HLXLD metabolites in rat urine at high and normal clinical dosages. The prototype constituents and their metabolites in urine were analyzed. The mass measurements were accurate within 8 ppm, and subsequent fragment ions offered higher quality structural information for interpretation of the fragmentation pathways of various compounds. A total of 85 compounds were detected in high dosages urine samples by a highly sensitive extracted ion chromatograms method, including 31 parent compounds and 54 metabolites. Our results indicated that phase 2 reactions (e.g. glucuronidation, glutathionidation and sulfation) were the main metabolic pathways of lactones, alkaloids and flavones, while phase I reactions (e.g. hydrogenation and hydroxylation) were the major metabolic reaction for coumarins, paeoniflorin and iridoids. This investigation provided important structural information on the metabolism of HLXLD and provided scientific evidence to obtain a more comprehensive metabolic profile. Copyright © 2015 John Wiley & Sons, Ltd.

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

USGS Publications Warehouse

Parkhurst, David L.; Wissmeier, Laurin

2015-01-01

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

Gas-phase reactions in extraterrestrial environments: laboratory investigations by crossed molecular beams.

PubMed

Balucani, Nadia; Casavecchia, Piergiorgio

2006-12-01

We have investigated gas-phase reactions of N((2)D) with the most abundant hydrocarbons in the atmosphere of Titan by the crossed molecular beam technique. In all cases, molecular products containing a novel CN bond are formed, thus suggesting possible routes of formation of gas-phase nitriles in the atmosphere of Titan and primordial Earth. The same approach has been recently extended to the study of radical-radical reactions, such as the reaction of atomic oxygen with the CH(3) and C(3)H(5) radicals. Products other than those already considered in the modeling of planetary atmospheres and interstellar medium have been identified.

Influence of Laser Power on the Microstructure and Mechanical Properties of a Laser Welded-Brazed Mg Alloy/Ni-Coated Steel Dissimilar Joint

NASA Astrophysics Data System (ADS)

Tan, Caiwang; Xiao, Liyuan; Liu, Fuyun; Chen, Bo; Song, Xiaoguo; Li, Liqun; Feng, Jicai

2017-05-01

In this work, we describe a method to improve the bonding of an immiscible Mg/steel system using Ni as an interlayer by coating it on the steel surface. Laser welding-brazing of AZ31B Mg alloy to Ni-coated Q235 steel using Mg-based filler was performed in a lap configuration. The influence of laser power on the weld characteristics, including joint appearance, formation of interfacial reaction layers and mechanical properties was investigated. The results indicated that the presence of the Ni-coating promoted the wetting of the liquid filler metal on the steel surface. A thermal gradient along the interface led to the formation of heterogeneous interfacial reaction layers. When using a low laser power of 1600 W, the reaction products were an FeAl phase in the direct laser irradiation zone, an AlNi phase close to the intermediate zone and mixtures of AlNi phase and an (α-Mg + Mg2Ni) eutectic structure near the interface at the seam head zone. For high powers of more than 2000 W, the FeAl phase grew thicker in the direct laser irradiation zone and a new Fe(Ni) transition layer formed at the interface of the intermediate zone and the seam head zone. However, the AlNi phase and (α-Mg + Mg2Ni) eutectic structure were scattered at the Mg seam. All the joints fractured at the fusion zone, indicating that the improved interface was not the weakest joint region. The maximum tensile-shear strength of the Mg/Ni-coated steel joint reached 190 N/mm, and the joint efficiency was 70% with respect to the Mg alloy base metal.

Collision induced dissociation of protonated N-nitrosodimethylamine by ion trap mass spectrometry: Ultimate carcinogens in gas phase

NASA Astrophysics Data System (ADS)

Kulikova, Natalia; Baker, Michael; Gabryelski, Wojciech

2009-12-01

Collision induced dissociation of protonated N-nitrosodimethylamine (NDMA) and isotopically labeled N-nitrosodimethyl-d6-amine (NDMA-d6) was investigated by sequential ion trap mass spectrometry to establish mechanisms of gas phase reactions leading to intriguing products of this potent carcinogen. The fragmentation of (NDMA + H+) occurs via two dissociation pathways. In the alkylation pathway, homolytic cleavage of the N-O bond of N-dimethyl, N'-hydroxydiazenium ion generates N-dimethyldiazenium distonic ion which reacts further by a CH3 radical loss to form methanediazonium ion. Both methanediazonium ion and its precursor are involved in ion/molecule reactions. Methanediazonium ion showed to be capable of methylating water and methanol molecules in the gas phase of the ion trap and N-dimethyldiazenium distonic ion showed to abstract a hydrogen atom from a solvent molecule. In the denitrosation pathway, a tautomerization of N-dimethyl, N'-hydroxydiazenium ion to N-nitrosodimethylammonium intermediate ion results in radical cleavage of the N-N bond of the intermediate ion to form N-dimethylaminium radical cation which reacts further through [alpha]-cleavage to generate N-methylmethylenimmonium ion. Although the reactions of NDMA in the gas phase are different to those for enzymatic conversion of NDMA in biological systems, each activation method generates the same products. We will show that collision induced dissociation of N-nitrosodiethylamine (NDEA) and N-nitrosodipropylamine (NDPA) is also a feasible approach to gain information on formation, stability, and reactivity of alkylating agents originating from NDEA and NDPA. Investigating such biologically relevant, but highly reactive intermediates in the condensed phase is hampered by the short life-times of these transient species.

A sensitivity analysis method for the body segment inertial parameters based on ground reaction and joint moment regressor matrices.

PubMed

Futamure, Sumire; Bonnet, Vincent; Dumas, Raphael; Venture, Gentiane

2017-11-07

This paper presents a method allowing a simple and efficient sensitivity analysis of dynamics parameters of complex whole-body human model. The proposed method is based on the ground reaction and joint moment regressor matrices, developed initially in robotics system identification theory, and involved in the equations of motion of the human body. The regressor matrices are linear relatively to the segment inertial parameters allowing us to use simple sensitivity analysis methods. The sensitivity analysis method was applied over gait dynamics and kinematics data of nine subjects and with a 15 segments 3D model of the locomotor apparatus. According to the proposed sensitivity indices, 76 segments inertial parameters out the 150 of the mechanical model were considered as not influent for gait. The main findings were that the segment masses were influent and that, at the exception of the trunk, moment of inertia were not influent for the computation of the ground reaction forces and moments and the joint moments. The same method also shows numerically that at least 90% of the lower-limb joint moments during the stance phase can be estimated only from a force-plate and kinematics data without knowing any of the segment inertial parameters. Copyright © 2017 Elsevier Ltd. All rights reserved.

Advances in quantum and molecular mechanical (QM/MM) simulations for organic and enzymatic reactions.

PubMed

Acevedo, Orlando; Jorgensen, William L

2010-01-19

Application of combined quantum and molecular mechanical (QM/MM) methods focuses on predicting activation barriers and the structures of stationary points for organic and enzymatic reactions. Characterization of the factors that stabilize transition structures in solution and in enzyme active sites provides a basis for design and optimization of catalysts. Continued technological advances allowed for expansion from prototypical cases to mechanistic studies featuring detailed enzyme and condensed-phase environments with full integration of the QM calculations and configurational sampling. This required improved algorithms featuring fast QM methods, advances in computing changes in free energies including free-energy perturbation (FEP) calculations, and enhanced configurational sampling. In particular, the present Account highlights development of the PDDG/PM3 semi-empirical QM method, computation of multi-dimensional potentials of mean force (PMF), incorporation of on-the-fly QM in Monte Carlo (MC) simulations, and a polynomial quadrature method for efficient modeling of proton-transfer reactions. The utility of this QM/MM/MC/FEP methodology is illustrated for a variety of organic reactions including substitution, decarboxylation, elimination, and pericyclic reactions. A comparison to experimental kinetic results on medium effects has verified the accuracy of the QM/MM approach in the full range of solvents from hydrocarbons to water to ionic liquids. Corresponding results from ab initio and density functional theory (DFT) methods with continuum-based treatments of solvation reveal deficiencies, particularly for protic solvents. Also summarized in this Account are three specific QM/MM applications to biomolecular systems: (1) a recent study that clarified the mechanism for the reaction of 2-pyrone derivatives catalyzed by macrophomate synthase as a tandem Michael-aldol sequence rather than a Diels-Alder reaction, (2) elucidation of the mechanism of action of fatty acid amide hydrolase (FAAH), an unusual Ser-Ser-Lys proteolytic enzyme, and (3) the construction of enzymes for Kemp elimination of 5-nitrobenzisoxazole that highlights the utility of QM/MM in the design of artificial enzymes.

Quantum mechanical study of solvent effects in a prototype S{sub N}2 reaction in solution: Cl{sup −} attack on CH{sub 3}Cl

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

Kuechler, Erich R.; Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455-0431; York, Darrin M., E-mail: york@biomaps.rutgers.edu

2014-02-07

The nucleophilic attack of a chloride ion on methyl chloride is an important prototype S{sub N}2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resultingmore » free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models.« less

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl- attack on CH3Cl

NASA Astrophysics Data System (ADS)

Kuechler, Erich R.; York, Darrin M.

2014-02-01

The nucleophilic attack of a chloride ion on methyl chloride is an important prototype SN2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resulting free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models.

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl- attack on CH3Cl.

PubMed

Kuechler, Erich R; York, Darrin M

2014-02-07

The nucleophilic attack of a chloride ion on methyl chloride is an important prototype SN2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resulting free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models.

LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 1: Theory and numerical solution procedures

NASA Technical Reports Server (NTRS)

Radhakrishnan, Krishnan

1994-01-01

LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 1 of a series of three reference publications that describe LENS, provide a detailed guide to its usage, and present many example problems. Part 1 derives the governing equations and describes the numerical solution procedures for the types of problems that can be solved. The accuracy and efficiency of LSENS are examined by means of various test problems, and comparisons with other methods and codes are presented. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

Theoretical perspectives on the mechanism and kinetics of the OH radical-initiated gas-phase oxidation of PCB126 in the atmosphere.

PubMed

Dang, Juan; Shi, Xiangli; Zhang, Qingzhu; Wang, Wenxing

2015-06-01

Polychlorinated biphenyls (PCBs) primarily exist in the gas phase in air and may undergo atmospheric oxidation degradations, particularly the oxidation reaction initiated by OH radicals. In this work, the mechanism of the OH radical-initiated atmospheric oxidation of the most toxic PCB congener 3,3',4,4',5-pentachlorobiphenyl (PCB126) was investigated by using quantum chemistry methods. The rate constants of the crucial elementary reactions were estimated by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The oxidation products of the reaction of PCB126 with OH radicals include 3,3',4,4',5-pentachlorobiphenyl-ols, chlorophenols, 2,3,4,7,8-pentachlorodibenzofuran, 2,3,4,6,7-pentachlorodibenzofuran, dialdehydes, 3,3',4,4',5-pentachloro-5'-nitro-biphenyl, and 4,5-dichloro-2-nitrophenol. Particularly, the formation of polychlorinated dibenzofurans (PCDFs) from the atmospheric oxidation of PCBs is revealed for the first time. The overall rate constant of the OH addition reaction is 2.52×10(-13)cm(3)molecule(-1)s(-1) at 298K and 1atm. The atmospheric lifetime of PCB126 determined by OH radicals is about 47.08days which indicates that PCB126 can be transported long distances from local to global scales. Copyright © 2015 Elsevier B.V. All rights reserved.

Nanoplate-like tungsten trioxide (hydrate) films prepared by crystal-seed-assisted hydrothermal reaction

NASA Astrophysics Data System (ADS)

Wang, P.; Yang, L.; Dai, B.; Yang, Z.; Guo, S.; Zhu, J.

2017-07-01

Vertically-aligned WO3 nanoplates on transparent conducting fluorine-doped tin oxide (FTO) glass were prepared by a facile template-free crystal-seed-assisted hydrothermal method. The effects of the hydrothermal temperature and reaction time on the crystal structure and morphology of the products were investigated by XRD and SEM. The XRD results showed that the as-prepared thin films obtained below 150∘C comprised orthorhombic WO3 ṡ H2O and completely converted to monoclinic WO3 at 180∘C. It was also noted that there was a phase transformation from orthorhombic to monoclinic by increasing the reaction time from 1 to 12 h. SEM analysis revealed that WO3 thin films are composed of plate-like nanostructures.

Identification and characterization of monomeric, volatile SiCl3NH2 as product of the reaction between SiCl4 and NH3: an important intermediate on the way to silicon nitride?

PubMed

Himmel, Hans-Jörg; Schiefenhövel, Nils; Binnewies, Michael

2003-03-17

We studied the reaction of SiCl(4) with NH(3) by mass spectrometry and IR spectroscopy. By means of mass spectrometry, SiCl(3)NH(2) was for the first time identified as an intermediate generated in significant amounts in the course of the reaction. In additional experiments, SiCl(3)NH(2) was formed as a stable gaseous product of the ammonolysis of SiCl(4), and the product was identified and characterized in detail by IR spectroscopic methods (gas phase and matrix isolation) in combination with quantum-chemical calculations. The calculations also gave access to important thermodynamical data.

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

NASA Technical Reports Server (NTRS)

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

1984-01-01

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

Heterogeneous reaction of particulate chlorpyrifos with NO3 radicals: Products, pathways, and kinetics

NASA Astrophysics Data System (ADS)

Li, Nana; Zhang, Peng; Yang, Bo; Shu, Jinian; Wang, Youfeng; Sun, Wanqi

2014-08-01

Chlorpyrifos is a typical chlorinated organophosphorus pesticide. The heterogeneous reaction of chlorpyrifos particles with NO3 radicals was investigated using a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and a real-time atmospheric gas analysis mass spectrometer. Chlorpyrifos oxon, 3,5,6-trichloro-2-pyridinol, O,O-diethyl O-hydrogen phosphorothioate, O,O-diethyl ester thiophosphoric acid, diethyl hydrogen phosphate and a phosphinyl disulfide compound were identified as the main degradation products. The heterogeneous reaction pathways were proposed and their kinetic processes were investigated via a mixed-phase relative rate method. The observed effective rate constant is 3.4 ± 0.2 × 10-12 cm3 molecule-1 s-1.

Mineral sulphide-lime reactions and effect of CaO/C mole ratio during carbothermic reduction of complex mineral sulphides

NASA Astrophysics Data System (ADS)

Hara, Yotamu Stephen Rainford

2014-01-01

Mineral sulphide (MS)-lime (CaO) ion exchange reactions (MS + CaO = MO + CaS) and the effect of CaO/C mole ratio during carbothermic reduction (MS + CaO + C = M + CaS + CO(g)) were investigated for complex froth flotation mineral sulphide concentrates. Phases in the partially and fully reacted samples were characterised by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The primary phases during mineral sulphide-lime ion exchange reactions are Fe3O4, CaSO4 Cu2S, and CaS. A complex liquid phase of Ca2CuFeO3S forms during mineral sulphide-lime exchange reactions above 1173 K. The formation mechanisms of Ca2CuFeO3S liquid phase are determined by characterising the partially reacted samples. The reduction rate and extent of mineral sulphides in the presence of CaO and C increase with the increase in CaO/C ratio. The metallic phases are surrounded by the CaS rich phase at CaO/C > 1, but the metallic phases and CaS are found as separate phases at CaO/C < 1. Experimental results show that the stoichiometric ratio of carbon should be slightly higher than that of CaO. The reactions between CaO and gangue minerals (SiO2 and Al2O3) are only observed at CaO/C > 1 and the reacted samples are excessively sintered.

Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

NASA Technical Reports Server (NTRS)

Ahlborg, Nadia L.; Zhu, Dongming

2013-01-01

The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

Lagrangian descriptors of driven chemical reaction manifolds.

PubMed

Craven, Galen T; Junginger, Andrej; Hernandez, Rigoberto

2017-08-01

The persistence of a transition state structure in systems driven by time-dependent environments allows the application of modern reaction rate theories to solution-phase and nonequilibrium chemical reactions. However, identifying this structure is problematic in driven systems and has been limited by theories built on series expansion about a saddle point. Recently, it has been shown that to obtain formally exact rates for reactions in thermal environments, a transition state trajectory must be constructed. Here, using optimized Lagrangian descriptors [G. T. Craven and R. Hernandez, Phys. Rev. Lett. 115, 148301 (2015)PRLTAO0031-900710.1103/PhysRevLett.115.148301], we obtain this so-called distinguished trajectory and the associated moving reaction manifolds on model energy surfaces subject to various driving and dissipative conditions. In particular, we demonstrate that this is exact for harmonic barriers in one dimension and this verification gives impetus to the application of Lagrangian descriptor-based methods in diverse classes of chemical reactions. The development of these objects is paramount in the theory of reaction dynamics as the transition state structure and its underlying network of manifolds directly dictate reactivity and selectivity.

Composite coating for low friction and wear applications and method thereof

DOEpatents

Besmann, T.M.; Blau, P.J.; Lee, W.Y.; Bae, Y.W.

1998-01-20

An article having a multiphase composite lubricant coating of a hard refractory matrix phase of titanium nitride dispersed with particles of a solid lubricating phase of molybdenum disulfide is prepared by heating the article to temperatures between 350 and 850 C in a reaction vessel at a reduced pressure and passing a gaseous mixture of Ti((CH{sub 3}){sub 2}N){sub 4}, MoF{sub 6}, H{sub 2}S and NH{sub 3} over the heated article forming a multiphase composite lubricant coating on the article. 1 fig.

CVD method of forming self-lubricating composites

DOEpatents

Besmann, T.M.; Blau, P.J.; Lee, W.Y.; Bae, Y.W.

1998-12-01

An article having a multiphase composite lubricant coating of a hard refractory matrix phase of titanium nitride dispersed with particles of a solid lubricating phase of molybdenum disulfide is prepared by heating the article to temperatures between 350 and 850 C in a reaction vessel at a reduced pressure and passing a gaseous mixture of Ti((CH{sub 3}){sub 2}N){sub 4}, MoF{sub 6}, H{sub 2}S and NH{sub 3} over the heated article forming a multiphase composite lubricant coating on the article. 1 fig.

Griffiths-like phase in high TC perovskite La2FeReO6 prepared in a controlled reducing atmosphere

NASA Astrophysics Data System (ADS)

Kaipamagalath, Aswathi; Palakkal, Jasnamol P.; Varma, Manoj R.

2018-05-01

The perovskite La2FeReO6 is prepared by solid-state reaction method. Calcination was done in a controlled reducing atmosphere. The structure of the compound is found to be orthorhombic with Pbnm space group. From the DC magnetic studies, the transition temperature (TC) of La2FeReO6 is found to be at 729 K. A Griffiths-like phase is present in the material with ferromagnetic short-range correlations above TC up to the Griffiths temperature TG = 863 K.

CVD method of forming self-lubricating composites

DOEpatents

Besmann, Theodore M.; Blau, Peter J.; Lee, Woo Y.; Bae, Yong W.

1998-01-01

An article having a multiphase composite lubricant coating of a hard refractory matrix phase of titanium nitride dispersed with particles of a solid lubricating phase of molybdenum disulfide is prepared by heating the article to temperatures between 350.degree. and 850.degree. C. in a reaction vessel at a reduced pressure and passing a gaseous mixture of Ti((CH.sub.3).sub.2 N).sub.4, MoF.sub.6, H.sub.2 S and NH.sub.3 over the heated article forming a multiphase composite lubricant coating on the article.

Composite coating for low friction and wear applications and method thereof

DOEpatents

Besmann, Theodore M.; Blau, Peter J.; Lee, Woo Y.; Bae, Yong W.

1998-01-01

An article having a multiphase composite lubricant coating of a hard refractory matrix phase of titanium nitride dispersed with particles of a solid lubricating phase of molybdenum disulfide is prepared by heating the article to temperatures between 350.degree. and 850.degree. C. in a reaction vessel at a reduced pressure and passing a gaseous mixture of Ti((CH.sub.3).sub.2 N).sub.4, MoF.sub.6, H.sub.2 S and NH.sub.3 over the heated article forming a multiphase composite lubricant coating on the article.

GAMMA AND X-RAY DOSIMETER AND DOSIMETRIC METHOD

DOEpatents

Taplin, G.V.; Douglas, C.H.; Sigoloff, S.C.

1958-08-19

An improvement in colorimetric gamma and x-ray dosimeter systems and a self-contained. hand carried dostmeter of the afore-mentioned type ts described. A novel point of the invention ltes in the addition of specific quantities of certain normalizing agents to the two phase chlorinated hydro-carbon-aqueous dyc colortmetric dosimeter to eliminate the after reaction and thereby extend the utility of such systein. The structure of the two phase colorimetric dosimeter tubes and the carrying case for the tubes of the portable dosimeter are unique features.

The high-throughput synthesis and phase characterisation of amphiphiles: a sweet case study.

PubMed

Feast, George C; Hutt, Oliver E; Mulet, Xavier; Conn, Charlotte E; Drummond, Calum J; Savage, G Paul

2014-03-03

A new method for the discovery of amphiphiles by using high-throughput (HT) methods to synthesise and characterise a library of galactose- and glucose-containing amphiphilic compounds is presented. The copper-catalysed azide–alkyne cycloaddition (CuAAC) “click” reaction between azide-tethered simple sugars and alkyne-substituted hydrophobic tails was employed to synthesise a library of compounds with systematic variations in chain length and unsaturation in a 24-vial array format. The liquid–crystalline phase behaviour was characterised in a HT manner by using synchrotron small-angle X-ray scattering (SSAXS). The observed structural variation with respect to chain parameters, including chain length and degree of unsaturation, is discussed, as well as hydration effects and degree of hydrogen bonding between head groups. The validity of our HT screening approach was verified by resynthesising a short-chain glucose amphiphile. A separate phase analysis of this compound confirmed the presence of numerous lyotropic liquid–crystalline phases.

Interface Reactions and Synthetic Reaction of Composite Systems

PubMed Central

Park, Joon Sik; Kim, Jeong Min

2010-01-01

Interface reactions in composite systems often determine their overall properties, since product phases usually formed at interfaces during composite fabrication processing make up a large portion of the composites. Since most composite materials represent a ternary or higher order materials system, many studies have focused on analyses of diffusion phenomena and kinetics in multicomponent systems. However, the understanding of the kinetic behavior increases the complexity, since the kinetics of each component during interdiffusion reactions need to be defined for interpreting composite behaviors. From this standpoint, it is important to clarify the interface reactions for producing compatible interfaces with desired product phases. A thermodynamic evaluation such as a chemical potential of involving components can provide an understanding of the diffusion reactions, which govern diffusion pathways and product phase formation. A strategic approach for designing compatible interfaces is discussed in terms of chemical potential diagrams and interface morphology, with some material examples.

In situ Mössbauer investigation of iron oxide catalyst in water gas shift reaction - Impact of oxyreduction potential and temperature

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Z.; Mitov, I.

2010-03-01

The aim of the study is to obtain the exact state of iron oxide catalyst active phase in reaction conditions, as well as the correlation between the active phase and catalytic properties of iron-containing catalysts. In situ Mössbauer spectroscopy is the major investigation technique. It is established that the change of reaction conditions (temperature and gas reaction mixture) lead to redistribution of the relative weight of spectra components and influence mainly tetrahedrally and octahedrally coordinated cations in Fe3O4 phase. It was concluded, that the active sites of the catalyst in studied reaction are probably pairs of Fe3++Fe2+-(Fe2.5+) ions, i.e. the mixed valance iron ions. The obtained catalytic activity can be explained with combination of the natural thermo-activated and catalytically induced electron exchange and better synchronizing of oxidation and reduction steps of the catalytic reaction.

Study of structural, spectroscopic and dielectric properties of multiferroic cadmium doped Samarium manganite synthesized by solid state reaction method

NASA Astrophysics Data System (ADS)

Gupta, Vandana; Raina, Bindu; Verma, Seema; Bamzai, K. K.

2018-05-01

Samarium manganite doped with cadmium having general formula Sm1-xCdxMnO3 for x = 0.05, 0.15 were synthesized by solid state reaction technique. These compositions were characterized by various techniques like X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and dielectric. XRD analysis confirms the single phase formation with pervoskites structure having orthorhombic phase. Densities were determined and compared with the results obtained by Archimedes principle. The scanning electron micrograph shows that the particle size distribution is almost homogeneous and spherical in shape. FTIR analysis confirms the presence of various atomic bonds within a molecule. A very large value of dielectric constant was observed at low frequencies due to the presence of grains and interfaces. The dielectric constant value decreases with increase in cadmium doping at samarium site.

Characterization of the reactive and dissociative behavior of transition metal oxide cluster ions in the gas phase.

PubMed

Maleknia, S; Brodbelt, J; Pope, K

1991-05-01

The reactive and dissociative behavior of molybdenum and tungsten oxide cluster ions has been studied in the gas phase using a triple quadrupole mass spectrometer. Cluster ions (MO3) n (-) were formed via a simple thermal desorption/electron capture negative ionization method, and their structures were characterized by collision-activated dissociation (CAD). Typically, the clusters fragment by losses of neutral (MO3) units. Reactions of the oxide cluster ions with ethylene oxide, cyclohexene oxide, ethylene sulfide cyclohexene sulfide, 2,3-butanedione, and 2,4-pentanedione were examined, and product ions were characterized by CAD. The clusters react with ethylene oxide by addition of ethylene oxide or net addition of oxygen, whereas the clusters react with ethylene sulfide via net addition of one or two sulfur atoms. Reactions of the clusters with the diones result in addition of one or two dione units, in some cases with dehydration.

A fully-automated one-pot synthesis of [18F]fluoromethylcholine with reduced dimethylaminoethanol contamination via [18F]fluoromethyl tosylate.

PubMed

Rodnick, Melissa E; Brooks, Allen F; Hockley, Brian G; Henderson, Bradford D; Scott, Peter J H

2013-08-01

A novel one-pot method for preparing [(18)F]fluoromethylcholine ([(18)F]FCH) via in situ generation of [(18)F]fluoromethyl tosylate ([(18)F]FCH2OTs), and subsequent [(18)F]fluoromethylation of dimethylaminoethanol (DMAE), has been developed. [(18)F]FCH was prepared using a GE TRACERlab FXFN, although the method should be readily adaptable to any other fluorine-(18) synthesis module. Initially ditosylmethane was fluorinated to generate [(18)F]FCH2OTs. DMAE was then added and the reaction was heated at 120 °C for 10 min to generate [(18)F]FCH. After this time, reaction solvent was evaporated, and the crude reaction mixture was purified by solid-phase extraction using C(18)-Plus and CM-Light Sep-Pak cartridges to provide [(18)F]FCH formulated in USP saline. The formulated product was passed through a 0.22 µm filter into a sterile dose vial, and submitted for quality control testing. Total synthesis time was 1.25 h from end-of-bombardment. Typical non-decay-corrected yields of [(18)F]FCH prepared using this method were 91 mCi (7% non-decay corrected based upon ~1.3 Ci [(18)F]fluoride), and doses passed all other quality control (QC) tests. A one-pot liquid-phase synthesis of [(18)F]FCH has been developed. Doses contain extremely low levels of residual DMAE (31.6 µg/10 mL dose or ~3 ppm) and passed all other requisite QC testing, confirming their suitability for use in clinical imaging studies. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ternary Phase-Separation Investigation of Sol-Gel Derived Silica from Ethyl Silicate 40

PubMed Central

Wang, Shengnan; Wang, David K.; Smart, Simon; Diniz da Costa, João C.

2015-01-01

A ternary phase-separation investigation of the ethyl silicate 40 (ES40) sol-gel process was conducted using ethanol and water as the solvent and hydrolysing agent, respectively. This oligomeric silica precursor underwent various degrees of phase separation behaviour in solution during the sol-gel reactions as a function of temperature and H2O/Si ratios. The solution composition within the immiscible region of the ES40 phase-separated system shows that the hydrolysis and condensation reactions decreased with decreasing reaction temperature. A mesoporous structure was obtained at low temperature due to weak drying forces from slow solvent evaporation on one hand and formation of unreacted ES40 cages in the other, which reduced network shrinkage and produced larger pores. This was attributed to the concentration of the reactive sites around the phase-separated interface, which enhanced the condensation and crosslinking. Contrary to dense silica structures obtained from sol-gel reactions in the miscible region, higher microporosity was produced via a phase-separated sol-gel system by using high H2O/Si ratios. This tailoring process facilitated further condensation reactions and crosslinking of silica chains, which coupled with stiffening of the network, made it more resistant to compression and densification. PMID:26411484

Physical and chemical interactions at the interface between atmospheric pressure plasmas and aqueous solutions

NASA Astrophysics Data System (ADS)

Lindsay, Alexander; Byrns, Brandon; Knappe, Detlef; Graves, David; Shannon, Steven

2014-10-01

Transport and reactions of charged species, neutrals, and photons at the interface between plasmas and liquids must be better quantified. The work presented here combines theoretical and experimental investigations of conditions in the gas and liquid phases in proximity to the interface for various discharges. OES is used to determine rotational and vibrational temperatures of OH, NO, and N2+; the relationship between these temperatures that characterize the distribution of internal energy states and gas and electron kinetic temperatures is considered. The deviation of OH rotational states from equilibrium under high humidity conditions is also presented. In contradiction with findings of other groups, high energy rotational states appear to become underpopulated with increasing humidity. In the aqueous phase, concentrations of longer-lived species such as nitrate, nitrite, hydrogen peroxide, and ozone are determined using ion chromatography and colorimetric methods. Spin-traps and electron paramagnetic resonance (EPR) are investigated for characterization of short-lived aqueous radicals like OH, O2-, NO, and ONOO-. Finally, experimental results are compared to a numerical model which couples transport and reactions within and between the bulk gas and liquid phases.

Hydrogen evolution from aqueous-phase photocatalytic reforming of ethylene glycol over Pt/TiO2 catalysts: Role of Pt and product distribution

NASA Astrophysics Data System (ADS)

Li, Fuying; Gu, Quan; Niu, Yu; Wang, Renzhang; Tong, Yuecong; Zhu, Shuying; Zhang, Hualei; Zhang, Zizhong; Wang, Xuxu

2017-01-01

Pt nanoparticles were loaded on anatase TiO2 by the photodeposition method to investigate their photocatalytic activity for H2 evolution in an aqueous solution containing a certain amount of ethylene glycol (EG) as the sacrificial agent. The surface properties and chemical states of the Pt/TiO2 sample were characterized by X-ray powder diffraction analysis, Brunauer-Emmett-Teller surface area analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance, and electrochemical resistance. The aqueous-phase photocatalytic EG reforming using Pt/TiO2 and anatase TiO2 generated not only H2 and CO2, but also CO, CH4, C2H6, and C2H4. Moreover, the amount of formate and acetate complexes in the solution increased gradually. The EG adsorption and gas-phase intermediates during photocatalytic reaction processes were investigated by the in situ FTIR spectrum. Finally, the photocatalytic EG reforming reaction mechanism was elucidated. This helped to better understand the role of a sacrificial agent in a photocatalytic hydrogen production.

Finite Element Analysis Modeling of Chemical Vapor Deposition of Silicon Carbide

DTIC Science & Technology

2014-06-19

thesis primarily focuses on mass transport by gas -phase flow and diffusion , chemical reaction in gas phase and on solid surfaces, and thin film...chemical vapor deposition (CVD). This thesis primarily focuses on mass transport by gas -phase flow and diffusion , chemical reaction in gas phase and...9 Fluid Flow…………………………………………..…………………..…………….9 Thermodynamics………………………………………..………………….….…….11 Chemical Reaction and Diffusion

Chemical methods for peptide and protein production.

PubMed

Chandrudu, Saranya; Simerska, Pavla; Toth, Istvan

2013-04-12

Since the invention of solid phase synthetic methods by Merrifield in 1963, the number of research groups focusing on peptide synthesis has grown exponentially. However, the original step-by-step synthesis had limitations: the purity of the final product decreased with the number of coupling steps. After the development of Boc and Fmoc protecting groups, novel amino acid protecting groups and new techniques were introduced to provide high quality and quantity peptide products. Fragment condensation was a popular method for peptide production in the 1980s, but unfortunately the rate of racemization and reaction difficulties proved less than ideal. Kent and co-workers revolutionized peptide coupling by introducing the chemoselective reaction of unprotected peptides, called native chemical ligation. Subsequently, research has focused on the development of novel ligating techniques including the famous click reaction, ligation of peptide hydrazides, and the recently reported α-ketoacid-hydroxylamine ligations with 5-oxaproline. Several companies have been formed all over the world to prepare high quality Good Manufacturing Practice peptide products on a multi-kilogram scale. This review describes the advances in peptide chemistry including the variety of synthetic peptide methods currently available and the broad application of peptides in medicinal chemistry.

Catalytic activity of calcium-based mixed metal oxides nanocatalysts in transesterification reaction of palm oil

NASA Astrophysics Data System (ADS)

Hassan, Noraakinah; Ismail, Kamariah Noor; Hamid, Ku Halim Ku; Hadi, Abdul

2017-12-01

Nowadays, biodiesel has become the forefront development as an alternative diesel fuel derived from biological sources such as oils of plant and fats. Presently, the conventional transesterification of vegetable oil to biodiesel gives rise to some technological problem. In this sense, heterogeneous nanocatalysts of calcium-based mixed metal oxides were synthesized through sol-gel method. It was found that significant increase of biodiesel yield, 91.75 % was obtained catalyzed by CaO-NbO2 from palm oil compared to pure CaO of 53.99 % under transesterification conditions (methanol/oil ratio 10:1, reaction time 3 h, catalyst concentration 4 wt%, reaction temperature 60 °C, and mixing speed of 600 rpm). The phase structure and crystallinity as well as the texture properties of the prepared catalysts were characterized by X-ray Diffraction (XRD) and the textural properties were characterized by N2 adsorption-desorption analysis. Sol-gel method has been known as versatile method in controlling the structural and chemical properties of the catalyst. Calcium-based mixed oxide synthesized from sol-gel method was found to exist as smaller crystallite size with high surface area.

Microwave assisted synthesis for A2E and development of LC-ESI-MS method for quantification of ocular bisretinoids in human retina.

PubMed

Kotnala, A; Senthilkumari, S; Halder, N; Kumar, A; Velpandian, T

2018-01-15

To develop a microwave assisted method for the rapid synthesis of A2E and also to develop a method to quantify N-retinylidene-N-retinylethanolamine(A2E), all-trans retinal dimer (ATRD), A2-glycerophospho ethanolamine (A2GPE), dihydropyridine phosphatidyl ethanolamine (A2DHPE) and monofuran A2E (MFA2E) in age matched retina. The development of microwave assisted synthesis of A2E, its purification and characterization for its utility in quantification in human retina. The semi-quantitative method development using LC-ESI-MS, LC-ESI-MS/MS and LC-APCI-MS/MS from pooled macula and peripheral retina for the bisretinoid analysis has been done. Maximum A2E conversion using microwave assisted process took place at 80°C for 45min with a yield of 55.01%. Highly sensitive and specific mass spectrometric method was developed using reverse phase C-18 separation with positive electrospray ionization and positive atmospheric phase chemical ionization of tandom mass spectrometry. A gradient mobile phase separation was achieved using water and methanol with 0.1% TFA. Multiple reaction monitoring acquisition for ESI and APCI was performed at ATRD m/z 551.2/522.2, A2GPE m/z 746.4/729.5, A2DHPEm/z 594.4/576.5, MFA2E m/z 608.2/591.2, A2E m/z 592.4/418.2. Method was validated using LC-ESI-SIM mode to determine selectivity, linearity, sensitivity, precision and accuracy. An attempt towards optimization of the synthetic procedure of A2E was made so as to reduce the lengthy reaction time without compromising the yield. Developed method was capable enough for the detection of low level of bisretinids in retina. Copyright © 2017 Elsevier B.V. All rights reserved.

Acoustical experiment of yogurt fermentation process.

PubMed

Ogasawara, H; Mizutani, K; Ohbuchi, T; Nakamura, T

2006-12-22

One of the important factors through food manufacturing is hygienic management. Thus, food manufactures prove their hygienic activities by taking certifications like a Hazard Analysis and Critical Control Point (HACCP). This concept also applies to food monitoring. Acoustical measurements have advantage for other measurement in food monitoring because they make it possible to measure with noncontact and nondestructive. We tried to monitor lactic fermentation of yogurt by a probing sensor using a pair of acoustic transducers. Temperature of the solution changes by the reaction heat of fermentation. Consequently the sound velocity propagated through the solution also changes depending on the temperature. At the same time, the solution change its phase from liquid to gel. The transducers usage in the solution indicates the change of the temperature as the change of the phase difference between two transducers. The acoustic method has advantages of nondestructive measurement that reduces contamination of food product by measuring instrument. The sensor was inserted into milk with lactic acid bacterial stain of 19 degrees C and monitored phase retardation of propagated acoustic wave and its temperature with thermocouples in the mild. The monitoring result of fermentation from milk to Caspian Sea yogurt by the acoustic transducers with the frequency of 3.7 MHz started to show gradient change in temperature caused by reaction heat of fermentation but stop the gradient change at the end although the temperature still change. The gradient change stopped its change because of phase change from liquid to gel. The present method will be able to measure indirectly by setting transducers outside of the measuring object. This noncontact sensing method will have great advantage of reduces risk of food contamination from measuring instrument because the measurement probes are set out of fermentation reactor or food containers. Our proposed method will contribute to the hygienization for the food manufacture industry.

Frequency spirals.

PubMed

Ottino-Löffler, Bertrand; Strogatz, Steven H

2016-09-01

We study the dynamics of coupled phase oscillators on a two-dimensional Kuramoto lattice with periodic boundary conditions. For coupling strengths just below the transition to global phase-locking, we find localized spatiotemporal patterns that we call "frequency spirals." These patterns cannot be seen under time averaging; they become visible only when we examine the spatial variation of the oscillators' instantaneous frequencies, where they manifest themselves as two-armed rotating spirals. In the more familiar phase representation, they appear as wobbly periodic patterns surrounding a phase vortex. Unlike the stationary phase vortices seen in magnetic spin systems, or the rotating spiral waves seen in reaction-diffusion systems, frequency spirals librate: the phases of the oscillators surrounding the central vortex move forward and then backward, executing a periodic motion with zero winding number. We construct the simplest frequency spiral and characterize its properties using analytical and numerical methods. Simulations show that frequency spirals in large lattices behave much like this simple prototype.

Prebiotic molecules formation through the gas-phase reaction between HNO and CH2CHOH2+

NASA Astrophysics Data System (ADS)

Redondo, Pilar; Martínez, Henar; Largo, Antonio; Barrientos, Carmen

2017-07-01

Context. Knowing how the molecules that are present in the ISM can evolve to more complex ones is an interesting topic in interstellar chemistry. The study of possible reactions between detected species can help to understand the evolution in complexity of the interstellar matter and also allows knowing the formation of new molecules which could be candidates to be detected. We focus our attention on two molecules detected in space, vinyl alcohol (CH2CHOH) and azanone (HNO). Aims: We aim to carry out a theoretical study of the ion-molecule reaction between protonated vinyl alcohol and azanone. The viability of formation of complex organic molecules (COMs) from these reactants is expected to provide some insight into the formation of prebiotic species through gas phase reactions. Methods: The reaction of protonated vinyl alcohol with azanone has been theoretically studied by using ab initio methods. Stationary points on the potential energy surface (PES) were characterized at the second-order Moller-Plesset level in conjunction with the aug-cc-pVTZ (correlation-consistent polarized valence triple-zeta) basis set. In addition, the electronic energies were refined by means of single-point calculations at the CCSD(T) level (coupled cluster single and double excitation model augmented with a non-iterative treatment of triple excitations) with the same basis set. Results: From a thermodynamic point of view, twelve products, composed of carbon, oxygen, nitrogen, and hydrogen which could be precursors in the formation of more complex biological molecules, can be obtained from this reaction. Among these, we focus especially on ionized glycine and two of its isomers. The analysis of the PES shows that only formation of cis- and trans-O-protonated imine acetaldehyde, CH2NHCOH+ and, CHNHCHOH+, are viable under interstellar conditions. Conclusions: The reaction of protonated vinyl alcohol with azanone can evolve in the interstellar medium to more complex organic molecules of prebiotic interest. Our results suggest that imine acetaldehyde could be a feasible candidate molecule to be searched for in space.

Use of X-ray diffraction to quantify amorphous supplementary cementitious materials in anhydrous and hydrated blended cements

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

Snellings, R., E-mail: ruben.snellings@epfl.ch; Salze, A.; Scrivener, K.L., E-mail: karen.scrivener@epfl.ch

2014-10-15

The content of individual amorphous supplementary cementitious materials (SCMs) in anhydrous and hydrated blended cements was quantified by the PONKCS [1] X-ray diffraction (XRD) method. The analytical precision and accuracy of the method were assessed through comparison to a series of mixes of known phase composition and of increasing complexity. A 2σ precision smaller than 2–3 wt.% and an accuracy better than 2 wt.% were achieved for SCMs in mixes with quartz, anhydrous Portland cement, and hydrated Portland cement. The extent of reaction of SCMs in hydrating binders measured by XRD was 1) internally consistent as confirmed through the standardmore » addition method and 2) showed a linear correlation to the cumulative heat release as measured independently by isothermal conduction calorimetry. The advantages, limitations and applicability of the method are discussed with reference to existing methods that measure the degree of reaction of SCMs in blended cements.« less

A Fluorogenic Aromatic Nucleophilic Substitution Reaction for Demonstrating Normal-Phase Chromatography and Isolation of Nitrobenzoxadiazole Chromophores

ERIC Educational Resources Information Center

Key, Jessie A.; Li, Matthew D.; Cairo, Christopher W.

2011-01-01

Normal-phase chromatography is an essential technique for monitoring chemical reactions, identifying the presence of specific components, as well as the purification of organic compounds. An experiment to facilitate the instruction and understanding of the concepts behind normal-phase chromatography at the introductory and intermediate…

CO.sub.2 separation from low-temperature flue gases

DOEpatents

Dilmore, Robert; Allen, Douglas; Soong, Yee; Hedges, Sheila

2010-11-30

Two methods are provide for the separation of carbon dioxide from the flue gases. The first method utilizes a phase-separating moiety dissolved in an aqueous solution of a basic moiety to capture carbon dioxide. The second method utilizes a phase-separating moiety as a suspended solid in an aqueous solution of a basic moiety to capture carbon dioxide. The first method takes advantage of the surface-independent nature of the CO.sub.2 absorption reactions in a homogeneous aqueous system. The second method also provides permanent sequestration of the carbon dioxide. Both methods incorporate the kinetic rate enhancements of amine-based scrubbing while eliminating the need to heat the entire amine solution (80% water) in order to regenerate and release CO.sub.2. Both methods also take advantage of the low-regeneration temperatures of CO.sub.2-bearing mineral systems such as Na.sub.2CO.sub.3/NaHCO.sub.3 and K.sub.2CO.sub.3/KHCO.sub.3.

Multiphase organic synthesis in microchannel reactors.

PubMed

Kobayashi, Juta; Mori, Yuichiro; Kobayashi, Shū

2006-07-17

"Miniaturization" is one of the most important aspects in today's technology. Organic chemistry is no exception. The search for highly effective, controllable, environmentally friendly methods for preparing products is of prime importance. The development of multiphase organic reactions in microchannel reactors has gained significant importance in recent years to allow novel reactivity, and has led to many fruitful results that are not attainable in conventional reactors. This Focus Review aims to shed light on how effectively multiphase organic reactions can be conducted with microchannel reactors by providing examples of recent remarkable studies, which have been grouped on the basis of the phases involved.

Monte Carlo PDF method for turbulent reacting flow in a jet-stirred reactor

NASA Astrophysics Data System (ADS)

Roekaerts, D.

1992-01-01

A stochastic algorithm for the solution of the modeled scalar probability density function (PDF) transport equation for single-phase turbulent reacting flow is described. Cylindrical symmetry is assumed. The PDF is represented by ensembles of N representative values of the thermochemical variables in each cell of a nonuniform finite-difference grid and operations on these elements representing convection, diffusion, mixing and reaction are derived. A simplified model and solution algorithm which neglects the influence of turbulent fluctuations on mean reaction rates is also described. Both algorithms are applied to a selectivity problem in a real reactor.

Introduction of Differential Scanning Calorimetry in a General Chemistry Laboratory Course: Determination of Thermal Properties of Organic Hydrocarbons

ERIC Educational Resources Information Center

D'Amelia, Ronald; Franks, Thomas; Nirode, William F.

2007-01-01

In first-year general chemistry undergraduate courses, thermodynamics and thermal properties such as melting points and changes in enthalpy ([Delta]H) and entropy ([Delta]S) of phase changes are frequently discussed. Typically, classical calorimetric methods of analysis are used to determine [Delta]H of reactions. Differential scanning calorimetry…

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

DeTuri, V.F.; Ervin, K.M.

Energy-resolved competitive collision-induced dissociation methods are used to measure the gas-phase acidities of a series of alcohols (methanol, ethanol, 2-propanol, and 2-methyl-2-propanol). The competitive dissociation reactions of fluoride-alcohol, [F{sup {minus}}{center{underscore}dot}HOR], alkoxide-water, [RO{sup {minus}}{center{underscore}dot}HOH], and alkoxide-methanol [RO{+-}{center{underscore}dot}HOCH{sub 3}] proton-bound complexes are studied using a guided ion beam tandem mass spectrometer. The reaction cross sections and product branching fractions to the two proton transfer channels are measured as a function of collision energy. The enthalpy difference between the two product channels is found by modeling the reaction cross sections near threshold using RRKM theory to account for the energy-dependent product branching ratiomore » and kinetic shift. From the enthalpy difference, the alcohol gas-phase acidities are determined relative to the well-known values of HF and H{sub 2}O. The measured gas-phase acidities are {Delta}{sub acid}H{sub 298}(CH{sub 3}OH) = 1599 {+-} 3 kJ/mol, {Delta}{sub acid}H{sub 298}(CH{sub 3}CH{sub 2}OH) = 1586 {+-} 5 kJ/mol, {Delta}{sub acid}H{sub 298}((CH{sub 3}){sub 2}CHOH) = 1576 {+-} 4 kJ/mol, and {Delta}{sub acid}H{sub 298}((CH{sub 3}){sub 3}COH) = 1573 {+-} 3 kJ/mol.« less

Hymenoptera Venom Immunotherapy: Tolerance and Efficacy of an Ultrarush Protocol versus a Rush and a Slow Conventional Protocol

PubMed Central

Patella, Vincenzo; Florio, Giovanni; Giuliano, Ada; Oricchio, Carmine; Spadaro, Giuseppe; Marone, Gianni; Genovese, Arturo

2012-01-01

Background and Objective. Various venom immunotherapy (VIT) protocols are available for Hymenoptera allergy. Although adverse reactions (ADRs) to VIT are widely reported, controlled trials are still needed. We conducted a randomized prospective study to evaluate ADRs and the efficacy of three VIT regimens. Methods. 76 patients with Hymenoptera allergy, aged 16–76 years, were randomized to receive an ultrarush protocol (group A: 27 patients), a rush protocol (group B: 25), or a slow protocol (group C: 24). Aqueous venom extract was used in incremental phase and an adsorbed depot in maintenance phase. ADRs and accidental Hymenoptera stings during VIT were used to evaluate efficacy. Results. During incremental treatment, ADRs occurred in 1.99%, 3.7%, and 3.9% of patients in groups A, B, and C, and in 0.99%, 1.46%, and 2.7%, respectively, during maintenance. ADRs were significantly fewer in group A (incremental + maintenance phase) than in group C (1.29% versus 3.2%; P = 0.013). Reactions to accidental Hymenoptera stings did not differ among groups (1.1%, 1.2%, and 1.1%). Conclusion. Ultrarush was as effective as the rush and slow protocols and was associated with a low incidence of reactions to stings. This study indicates that ultrarush VIT is a valid therapeutic option for Hymenoptera allergy. PMID:22693521

Mechanism of ascorbic acid interference in biochemical tests that use peroxide and peroxidase to generate chromophore.

PubMed

Martinello, Flávia; Luiz da Silva, Edson

2006-11-01

Ascorbic acid interferes negatively in peroxidase-based tests (Trinder method). However, the precise mechanism remains unclear for tests that use peroxide, a phenolic compound and 4-aminophenazone (4-AP). We determined the chemical mechanism of this interference, by examining the effects of ascorbic acid in the reaction kinetics of the production and reduction of the oxidized chromophore in urate, cholesterol, triglyceride and glucose tests. Reaction of ascorbic acid with the Trinder method constituents was also verified. Ascorbic acid interfered stoichiometrically with all tests studied. However, it had two distinct effects on the reaction rate. In the urate test, ascorbic acid decreased the chromophore formation with no change in its production kinetics. In contrast, in cholesterol, triglyceride and glucose tests, an increase in the lag phase of color development occurred. Of all the Trinder constituents, only peroxide reverted the interference. In addition, ascorbic acid did not interfere with oxidase activity nor reduce significantly the chromophore formed. Peroxide depletion was the predominant chemical mechanism of ascorbic acid interference in the Trinder method with phenolics and 4-AP. Distinctive effects of ascorbic acid on the reaction kinetics of urate, cholesterol, glucose and triglyceride might be due to the rate of peroxide production by oxidases.

A ring polymer molecular dynamics study of the isotopologues of the H + H2 reaction.

PubMed

Suleimanov, Yury V; de Tudela, Ricardo Pérez; Jambrina, Pablo G; Castillo, Jesús F; Sáez-Rábanos, Vicente; Manolopoulos, David E; Aoiz, F Javier

2013-03-14

The inclusion of Quantum Mechanical (QM) effects such as zero point energy (ZPE) and tunneling in simulations of chemical reactions, especially in the case of light atom transfer, is an important problem in computational chemistry. In this respect, the hydrogen exchange reaction and its isotopic variants constitute an excellent benchmark for the assessment of approximate QM methods. In particular, the recently developed ring polymer molecular dynamics (RPMD) technique has been demonstrated to give very good results for bimolecular chemical reactions in the gas phase. In this work, we have performed a detailed RPMD study of the H + H(2) reaction and its isotopologues Mu + H(2), D + H(2) and Heμ + H(2), at temperatures ranging from 200 to 1000 K. Thermal rate coefficients and kinetic isotope effects have been computed and compared with exact QM calculations as well as with quasiclassical trajectories and experiment. The agreement with the QM results is good for the heaviest isotopologues, with errors ranging from 15% to 45%, and excellent for Mu + H(2), with errors below 15%. We have seen that RPMD is able to capture the ZPE effect very accurately, a desirable feature of any method based on molecular dynamics. We have also verified Richardson and Althorpe's prediction [J. O. Richardson and S. C. Althorpe, J. Chem. Phys., 2009, 131, 214106] that RPMD will overestimate thermal rates for asymmetric reactions and underestimate them for symmetric reactions in the deep tunneling regime. The ZPE effect along the reaction coordinate must be taken into account when assigning the reaction symmetry in the multidimensional case.

C-terminal peptide extension via gas-phase ion/ion reactions

PubMed Central

Peng, Zhou; McLuckey, Scott A.

2015-01-01

The formation of peptide bonds is of great importance from both a biological standpoint and in routine organic synthesis. Recent work from our group demonstrated the synthesis of peptides in the gas-phase via ion/ion reactions with sulfo-NHS reagents, which resulted in conjugation of individual amino acids or small peptides to the N-terminus of an existing ‘anchor’ peptide. Here, we demonstrate a complementary approach resulting in the C-terminal extension of peptides. Individual amino acids or short peptides can be prepared as reagents by incorporating gas phase-labile protecting groups to the reactive C-terminus and then converting the N-terminal amino groups to the active ketenimine reagent. Gas-phase ion/ion reactions between the anionic reagents and doubly protonated “anchor” peptide cations results in extension of the “anchor” peptide with new amide bond formation at the C-terminus. We have demonstrated that ion/ion reactions can be used as a fast, controlled, and efficient means for C-terminal peptide extension in the gas phase. PMID:26640400

Dynamics of CrO 3 –Fe 2 O 3 Catalysts during the High-Temperature Water-Gas Shift Reaction: Molecular Structures and Reactivity

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

Keturakis, Christopher J.; Zhu, Minghui; Gibson, Emma K.

2016-06-13

A series of supported CrO 3/Fe 2O 3 catalysts were investigated for the high-temperature water-gas shift (WGS) and reverse-WGS reactions and extensively characterized using in situ and operando IR, Raman, and XAS spectroscopy during the high-temperature WGS/RWGS reactions. The in situ spectroscopy examinations reveal that the initial oxidized catalysts contain surface dioxo (O=) 2Cr 6+O 2 species and a bulk Fe 2O 3 phase containing some Cr 3+ substituted into the iron oxide bulk lattice. Operando spectroscopy studies during the high-temperature WGS/RWGS reactions show that the catalyst transforms during the reaction. The crystalline Fe 2O 3 bulk phase becomes Femore » 3O 4 ,and surface dioxo (O=) 2Cr 6+O 2 species are reduced and mostly dissolve into the iron oxide bulk lattice. Consequently, the chromium–iron oxide catalyst surface is dominated by FeO x sites, but some minor reduced surface chromia sites are also retained. The Fe 3–-xCr xO 4 solid solution stabilizes the iron oxide phase from reducing to metallic Fe0 and imparts an enhanced surface area to the catalyst. Isotopic exchange studies with C 16O 2/H 2 → C 18O 2/H 2 isotopic switch directly show that the RWGS reaction proceeds via the redox mechanism and only O* sites from the surface region of the chromium–iron oxide catalysts are involved in the RWGS reaction. The number of redox O* sites was quantitatively determined with the isotope exchange measurements under appropriate WGS conditions and demonstrated that previous methods have undercounted the number of sites by nearly 1 order of magnitude. The TOF values suggest that only the redox O* sites affiliated with iron oxide are catalytic active sites for WGS/RWGS, though a carbonate oxygen exchange mechanism was demonstrated to exist, and that chromia is only a textural promoter that increases the number of catalytic active sites without any chemical promotion effect.« less

Enhanced magnetization in morphologically and magnetically distinct BiFeO3 and La0.7Sr0.3MnO3 composites

NASA Astrophysics Data System (ADS)

Pillai, Shreeja; Reshi, Hilal Ahmad; Bagwaiya, Toshi; Banerjee, Alok; Shelke, Vilas

2017-09-01

Nanomaterials exhibit properties different from those of their bulk counterparts. The modified magnetic characteristics of manganite nanoparticles were exploited to improve magnetization in multiferroic BiFeO3 compound. We studied the composite of two morphologically and magnetically distinct compounds BiFeO3 (BFO) and La0.7Sr0.3MnO3 (LSMO). The microcrystalline BiFeO3 sample was prepared by solid state reaction method and the nanocrystalline La0.7Sr0.3MnO3 by sol-gel method. Composites with nominal compositions (1-x)BiFeO3-(x)La0.7Sr0.3MnO3 were prepared by modified solid state reaction method. The phase purity and crystal structures were checked by using X-ray diffraction. The formation of composites with phase separated BFO and LSMO was confirmed using Raman and Fourier Transform Infrared spectroscopy studies. The composite samples showed relatively high value of magnetization with finite coercivity. This improvement in magnetic behavior is ascribed to the coexistence of multiple magnetic orderings in composite samples. We scrutinized the possibility of oxygen vacancy or Fe mixed valency formation in the samples using X-ray photoelectron spectroscopy technique.

Workshop Report: Fundamental Reactions in Solid Propellant Combustion

DTIC Science & Technology

1979-05-01

combustion conditions. 6. What effect might a pressure-induced phase transition to a polymorph other than 6- HMX have on the pressure slope break during...pure HMX as well. Nevertheless, it is recommended that the high pressure polymorphs of HMX and RDX be determined. It was also felt that there...plateau burning phenomena E. Solid phase, surface, gas phase reactions F. Phase transitions : melting, vaporization, polymorphs G. Flame

Scaling down the size and increasing the throughput of glycosyltransferase assays: activity changes on stem cell differentiation.

PubMed

Patil, Shilpa A; Chandrasekaran, E V; Matta, Khushi L; Parikh, Abhirath; Tzanakakis, Emmanuel S; Neelamegham, Sriram

2012-06-15

Glycosyltransferases (glycoTs) catalyze the transfer of monosaccharides from nucleotide-sugars to carbohydrate-, lipid-, and protein-based acceptors. We examined strategies to scale down and increase the throughput of glycoT enzymatic assays because traditional methods require large reaction volumes and complex chromatography. Approaches tested used (i) microarray pin printing, an appropriate method when glycoT activity was high; (ii) microwells and microcentrifuge tubes, a suitable method for studies with cell lysates when enzyme activity was moderate; and (iii) C(18) pipette tips and solvent extraction, a method that enriched reaction product when the extent of reaction was low. In all cases, reverse-phase thin layer chromatography (RP-TLC) coupled with phosphorimaging quantified the reaction rate. Studies with mouse embryonic stem cells (mESCs) demonstrated an increase in overall β(1,3)galactosyltransferase and α(2,3)sialyltransferase activity and a decrease in α(1,3)fucosyltransferases when these cells differentiate toward cardiomyocytes. Enzymatic and lectin binding data suggest a transition from Lewis(x)-type structures in mESCs to sialylated Galβ1,3GalNAc-type glycans on differentiation, with more prominent changes in enzyme activity occurring at later stages when embryoid bodies differentiated toward cardiomyocytes. Overall, simple, rapid, quantitative, and scalable glycoT activity analysis methods are presented. These use a range of natural and synthetic acceptors for the analysis of complex biological specimens that have limited availability. Copyright © 2012 Elsevier Inc. All rights reserved.

Hydrothermal treatment of hazardous energetic materials waste

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

Brill, T.B.; Schoppelrei, J.W.; Maiella, P.G.

1995-12-31

Destruction of energetic materials by hydrothermal methods presents a potential for strongly exothermic oxidation-reduction reactions, which, if localized at a site in the reactor, create {open_quotes}hot spots{close_quotes}. To investigate highly exothermic hydrothermal reactions, real-time spectroscopic measurements in the stream by infrared and Raman spectroscopy offer opportunities. Flow reactor-spectroscopy cells were developed for such studies, focusing on approximately oxygen-balanced nitrate salts for which highly exothermic reactions can occur. In addition, the kinetics of formation of later stage products were studied because these products are likely to be released to the environment and to be regulated. An experiment was designed to simulatemore » the occurence of a phase separation in a reactor followed by rapid exothermic reaction. By varying the pressure, water content, and hydrogen content in the reaction volume of the cell, the freeze out temperatures required to set the carbon monoxide/carbon dioxide ratio were determined to be 1300 to 1470 K. Such high temperatures suggest that localized hot spots can exist which greatly exceed the overall set temperature of the reactor. This scenario can occur if a phase separation occurs to isolate ethylenediammonium dinitrate in quantities as small as tenths of milligrams. Studies of the oxidation-reduction reactions of nitrate ion with the counter ion show that the oxidizing power of the nitrate ion is realized provided a readily oxidizable cation such as hydroxylammonium is present. When the cation has a low reactivity, such as quanidinium, a much higher reaction temperature is required before the nitrate ion reacts. At this temperature, the cation may have already begun to decompose by a hydrothermal route.« less

Rate Constants and Activation Energies for Gas‐Phase Reactions of Three Cyclic Volatile Methyl Siloxanes with the Hydroxyl Radical

PubMed Central

Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie

2015-01-01

ABSTRACT Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second‐order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140‐mL gas‐phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D4 and D5 with the OH radical are 1.9 × 10−12 (95% confidence interval (CI): (1.7–2.2) × 10−12) and 2.6 × 10−12 (CI: (2.3–2.9) × 10−12) cm3 molecule−1 s−1, respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D6 is 2.8 × 10−12 (CI: (2.5–3.2) × 10−12) cm3 molecule−1 s−1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D5 were 33% higher than for D4 (CI: 30–37%), whereas the rates for D6 were only 8% higher than for D5 (CI: 5–10%). The activation energies of the reactions of D4, D5, and D6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol. PMID:27708500

Rate Constants and Activation Energies for Gas-Phase Reactions of Three Cyclic Volatile Methyl Siloxanes with the Hydroxyl Radical.

PubMed

Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie; Macleod, Matthew

2015-07-01

Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second-order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ), and dodecamethylcyclohexasiloxane (D 6 ) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140-mL gas-phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D 4 and D 5 with the OH radical are 1.9 × 10 -12 (95% confidence interval (CI): (1.7-2.2) × 10 -12 ) and 2.6 × 10 -12 (CI: (2.3-2.9) × 10 -12 ) cm 3 molecule -1 s -1 , respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D 6 is 2.8 × 10 -12 (CI: (2.5-3.2) × 10 -12 ) cm 3 molecule -1 s -1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D 5 were 33% higher than for D 4 (CI: 30-37%), whereas the rates for D 6 were only 8% higher than for D 5 (CI: 5-10%). The activation energies of the reactions of D 4 , D 5 , and D 6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol.

Development of gait segmentation methods for wearable foot pressure sensors.

PubMed

Crea, S; De Rossi, S M M; Donati, M; Reberšek, P; Novak, D; Vitiello, N; Lenzi, T; Podobnik, J; Munih, M; Carrozza, M C

2012-01-01

We present an automated segmentation method based on the analysis of plantar pressure signals recorded from two synchronized wireless foot insoles. Given the strict limits on computational power and power consumption typical of wearable electronic components, our aim is to investigate the capability of a Hidden Markov Model machine-learning method, to detect gait phases with different levels of complexity in the processing of the wearable pressure sensors signals. Therefore three different datasets are developed: raw voltage values, calibrated sensor signals and a calibrated estimation of total ground reaction force and position of the plantar center of pressure. The method is tested on a pool of 5 healthy subjects, through a leave-one-out cross validation. The results show high classification performances achieved using estimated biomechanical variables, being on average the 96%. Calibrated signals and raw voltage values show higher delays and dispersions in phase transition detection, suggesting a lower reliability for online applications.

Actinide extraction methods

DOEpatents

Peterman, Dean R [Idaho Falls, ID; Klaehn, John R [Idaho Falls, ID; Harrup, Mason K [Idaho Falls, ID; Tillotson, Richard D [Moore, ID; Law, Jack D [Pocatello, ID

2010-09-21

Methods of separating actinides from lanthanides are disclosed. A regio-specific/stereo-specific dithiophosphinic acid having organic moieties is provided in an organic solvent that is then contacted with an acidic medium containing an actinide and a lanthanide. The method can extend to separating actinides from one another. Actinides are extracted as a complex with the dithiophosphinic acid. Separation compositions include an aqueous phase, an organic phase, dithiophosphinic acid, and at least one actinide. The compositions may include additional actinides and/or lanthanides. A method of producing a dithiophosphinic acid comprising at least two organic moieties selected from aromatics and alkyls, each moiety having at least one functional group is also disclosed. A source of sulfur is reacted with a halophosphine. An ammonium salt of the dithiophosphinic acid product is precipitated out of the reaction mixture. The precipitated salt is dissolved in ether. The ether is removed to yield the dithiophosphinic acid.

Phase transformations in the reaction cell of TiNi-based sintered systems

NASA Astrophysics Data System (ADS)

Artyukhova, Nadezhda; Anikeev, Sergey; Yasenchuk, Yuriy; Chekalkin, Timofey; Gunther, Victor; Kaftaranova, Maria; Kang, Ji-Hoon; Kim, Ji-Soon

2018-05-01

The present work addresses the structural-phase state changes of porous TiNi-based compounds fabricated by reaction sintering (RS) of Ti and Ni powders with Co, Mo, and no additives introduced. The study also emphasizes the features of a reaction cell (RC) during the transition from the solid- to liquid-phase sintering. Mechanisms of phase transformations occurring in the solid phase, involving the low-melting Ti2Ni phase within the RC, have been highlighted. Also, the intermediate Ti2Ni phase had a crucial role to provide both the required RS behavior and modified phase composition of RS samples, and besides, it is found to be responsible for the near-equiatomic TiNi saturation of the melt. Both cobalt and molybdenum additives are shown to cause additional structuring of the transition zone (TZ) at the Ti2Ni‑TiNi interface and broadening of this zone. The impact of Co and Mo on the Ti2Ni phase is evident through fissuring of this phase layer, which is referred to solidified stresses increased in the layer due to post-alloying defects in the structure.

Visualization of the equilibrium position of colloidal particles at fluid-water interfaces by deposition of nanoparticles

NASA Astrophysics Data System (ADS)

Sabapathy, Manigandan; Kollabattula, Viswas; Basavaraj, Madivala G.; Mani, Ethayaraja

2015-08-01

We present a general yet simple method to measure the contact angle of colloidal particles at fluid-water interfaces. In this method, the particles are spread at the required fluid-water interface as a monolayer. In the water phase a chemical reaction involving reduction of a metal salt such as aurochloric acid is initiated. The metal grows as a thin film or islands of nanoparticles on the particle surface exposed to the water side of the interface. Analyzing the images of particles by high resolution scanning microscopy (HRSEM), we trace the three phase contact line up to which deposition of the metal film occurs. From geometrical relations, the three phase contact angle is then calculated. We report the measurements of the contact angle of silica and polystyrene (PS) particles at different interfaces such as air-water, decane-water and octanol-water. We have also applied this method to measure the contact angle of surfactant treated polystyrene particles at the air-water interface, and we find a non-monotonic change of the contact angle with the concentration of the surfactant. Our results are compared with the well-known gel trapping technique and we find good comparison with previous measurements.We present a general yet simple method to measure the contact angle of colloidal particles at fluid-water interfaces. In this method, the particles are spread at the required fluid-water interface as a monolayer. In the water phase a chemical reaction involving reduction of a metal salt such as aurochloric acid is initiated. The metal grows as a thin film or islands of nanoparticles on the particle surface exposed to the water side of the interface. Analyzing the images of particles by high resolution scanning microscopy (HRSEM), we trace the three phase contact line up to which deposition of the metal film occurs. From geometrical relations, the three phase contact angle is then calculated. We report the measurements of the contact angle of silica and polystyrene (PS) particles at different interfaces such as air-water, decane-water and octanol-water. We have also applied this method to measure the contact angle of surfactant treated polystyrene particles at the air-water interface, and we find a non-monotonic change of the contact angle with the concentration of the surfactant. Our results are compared with the well-known gel trapping technique and we find good comparison with previous measurements. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03369a

Organised surfactant assemblies in analytical atomic spectrometry

NASA Astrophysics Data System (ADS)

Sanz-Medel, Alfredo; Fernandez de la Campa, Maria del Rosario; Gonzalez, Elisa Blanco; Fernandez-Sanchez, Maria Luisa

1999-02-01

The use of surfactant-based organised assemblies in analytical atomic spectroscopy is extensively and critically reviewed along three main lines: first, the ability of organised media to enhance detection of atomic spectroscopic methods by favourable manipulation of physical and chemical properties of the sample solution second, the extension of separation mechanisms by resorting to organised media and third a discussion of synergistic combinations of liquid chromatography separations and atomic detectors via the use of vesicular mobile phases. Changes in physical properties of sample solutions aspirated in atomic spectrometry by addition of surfactants can be advantageously used in at least four different ways: (i) to improve nebulisation efficiency; (ii) to enhance wettability of solid surfaces used for atomisation; (iii) to improve compatibility between aqueous and organic phases; and (iv) to achieve good dispersion of small particles in "slurry" techniques. Controversial results and statements published so far are critically discussed. The ability of surfactant-based organised assemblies, such as micelles and vesicles, to organise reactants at the molecular level has also been applied to enhance the characteristics of chemical generation of volalite species of metals and semi-metals (e.g., hydride or ethylide generation of As, Pb, Cd, Se, Sn, and cold vapour Hg generation) used in atomic methods. Enhancements in efficiency/transport of volatile species, increases in the reaction kinetics, stabilisation of some unstable species and changes in the selectivity of the reactions by surfactants are dealt with. Non-chromatographic cloud-point separations to design pre-concentration procedures with subsequent metal determination by atomic methods are addressed along with chromatographic separations of expanded scope by addition of surfactants to the conventional aqueous mobile phases of reversed-phase high-performance liquid chromatography. Finally, the synergistic effect of using vesicles to improve both the separation capabilities of reversed-phase HPLC and the detectability of atomic detectors by on-line vesicular hydride generation is described. In particular, the possible separation mechanisms responsible for micellar and vesicular mobile phases in reversed-phase chromatographies are analysed and compared. The possible effect of modification of stationary phases by monomers of the surfactants should also be taken into account. The application of such on-line couplings to develop new hybrid approaches to tackle modern problems of trace element speciation for As, Hg, Se, and Cd completes this revision of the present interface between analytical atomic spectroscopy and surfactant-based organised assemblies.

Preparation of pigments for space-stable thermal control coatings

NASA Technical Reports Server (NTRS)

Campbell, W. B.; Smith, R. G.

1972-01-01

The identification and control of vapor phase reaction kinetics to produce pigments by homogeneous nucleation were achieved. A vapor phase apparatus was designed, fabricated, and calibrated through 1800 C. Vapor phase reactions were analyzed, calculations made, and powders of alumina, rutile, zinc orthotitanate (in a mixed phase), calcium tungstate, and lanthana were produced by homogeneous nucleation. Electron microscopy shows uniform particle morphology and size, and supports anticipated advantages of vapor-phase homogeneous nucleation; namely, purity, freedom from defects, and uniform particle sizing without grinding.

Tinnitus as an alarm bell: stress reaction tinnitus model.

PubMed

Alpini, D; Cesarani, A

2006-01-01

Stress is a significant factor influencing the clinical course of tinnitus. Auditory system is particularly sensitive to the effects of different stress factors (chemical, oxidative, emotional, etc.). Different stages of reaction (alarm, resistance, exhaustion) lead to different characteristics of tinnitus and different therapeutic approaches. Individual characteristics of stress reaction may explain different aspects of tinnitus in various patients with different responses to treatment, despite similar audiological and etiological factors. A model based on individual reactions to stress factors (stress reaction tinnitus model) could explain tinnitus as an alarm signal, just like an 'alarm bell', informing the patient that something potentially dangerous for subject homeostasis is happening. Tinnitus could become a disabling symptom when the subject is chronically exposed to a stress factor and is unable to switch off the alarm. Stress signals, specific for each patient, have to be identified during the 'alarm' phase in order to prevent an evolution toward the 'resistance' and 'exhaustion' phases. In these phases, identification of stressor is no more sufficient, due to the organization of a 'paradoxical auditory memory' and a 'pathologically shifted attention to tinnitus'. Identification of stress reaction phase requires accurate otolaryngology and anamnesis combined with audiological matching tests (Feldman Masking Test, for example) and psychometric questionnaires (Tinnitus Reaction and Tinnitus Cognitive Questionnaires). Copyright (c) 2006 S. Karger AG, Basel.

The Reaction Mechanism and Kinetics for the Reaction of OH Radicals with Atmospheric Metolachlor

NASA Astrophysics Data System (ADS)

Chen, Chao; Zhou, Qin; Zheng, Jian; Jin, Xinhui; Ma, Wanyong; Zhou, Jianhua

2018-07-01

Metolachlor [2-chloro- N-(2-ethyl-6-methylphenyl)- N-(2-methoxy-1-methylethyl)acetamide], has been used as a chloroacetanilide herbicide to control annual grass weeds and broadleaf weeds in corn, cotton, peanuts, soybeans and beans. In this paper, aRS-metolachlor has been used as a model to investigate the reaction of OH radicals with atmospheric metolachlor. The reaction mechanism was obtained at the MPWB1K/6-311 + g(3 df,2 p)//MPWB1K/6-31 + g( d, p) level of theory and the rate constants were deduced over the temperature range of 180-370 K using canonical variational transition state (CVT) theory with the small curvature tunneling (SCT) method. The atmospheric lifetime of aRS-metolachlor determined by OH radicals is about 3.97 h, which indicates that it can be degradaded in the gas phase easily and doesn't have the potential for long-range transport.

Mechanistic and kinetic investigation on OH-initiated oxidation of tetrabromobisphenol A.

PubMed

He, Maoxia; Li, Xin; Zhang, Shiqing; Sun, Jianfei; Cao, Haijie; Wang, Wenxing

2016-06-01

Detailed mechanism of the OH-initiated transformation of tetrabromobisphenol A (TBBPA) has been investigated by quantum chemical methods in this paper. Abstraction reactions of hydrogen atoms from the OH groups and CH3 groups of TBBPA are the dominant pathways of the initial reactions. The produced phenolic-type radical and alkyl-type radical may transfer to 4,4'-(ethene-1,1-diyl)bis(2,6-dibromophenol), 4-acetyl-2,6-dibromophenol and 2,6-dibromobenzoquinone at high temperature. In water, major products are 2,6-dibromo-p-hydroquinone, 4-isopropylene-2,6-dibromophenol and 4-(2-hydroxyisopropyl)-2,6-dibromophenol resulting from the addition reactions. Total rate constants of the initial reaction are 1.02 × 10(-12) cm(3) molecule(-1) s(-1) in gas phase and 1.93 × 10(-12) cm(3) molecule(-1) s(-1) in water at 298 K. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of Heat-Treatment Temperature on the Interfacial Reaction Between Oxide Inclusions and Si-Mn Killed Steel

NASA Astrophysics Data System (ADS)

Zhang, Xueliang; Yang, Shufeng; Liu, Chengsong; Li, Jingshe; Hao, Weixing

2018-06-01

The effect of heat-treatment temperature on the interfacial reaction between MnO-SiO2-FeO oxide and Fe-Mn-Si alloy was investigated by the diffusion couple method in the temperature range of 1173-1573 K. The reaction at the interface between the alloy and oxide was not obvious during treatment at 1173 K, but, with increasing heat-treatment temperature, the interfacial reaction was strengthened and the proportion of the MnO·SiO2 phase in the oxide increased. The width of the particle-precipitation zone in the alloy increased with increasing temperature from 1173 K to 1473 K but decreased at 1573 K owing to coarsening of the precipitated particles. In addition, Mn2+ and Si4+ in the oxide significantly diffused into the alloy at 1573 K, resulting in an obvious increase of the Mn and Si contents in the alloy near the interface.