Catalytic membrane in denitrification of water: a means to facilitate intraporous diffusion of reactants

NARCIS (Netherlands)

Ilinich, O.M.; Cuperus, F.P.; Gemert, van R.W.; Gribov, E.N.; Nosova, L.V.

2000-01-01

The series of mono- and bi-metallic catalysts with Pd and/or Cu supported over γ-Al 2O 3 was investigated with respect to reduction of nitrate and nitrite ions in water by hydrogen. Pronounced limitations of catalytic performance due to intraporous diffusion of the reactants were observed in the

Heavy-ion radiation chemistry

International Nuclear Information System (INIS)

Imamura, Masashi

1975-01-01

New aspect of heavy ion radiation chemistry is reviewed. Experiment has been carried out with carbon ions and nitrogen ions accelerated by a 160 cm cyclotron of the Institute of Physical and Chemical Research. The results of experiments are discussed, taking into consideration the effects of core radius depending on heavy ion energy and of the branch tracks of secondary electrons outside the core on chemical reaction and the yield of products. The effect of core size on chemical reaction was not able to be observed, because the incident energy of heavy ions was only several tens of MeV. Regarding high radical density, attention must be given to the production of oxygen in the core. It is possible to produce O 2 in the core in case of high linear energy transfer (LET), while no production of O 2 in case of low LET radiation. This may be one of study problems in future. LET effects on the yield of decomposed products were examined on acetone, methyl-ethyl-ketone and diethyl ketone, using heavy ions (C and N) as well as gamma radiation and helium ions. These three ketones showed that the LET change of two gaseous products, H 2 and CO, was THF type. There are peaks at 50-70 eV/A in the yield of both products. The peaks suggest the occurrence of ''saturation'' in decomposition. Attention was drawn to acetone containing a small amount (2 wt.%) of H 2 O. H 2 O and CO produced from this system differ from those in the pure system. The hydrogen connection formed by such a small amount of H 2 O may mediate the energy transfer. Sodium acetate tri-hydrate produces CH 3 radical selectively by gamma-ray irradiation at 77 K. In this case, the production of CH 2 COO - increases with the increase of LET of radiation. This phenomenon may be an important study problem. (Iwakiri, K.)

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

Science.gov (United States)

Kong, Peter C

2013-11-26

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

Ion microbeam irradiation for radiobiology and radical chemistry: status and prospect

Energy Technology Data Exchange (ETDEWEB)

Khodja, H, E-mail: hicham.khodja@cea.fr [CEA, IRAMIS, SIS2M, LEEL, 91191 Gif-sur-Yvette (France); CNRS, UMR 3299, SIS2M, LEEL, 91191 Gif-sur-Yvette (France)

2011-01-01

Ion microbeams are commonly used to study local irradiation effects in living cells, as it has been established that ion beam irradiations can lead to deleterious changes in cells that are not struck directly by the microbeam. Such changes, which take place over distances long compared to the size of the irradiation spot and for times long compared to the time of irradiation, are collectively termed radiation-induced bystander effect or RIBE. Free-radical chemistry is frequently invoked to explain the RIBE but no unified model is available at present. Ion microbeams when coupled with advanced methods for observing free radicals are the tools of choice for investigating the chemistry and biological processes governing RIBE.

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

Science.gov (United States)

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

2015-09-01

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

Cryogenic ion chemistry and spectroscopy.

Science.gov (United States)

Wolk, Arron B; Leavitt, Christopher M; Garand, Etienne; Johnson, Mark A

2014-01-21

The use of mass spectrometry in macromolecular analysis is an incredibly important technique and has allowed efficient identification of secondary and tertiary protein structures. Over 20 years ago, Chemistry Nobelist John Fenn and co-workers revolutionized mass spectrometry by developing ways to non-destructively extract large molecules directly from solution into the gas phase. This advance, in turn, enabled rapid sequencing of biopolymers through tandem mass spectrometry at the heart of the burgeoning field of proteomics. In this Account, we discuss how cryogenic cooling, mass selection, and reactive processing together provide a powerful way to characterize ion structures as well as rationally synthesize labile reaction intermediates. This is accomplished by first cooling the ions close to 10 K and condensing onto them weakly bound, chemically inert small molecules or rare gas atoms. This assembly can then be used as a medium in which to quench reactive encounters by rapid evaporation of the adducts, as well as provide a universal means for acquiring highly resolved vibrational action spectra of the embedded species by photoinduced mass loss. Moreover, the spectroscopic measurements can be obtained with readily available, broadly tunable pulsed infrared lasers because absorption of a single photon is sufficient to induce evaporation. We discuss the implementation of these methods with a new type of hybrid photofragmentation mass spectrometer involving two stages of mass selection with two laser excitation regions interfaced to the cryogenic ion source. We illustrate several capabilities of the cryogenic ion spectrometer by presenting recent applications to peptides, a biomimetic catalyst, a large antibiotic molecule (vancomycin), and reaction intermediates pertinent to the chemistry of the ionosphere. First, we demonstrate how site-specific isotopic substitution can be used to identify bands due to local functional groups in a protonated tripeptide designed to

Study of the ionization of alkane-electron scavenger reactant mixtures irradiated by 60Co gamma rays

International Nuclear Information System (INIS)

Bonnet, Jacques.

1977-01-01

This study deals with ionization of alkane-electron scavenger reactant mixtures, irradiated by 60 Co γ-rays. It is shown that the extrapolated free-ion yields (extrapolated yield method) decrease with the reactant concentration. On the basis of ONSAGER model and theoretical treatment of MOZUMDER, the cross sections of epithermal electron attachment in hexane, cyclohexane, 2,2-dimethylbutane, cyclopentane, 2,2,4-trimethylpentane for CCl 4 , C 7 F 14 , C 6 H 5 Br, C 6 H 5 Cl, C 6 F 14 , (C 6 H 5 ) 2 are determined. A comparison between gas-phase and liquid-phase cross sections is established [fr

An alkali ion source based on graphite intercalation compounds for ion mobility spectrometry

International Nuclear Information System (INIS)

Tabrizchi, Mahmoud; Hosseini, Zahra S

2008-01-01

A variety of alkali cation emitters were developed as the ion source for ion mobility spectrometry. The cation emitters were constructed based on alkali ion graphite intercalation compounds (GICs). The compounds were prepared by fusing alkali salts with ground graphite. In order to produce alkali ions, the compounds were loaded on a filament and heated to red. Reactant ions of the form alk + ions were observed for the alkali salts NaCl, KCl.LiCl, CsCl and SrCl. In addition to Na + ions, K + ions were observed at the beginning of thermionic emission from Na-GIC. This is due to the low ionization potential of potassium that exists in trace amounts in sodium salts. In addition to the potassium ion, Na + was observed in the case of LiCl salt. The Na + and K + peaks originating from impurities totally disappeared after about 40 min. However, the thermionic emission of the main ion of the corresponding salt lasted for several days. No negative ions were observed upon reversing the drift field. Selected organic compounds (methyl isobutyl ketone, dimethyl sulfoxide, acetone and tetrahydrofuran) were also ionized via alkali cation attachment reaction. Distinct ion mobility patterns were observed for different substances using one type of alkali reactant ion. However, the ion mobility pattern for a given substance changed when a different alkali reactant ion was used. Ammonia and amines were not ionized when this source was used

Cold Plasma: simple tool for convenient utilitarian chemistry in homogeneous and heterogeneous environments

International Nuclear Information System (INIS)

Das, Tomi Nath; Dey, Ghasi Ram

2015-07-01

Cold Plasma based experimental facilities have been commissioned (XI-XII Plan periods) in Radiation and Photochemistry Division, BARC to carry out free radical and excited state-induced chemistry in single- and mixed-phase milieu. In any reaction medium, Dielectric Barrier assisted Electric Discharge generates in situ non-equilibrium plasma constituting of electrons and photons (< 10 eV each) and chemically reactive ions, excited species and free radical transients near room temperature and pressure. Choice of reactants and nature of other added ingredient(s), type of interacting surface(s) and the dielectric characteristics, the rate and amount of electric energy dissipated within etc. control various reactions’ propensities and the natures of final products, following either routine or novel, atypical chemistry. A selection of results obtained from our laboratory highlight the development and the potential use of this technology. Constant improvements in Cold Plasma reactor types, and design, fabrication and assembly of a real-time measurement system, aiming to probe mechanistic chemistry, are also underway. (author)

Organic chemistry - Fast reactions 'on water'

NARCIS (Netherlands)

Klijn, JE; Engberts, JBFN

2005-01-01

Efficient reactions in aqueous organic chemistry do not require soluble reactants, as had been thought. A newly developed ‘on-water’ protocol is characterized by short reaction times, and the products are easy to isolate.

Ion mobility spectrometry–mass spectrometry studies of ion processes in air at atmospheric pressure and their application to thermal desorption of 2,4,6-trinitrotoluene

International Nuclear Information System (INIS)

Sabo, Martin; Malásková, Michaela; Matejčík, Štefan

2014-01-01

In this study we have investigated the negative reactant ion formation in a negative corona discharge (CD) using the corona discharge ion mobility spectrometry orthogonal acceleration time-of-flight (CD-IMS-oaTOF) technique. The reactant ions were formed in the CD operating in the reverse gas flow mode at an elevated temperature of 363.5 K in synthetic and ambient air. Under these conditions mainly O 2 − and their clusters were formed. We have also studied the influence of CCl 4 admixture to air (dopant gas) on the composition of the reactant ions, which resulted in the formation of Cl − and its clusters with a reduced ion mobility of 3.05 cm 2  V −1  s −1 as a major reactant ion peak. Additional IMS peaks with reduced ion mobilities of 2.49, 2.25 and 2.03 cm 2  V −1  s −1 were detected, and Cl −  · (NO 2 ) and Cl −  · (NO) n (n = 2, 3) anions were identified. The negative reactant ions were used to detect 2,4,6 trinitrotoluene (TNT) using the thermal desorption (TD) technique using a CD-IMS instrument. Using TD sampling and a negative CD ion source doped by CCl 4 we have achieved a limit of detection of 350 pg for direct surface analysis of TNT. (paper)

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

Science.gov (United States)

Stanis, Ronald J.; Lambert, Timothy N.

2016-12-06

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

Roles of surface chemistry on safety and electrochemistry in lithium ion batteries.

Science.gov (United States)

Lee, Kyu Tae; Jeong, Sookyung; Cho, Jaephil

2013-05-21

Motivated by new applications including electric vehicles and the smart grid, interest in advanced lithium ion batteries has increased significantly over the past decade. Therefore, research in this field has intensified to produce safer devices with better electrochemical performance. Most research has focused on the development of new electrode materials through the optimization of bulk properties such as crystal structure, ionic diffusivity, and electric conductivity. More recently, researchers have also considered the surface properties of electrodes as critical factors for optimizing performance. In particular, the electrolyte decomposition at the electrode surface relates to both a lithium ion battery's electrochemical performance and safety. In this Account, we give an overview of the major developments in the area of surface chemistry for lithium ion batteries. These ideas will provide the basis for the design of advanced electrode materials. Initially, we present a brief background to lithium ion batteries such as major chemical components and reactions that occur in lithium ion batteries. Then, we highlight the role of surface chemistry in the safety of lithium ion batteries. We examine the thermal stability of cathode materials: For example, we discuss the oxygen generation from cathode materials and describe how cells can swell and heat up in response to specific conditions. We also demonstrate how coating the surfaces of electrodes can improve safety. The surface chemistry can also affect the electrochemistry of lithium ion batteries. The surface coating strategy improved the energy density and cycle performance for layered LiCoO2, xLi2MnO3·(1 - x)LiMO2 (M = Mn, Ni, Co, and their combinations), and LiMn2O4 spinel materials, and we describe a working mechanism for these enhancements. Although coating the surfaces of cathodes with inorganic materials such as metal oxides and phosphates improves the electrochemical performance and safety properties of

Major ion chemistry of the Son River, India: Weathering processes ...

Indian Academy of Sciences (India)

Major ion chemistry of the Son River, India: Weathering processes, dissolved fluxes and water quality assessment. Chinmaya Maharana, Sandeep Kumar Gautam,. Abhay Kumar Singh and Jayant K Tripathi. J. Earth Syst. Sci. 124(6) cO Indian Academy of Sciences. Supplementary data ...

Lithium Ion Battery Chemistries from Renewable Energy Storage to Automotive and Back-up Power Applications

DEFF Research Database (Denmark)

Stan, Ana-Irina; Swierczynski, Maciej Jozef; Stroe, Daniel Ioan

2014-01-01

Lithium ion (Li-ion) batteries have been extensively used in consumer electronics because of their characteristics, such as high efficiency, long life, and high gravimetric and volumetric energy. In addition, Li-ion batteries are becoming the most attractive candidate as electrochemical storage...... systems for stationary applications, as well as power source for sustainable automotive and back-up power supply applications. This paper gives an overview of the Li-ion battery chemistries that are available at present in the market, and describes the three out of four main applications (except...... the consumers’ applications), grid support, automotive, and back-up power, for which the Li-ion batteries are suitable. Each of these applications has its own specifications and thus, the chemistry of the Li-ion battery should be chosen to fulfil the requirements of the corresponding application. Consequently...

Ion chemistry of some organic molecules studied by field ionization and field desorption mass spectrometry

International Nuclear Information System (INIS)

Greef, J. van der.

1980-01-01

The chemistry of isolated ions in the gas phase is strongly dependent on the internal energy which they have required upon formation. Since also the average lifetime of an ion depends on its internal energy, ion lifetime studies have been employed for many years to obtain a better insight in the relation between the chemistry and internal energy of gas phase ions. A very powerful tool for such studies is the field ionization kinetic (FIK) method, because it can provide a time-resolved picture of decompositions of ions with lifetimes varying from 10 -11 to 10 -5 s. The FIK method has been used in combination with 2 H, 13 C and 15 N labelling for mechanistic studies on the fragmentation of some selected ionised organic molecules. (Auth.)

Unique aqueous Li-ion/sulfur chemistry with high energy density and reversibility.

Science.gov (United States)

Yang, Chongyin; Suo, Liumin; Borodin, Oleg; Wang, Fei; Sun, Wei; Gao, Tao; Fan, Xiulin; Hou, Singyuk; Ma, Zhaohui; Amine, Khalil; Xu, Kang; Wang, Chunsheng

2017-06-13

Leveraging the most recent success in expanding the electrochemical stability window of aqueous electrolytes, in this work we create a unique Li-ion/sulfur chemistry of both high energy density and safety. We show that in the superconcentrated aqueous electrolyte, lithiation of sulfur experiences phase change from a high-order polysulfide to low-order polysulfides through solid-liquid two-phase reaction pathway, where the liquid polysulfide phase in the sulfide electrode is thermodynamically phase-separated from the superconcentrated aqueous electrolyte. The sulfur with solid-liquid two-phase exhibits a reversible capacity of 1,327 mAh/(g of S), along with fast reaction kinetics and negligible polysulfide dissolution. By coupling a sulfur anode with different Li-ion cathode materials, the aqueous Li-ion/sulfur full cell delivers record-high energy densities up to 200 Wh/(kg of total electrode mass) for >1,000 cycles at ∼100% coulombic efficiency. These performances already approach that of commercial lithium-ion batteries (LIBs) using a nonaqueous electrolyte, along with intrinsic safety not possessed by the latter. The excellent performance of this aqueous battery chemistry significantly promotes the practical possibility of aqueous LIBs in large-format applications.

Characterization of a Distributed Plasma Ionization Source (DPIS) for Ion Mobility Spectrometry and Mass Spectrometry

International Nuclear Information System (INIS)

Waltman, Melanie J.; Dwivedi, Prabha; Hill, Herbert; Blanchard, William C.; Ewing, Robert G.

2008-01-01

A recently developed atmospheric pressure ionization source, a distributed plasma ionization source (DPIS), was characterized and compared to commonly used atmospheric pressure ionization sources with both mass spectrometry and ion mobility spectrometry. The source consisted of two electrodes of different sizes separated by a thin dielectric. Application of a high RF voltage across the electrodes generated plasma in air yielding both positive and negative ions depending on the polarity of the applied potential. These reactant ions subsequently ionized the analyte vapors. The reactant ions generated were similar to those created in a conventional point-to-plane corona discharge ion source. The positive reactant ions generated by the source were mass identified as being solvated protons of general formula (H2O)nH+ with (H2O)2H+ as the most abundant reactant ion. The negative reactant ions produced were mass identified primarily as CO3-, NO3-, NO2-, O3- and O2- of various relative intensities. The predominant ion and relative ion ratios varied depending upon source construction and supporting gas flow rates. A few compounds including drugs, explosives and environmental pollutants were selected to evaluate the new ionization source. The source was operated continuously for several months and although deterioration was observed visually, the source continued to produce ions at a rate similar that of the initial conditions. The results indicated that the DPIS may have a longer operating life than a conventional corona discharge.

Lifecycle comparison of selected Li-ion battery chemistries under grid and electric vehicle duty cycle combinations

Science.gov (United States)

Crawford, Alasdair J.; Huang, Qian; Kintner-Meyer, Michael C. W.; Zhang, Ji-Guang; Reed, David M.; Sprenkle, Vincent L.; Viswanathan, Vilayanur V.; Choi, Daiwon

2018-03-01

Li-ion batteries are expected to play a vital role in stabilizing the electrical grid as solar and wind generation capacity becomes increasingly integrated into the electric infrastructure. This article describes how two different commercial Li-ion batteries based on LiNi0.8Co0.15Al0.05O2 (NCA) and LiFePO4 (LFP) chemistries were tested under grid duty cycles recently developed for two specific grid services: (1) frequency regulation (FR) and (2) peak shaving (PS) with and without being subjected to electric vehicle (EV) drive cycles. The lifecycle comparison derived from the capacity, round-trip efficiency (RTE), resistance, charge/discharge energy, and total used energy of the two battery chemistries are discussed. The LFP chemistry shows better stability for the energy-intensive PS service, while the NCA chemistry is more conducive to the FR service under the operating regimes investigated. The results can be used as a guideline for selection, deployment, operation, and cost analyses of Li-ion batteries used for different applications.

Stereospecific control of peptide gas-phase ion chemistry with cis and trans cyclo ornithine residues

Czech Academy of Sciences Publication Activity Database

Marek, Aleš; Nguyen, H. T. H.; Brož, Břetislav; Tureček, F.

2018-01-01

Roč. 53, č. 2 (2018), s. 124-137 ISSN 1076-5174 Institutional support: RVO:61388963 Keywords : cis and trans isomers * cyclo ornithine * peptide dissociations * peptide ion structures * stereochemistry Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 2.422, year: 2016

Comparing Amide-Forming Reactions Using Green Chemistry Metrics in an Undergraduate Organic Laboratory

Science.gov (United States)

Fennie, Michael W.; Roth, Jessica M.

2016-01-01

In this laboratory experiment, upper-division undergraduate chemistry and biochemistry majors investigate amide-bond-forming reactions from a green chemistry perspective. Using hydrocinnamic acid and benzylamine as reactants, students perform three types of amide-forming reactions: an acid chloride derivative route; a coupling reagent promoted…

On the Chemistry of Hydrides of N Atoms and O+ Ions

Science.gov (United States)

Awad, Zainab; Viti, Serena; Williams, David A.

2016-08-01

Previous work by various authors has suggested that the detection by Herschel/HIFI of nitrogen hydrides along the low-density lines of sight toward G10.6-0.4 (W31C) cannot be accounted for by gas-phase chemical models. In this paper we investigate the role of surface reactions on dust grains in diffuse regions, and we find that formation of the hydrides by surface reactions on dust grains with efficiency comparable to that for H2 formation reconciles models with observations of nitrogen hydrides. However, similar surface reactions do not contribute significantly to the hydrides of O+ ions detected by Herschel/HIFI that are present along many sight lines in the Galaxy. The O+ hydrides can be accounted for by conventional gas-phase chemistry either in diffuse clouds of very low density with normal cosmic-ray fluxes or in somewhat denser diffuse clouds with high cosmic-ray fluxes. Hydride chemistry in dense dark clouds appears to be dominated by gas-phase ion-molecule reactions.

Equalization equations in reactant resolution

Indian Academy of Sciences (India)

Unknown

given partitioning of the system in physical or functional space. The most frequently ... Then, the inter-reactant equilibrium is considered. The ... Global equilibrium. Even though the chemical potential in the case of global equilibrium is equalized by definition (see (1)), we repeat here the proof, for the current needs, using.

Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

Energy Technology Data Exchange (ETDEWEB)

Yi, Tanghong; Chen, Wei; Cheng, Lei; Bayliss, Ryan D.; Lin, Feng; Plews, Michael R.; Nordlund, Dennis; Doeff, Marca M.; Persson, Kristin A.; Cabana, Jordi (LBNL); (SLAC); (UIC); (UCB)

2017-02-07

Reversible intercalation reactions provide the basis for modern battery electrodes. Despite decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A_xK_1–xFeF₃ (A = Li, Na). By starting with KFeF₃, approximately 75% of K⁺ ions were subsequently replaced by Li⁺ and Na⁺ through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopy confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe^2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. This study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.

New fundamental equations of thermodynamics for systems in chemical equilibrium at a specified partial pressure of a reactant and the standard transformed formation properties of reactants

International Nuclear Information System (INIS)

Alberty, R.A.; Oppenheim, I.

1993-01-01

When temperature, pressure, and the partial pressure of a reactant are fixed, the criterion of chemical equilibrium can be expressed in terms of the transformed Gibbs energy G' that is obtained by using a Legendre transform involving the chemical potential of the reactant that is fixed. For reactions of ideal gases, the most natural variables to use in the fundamental equation are T, P', and P B , where P' is the partial pressure of the reactants other than the one that is fixed and P B is the partial pressure of the reactant that is fixed. The fundamental equation for G' yields the expression for the transformed entropy S', and a transformed enthalpy can be defined by the additional Legendre transform H'=G'+TS'. This leads to an additional form of the fundamental equation. The calculation of transformed thermodynamic properties and equilibrium compositions is discussed for a simple system and for a general multireaction system. The change, in a reaction, of the binding of the reactant that is at a specified pressure can be calculated using one of the six Maxwell equations of the fundamental equation in G'

Non-OH chemistry in oxidation flow reactors for the study of atmospheric chemistry systematically examined by modeling

Directory of Open Access Journals (Sweden)

Z. Peng

2016-04-01

Full Text Available Oxidation flow reactors (OFRs using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D, O(3P, and O3. In this study, we investigate the relative importance of other reactants to OH for the fate of reactant species in OFR under a wide range of conditions via box modeling. The relative importance of non-OH species is less sensitive to UV light intensity than to water vapor mixing ratio (H2O and external OH reactivity (OHRext, as both non-OH reactants and OH scale roughly proportionally to UV intensity. We show that for field studies in forested regions and also the urban area of Los Angeles, reactants of atmospheric interest are predominantly consumed by OH. We find that O(1D, O(3P, and O3 have relative contributions to volatile organic compound (VOC consumption that are similar or lower than in the troposphere. The impact of O atoms can be neglected under most conditions in both OFR and troposphere. We define “riskier OFR conditions” as those with either low H2O (< 0.1 % or high OHRext ( ≥  100 s−1 in OFR185 and > 200 s−1 in OFR254. We strongly suggest avoiding such conditions as the importance of non-OH reactants can be substantial for the most sensitive species, although OH may still dominate under some riskier conditions, depending on the species present. Photolysis at non-tropospheric wavelengths (185 and 254 nm may play a significant (> 20 % role in the degradation of some aromatics, as well as some oxidation intermediates, under riskier reactor conditions, if the quantum yields are high. Under riskier conditions, some biogenics can have

Application of ion chemistry to tropospheric VOC measurements

International Nuclear Information System (INIS)

Hansel, A.; Wisthaler, A.; Graus, M.; Grabmer, W.

2002-01-01

The main interest in tropospheric volatile organic compounds (VOCs) originating from biogenic sources such as forests and anthropogenic sources such as cities is because these reactive trace gases can have a significant impact on levels of oxidants such as ozone (O 3 ) and the hydroxyl radical (OH). The proton-transfer-reaction mass-spectrometry (PTR-MS) technique developed by Werner Lindingers Laboratory, utilizes positive ion chemistry to measure trace neutral concentrations in air. It has been applied in food research, medicine and environmental studies to gain gas phase information about VOCs at parts per trillion (pptv) levels.The real-time method relies on proton transfer reactions between H 3 O + primary ions and VOCs which have a higher proton affinity than water molecules. Organic trace gases such as hydrocarbons, carbonyls, alcohols, acetonitrile, and others can be monitored on-line.Results on tropospheric VOCs measurements in tropical regions and in cities are discussed. (nevyjel)

Cu-Click Compatible Triazabutadienes To Expand the Scope of Aryl Diazonium Ion Chemistry.

Science.gov (United States)

Cornali, Brandon M; Kimani, Flora W; Jewett, John C

2016-10-07

Triazabutadienes can be used to readily generate reactive aryl diazonium ions under mild, physiologically relevant conditions. These conditions are compatible with a range of functionalities that do not tolerate traditional aryl diazonium ion generation. To increase the utility of this aryl diazonium ion releasing chemistry an alkyne-containing triazabutadiene was synthesized. The copper-catalyzed azide-alkyne cycloaddition ("Cu-click") reaction was utilized to modify the alkyne-containing triazabutadiene and shown to be compatible with the nitrogen-rich triazabutadiene. One of the triazole products was tethered to a fluorophore, thus enabling the direct fluorescent labeling of a model protein.

Some aspects of metallic ion chemistry and dynamics in the mesosphere and thermosphere

Science.gov (United States)

Mathews, J. D.

1987-01-01

The relationship between the formation of sporadic layers of metallic ion and the dumping of these ions into the upper mesosphere is discussed in terms of the tidal wind, classical (i.e., windshear) and other more complex, perhaps highly nonlinear layer formation mechanisms, and a possible circulation mechanism for these ions. Optical, incoherent scatter radar, rocket, and satellite derived evidence for various layer formation mechanisms and for the metallic ion circulation system is reviewed. The results of simple one dimensional numerical model calculations of sporadic E and intermediate layer formation are presented along with suggestions for more advanced models of intense or blanketing sporadic E. The flux of metallic ions dumped by the tidal wind system into the mesosphere is estimated and compared with estimates of total particle flux of meteoric origin. Possible effects of the metallic ion flux and of meteoric dust on D region ion chemistry are discussed.

Bibliographies on radiation chemistry. 9. Metal ions and complexes. Part A: Cobalt, rhodium, iridium

Energy Technology Data Exchange (ETDEWEB)

Hoffman, M Z; Ross, A B

1986-01-01

The one-electron oxidation and reduction of metal ions and complexes can yield species in unusual oxidation states, and ligand-radicals coordinated to the central metal. These often unstable species can be mechanistically important intermediates in thermal, photochemical, and electrochemical reactions involving metal-containing substances. Their generation via radiolysis provides an alternate means of characterizing them using kinetic and spectroscopic techniques. We hope these bibliographies on the radiation chemistry of metal ions and complexes, presented according to periodic groups, will prove useful to researchers in metallo-redox chemistry. These bibliographies contain only primary literature sources; reviews are not included. However, a list of general review articles on the radiation chemistry of metal ions and complexes is presented here in the first section which covers cobalt, rhodium and iridium, Group 9 in the new IUPAC notation. Additional parts of the bibliography are planned, covering other periodic groups. Part A of the bibliography was prepared by a search of the Radiation Chemistry Data Center Bibliographic Data Base (RCDCbib) through January 1986 for papers on rhodium, iridium and cobalt compounds, and radiolysis (both continuous and pulsed). Papers in which the use of metal compounds was incidental to the primary objective of the study were excluded. Excluded also were publications in unrefereed and obscure sources such as meeting proceedings, internal reports, dissertations, and patents. The majority of the studies in the resultant compilation deal with experiments performed on solutions, mainly aqueous, although a substantial fraction is devoted to solid-state esr measurements. The references are listed in separate sections for each of the metals, and are presented in approximate chronological order.

MinION Analysis and Reference Consortium: Phase 2 data release and analysis of R9.0 chemistry.

Science.gov (United States)

Jain, Miten; Tyson, John R; Loose, Matthew; Ip, Camilla L C; Eccles, David A; O'Grady, Justin; Malla, Sunir; Leggett, Richard M; Wallerman, Ola; Jansen, Hans J; Zalunin, Vadim; Birney, Ewan; Brown, Bonnie L; Snutch, Terrance P; Olsen, Hugh E

2017-01-01

Long-read sequencing is rapidly evolving and reshaping the suite of opportunities for genomic analysis. For the MinION in particular, as both the platform and chemistry develop, the user community requires reference data to set performance expectations and maximally exploit third-generation sequencing. We performed an analysis of MinION data derived from whole genome sequencing of Escherichia coli K-12 using the R9.0 chemistry, comparing the results with the older R7.3 chemistry. We computed the error-rate estimates for insertions, deletions, and mismatches in MinION reads. Run-time characteristics of the flow cell and run scripts for R9.0 were similar to those observed for R7.3 chemistry, but with an 8-fold increase in bases per second (from 30 bps in R7.3 and SQK-MAP005 library preparation, to 250 bps in R9.0) processed by individual nanopores, and less drop-off in yield over time. The 2-dimensional ("2D") N50 read length was unchanged from the prior chemistry. Using the proportion of alignable reads as a measure of base-call accuracy, 99.9% of "pass" template reads from 1-dimensional ("1D")  experiments were mappable and ~97% from 2D experiments. The median identity of reads was ~89% for 1D and ~94% for 2D experiments. The total error rate (miscall + insertion + deletion ) decreased for 2D "pass" reads from 9.1% in R7.3 to 7.5% in R9.0 and for template "pass" reads from 26.7% in R7.3 to 14.5% in R9.0. These Phase 2 MinION experiments serve as a baseline by providing estimates for read quality, throughput, and mappability. The datasets further enable the development of bioinformatic tools tailored to the new R9.0 chemistry and the design of novel biological applications for this technology. K: thousand, Kb: kilobase (one thousand base pairs), M: million, Mb: megabase (one million base pairs), Gb: gigabase (one billion base pairs).

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

Science.gov (United States)

Banerjee, Rupak

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

GAS-PHASE CHEMISTRY OF THE CYANATE ION, OCN−

International Nuclear Information System (INIS)

Cole, Callie A.; Wang, Zhe-Chen; Bierbaum, Veronica M.; Snow, Theodore P.

2015-01-01

Cyanate (OCN − ) is the only ion to date whose presence has been confirmed in the icy mantles that coat interstellar dust grains. Understanding the chemical behavior of cyanate at a fundamental level is therefore integral to the advancement of astrochemistry. We seek to unravel the chemistry of this intriguing anion through a combination of gas-phase experiments and theoretical explorations. Our approach is twofold: first, employing a flowing afterglow-selected ion flow tube apparatus, the reactions between OCN − and three of the most abundant atomic species in the interstellar medium, hydrogen, nitrogen, and oxygen, are examined. Hydrogen atoms readily react by associative detachment, but the remarkable stability of OCN − does not give rise to an observable reaction with either nitrogen or oxygen atoms. To explain these results, the potential energy surfaces of several reactions are investigated at the B3LYP/6-311++G(d,p) level of theory. Second, collision induced dissociation experiments involving deprotonated uracil, thymine, and cytosine in an ion trap mass spectrometer reveal an interesting connection between these pyrimidine nucleobase anions and OCN − . Theoretical calculations at the B3LYP/6-311++G(d,p) level of theory are performed to delineate the mechanisms of dissociation and explore the possible role of OCN − as a biomolecule precursor

Chiral Selectivity in Inter-reactant Recognition and Electron Transfer of the Oxidation of Horse Heart Cytochrome c by Trioxalatocobaltate(III)

DEFF Research Database (Denmark)

Nazmutdinov, Renat R.; Bronshtein, Michael D.; Zinkicheva, Tamara T.

2016-01-01

We have studied electron transfer between cytochrome c and the chiral transition-metal complex pair Λ- and Δ-[Co(Ox)3]3− (Ox2− = oxalate) via strong ion-pair formation. Chirality was found in both ion-pair formation and electron transfer, with the Λ enantiomer the more strongly bound and faster r...... reacting. Investigations of the chirality using electron-transfer theory combined with quantum-chemical and statistical-mechanical calculations showed that chirality is solely in inter-reactant interaction and electronic overlap.......We have studied electron transfer between cytochrome c and the chiral transition-metal complex pair Λ- and Δ-[Co(Ox)3]3− (Ox2− = oxalate) via strong ion-pair formation. Chirality was found in both ion-pair formation and electron transfer, with the Λ enantiomer the more strongly bound and faster...

Reversible Redox Chemistry of Azo Compounds for Sodium-Ion Batteries.

Science.gov (United States)

Luo, Chao; Xu, Gui-Liang; Ji, Xiao; Hou, Singyuk; Chen, Long; Wang, Fei; Jiang, Jianjun; Chen, Zonghai; Ren, Yang; Amine, Khalil; Wang, Chunsheng

2018-03-05

Sustainable sodium-ion batteries (SSIBs) using renewable organic electrodes are promising alternatives to lithium-ion batteries for the large-scale renewable energy storage. However, the lack of high-performance anode material impedes the development of SSIBs. Herein, we report a new type of organic anode material based on azo group for SSIBs. Azobenzene-4,4'-dicarboxylic acid sodium salt is used as a model to investigate the electrochemical behaviors and reaction mechanism of azo compound. It exhibits a reversible capacity of 170 mAh g -1 at 0.2C. When current density is increased to 20C, the reversible capacities of 98 mAh g -1 can be retained for 2000 cycles, demonstrating excellent cycling stability and high rate capability. The detailed characterizations reveal that azo group acts as an electrochemical active site to reversibly bond with Na + . The reversible redox chemistry between azo compound and Na ions offer opportunities for developing long-cycle-life and high-rate SSIBs. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal ion-molecule reactions in oxygen-containing molecules

International Nuclear Information System (INIS)

Kumakura, Minoru

1981-02-01

The energetics of ions and the thermal ion-molecule reactions in oxygen-containing molecules have been studied with a modified time-of-flight mass spectrometer. It was found that the translational energy of ion can be easily obtained from analysis of the decay curve using the time-of-flight mass spectrometer. The condensation-elimination reactions proceeded via cross- and homo-elimination mechanism in which the nature of intermediate-complex could be correlated with the nature of reactant ion. It was elucidated that behavior of poly-atomic oxygen-containing ions on the condensation-elimination reactions is considerably influenced by their oxonium ion structures having functional groups. In addition, the rate constants of the condensation-elimination reactions have affected with the energy state of reactant ion and the dipole moment and/or the polarizability of neutral molecule. It was clarified that the rate constants of the ion-molecule clustering reactions in poly-atomic oxygen-containing molecules such as cyclic ether of six member rings are very large and the cluster ions are stable owing to the large number of vibrational degree of freedom in the cluster ions. (author)

Effects of D-region RF heating studied with the Sodankylä Ion Chemistry model

Directory of Open Access Journals (Sweden)

C.-F. Enell

2005-07-01

Full Text Available The upper mesosphere and lower thermosphere, or ionospheric D region, is an atmospheric layer which is difficult to access experimentally. A useful method that also has a large potential for further studies is artificial heating of electrons by means of powerful radio transmitters. Here we estimate the effect of D-region heating for a few typical cases of high electron density – daylight, typical auroral electron precipitation, and a solar proton event – by coupling a model of RF electron heating to the Sodankylä Ion Chemistry (SIC model. The predicted effects are among others an increase in the ratio of the concentration of negative ions to that of free electrons, and an increase in the absorption of cosmic noise as measured by riometers. For the model runs presented in this paper we have calculated the absorption for the frequency (38.2MHz of the IRIS imaging riometer in Kilpisjärvi, Finland, as observing the ionosphere above the EISCAT Heater in Tromsø, Norway. The predicted enhancements of the absorption are 0.2–0.8dB, an effect which is clearly detectable.

Keywords. Ionosphere (Active experiments; Ion chemistry and composition; Wave propagation

Effects of D-region RF heating studied with the Sodankylä Ion Chemistry model

Directory of Open Access Journals (Sweden)

C.-F. Enell

2005-07-01

Full Text Available The upper mesosphere and lower thermosphere, or ionospheric D region, is an atmospheric layer which is difficult to access experimentally. A useful method that also has a large potential for further studies is artificial heating of electrons by means of powerful radio transmitters. Here we estimate the effect of D-region heating for a few typical cases of high electron density – daylight, typical auroral electron precipitation, and a solar proton event – by coupling a model of RF electron heating to the Sodankylä Ion Chemistry (SIC model. The predicted effects are among others an increase in the ratio of the concentration of negative ions to that of free electrons, and an increase in the absorption of cosmic noise as measured by riometers. For the model runs presented in this paper we have calculated the absorption for the frequency (38.2MHz of the IRIS imaging riometer in Kilpisjärvi, Finland, as observing the ionosphere above the EISCAT Heater in Tromsø, Norway. The predicted enhancements of the absorption are 0.2–0.8dB, an effect which is clearly detectable. Keywords. Ionosphere (Active experiments; Ion chemistry and composition; Wave propagation

Solvent-Free Wittig Reaction: A Green Organic Chemistry Laboratory Experiment

Science.gov (United States)

Leung, Sam H.; Angel, Stephen A.

2004-01-01

Some Wittig reactions can be carried out by grinding the reactants in a mortar with a pestle for about 20 minutes, as per investigation. A laboratory experiment involving a solvent-free Wittig reaction that can be completed in a three-hour sophomore organic chemistry laboratory class period, are developed.

Chemistry of sprite discharges through ion-neutral reactions

Science.gov (United States)

Hiraki, Y.; Kasai, Y.; Fukunishi, H.

2008-07-01

We estimate the concentration changes, caused by streamer discharge in sprites, of ozone and related minor species as odd nitrogen (NOx) and hydrogen (HOx) families in the upper stratosphere and mesosphere. The streamer has an intense electric field and high electron density at its head, where a large number of chemically-radical ions and atoms are produced through electron impact on neutral molecules. After its propagation, densities of minor species can be perturbed through ion-neutral chemical reactions initiated by the relaxation of these radical products. We evaluate the production rates of ions and atoms using an electron kinetics model and by assuming that the electric field and electron density are in the head region. We calculate the density variations mainly for NOx, Ox, and HOx species using a one-dimensional model of the neutral and ion composition of the middle atmosphere, including the effect of the sprite streamer. Results at the nighttime condition show that the densities of NO, O3, H, and OH increase suddenly through reactions triggered by the first atomic nitrogen and oxygen product, and electrons just after streamer initiation. It is shown that NO and NO2 still remain for 1 h by a certain order of increase with their source-sink balance, predominantly around 60 km; for other species, increases in O3, OH, HO2, and H2O2 still remain in the range of 40 70 km. From this affirmative result of long-time behavior previously not presented, we emphasize that sprites would have the power to impact local chemistry at night. We also discuss the consistency with previous theoretical and observational studies, along with future suggestions.

Complex nonlinear behaviour of a fixed bed reactor with reactant recycle

DEFF Research Database (Denmark)

Recke, Bodil; Jørgensen, Sten Bay

1999-01-01

The fixed bed reactor with reactant recycle investigated in this paper can exhibit periodic solutions. These solutions bifurcate from the steady state in a Hopf bifurcation. The Hopf bifurcation encountered at the lowest value of the inlet concentration turns the steady state unstable and marks......,that the dynamic behaviour of a fixed bed reactor with reactant recycle is much more complex than previously reported....

Iminium ion chemistry of mitosene DNA alkylating agents. Enriched 13C NMR and isolation studies.

Science.gov (United States)

Ouyang, A; Skibo, E B

2000-05-16

Described herein is a study of the reductive alkylation chemistry of mitosene antitumor agents. We employed a 13C-enriched electrophilic center to probe the fate of the iminium ion resulting from reductive activation. The 13C-labeled center permitted the identification of complex products resulting from alkylation reactions. In the case of DNA reductive alkylation, the type and number of alkylation sites were readily assessed by 13C NMR. Although there has been much excellent work done in the area of mitosene chemistry and biochemistry, the present study provides a number of new findings: (1) The major fate of the iminium ion is head-to-tail polymerization, even in dilute solutions. (2) Dithionite reductive activation results in the formation of mitosene sulfite esters as well as the previously observed sulfonate adducts. (3) The mitosene iminium ion alkylates the adenosine 6-amino group as well as the guanosine 2-amino group. The identification of the latter adduct was greatly facilitated by the 13C-label at the electrophilic center. (4) The mitosene iminium ion alkylates DNA at both nitrogen and oxygen centers without any apparent base selectivity. The complexity of mitosene reductive alkylation of DNA will require continued adduct isolation studies.

New chemistry of the uranyl ion in non aqueous media

International Nuclear Information System (INIS)

Siffredi, G.

2008-12-01

This work deals with new aspects of the chemistry of the uranyl(VI) ion {UO 2 } 2+ in anhydrous polar organic solvents such as the activation of the reputedly inert U-O yl bond and the controlled reduction of this species which represent a particularly active field of research that attracts much attention for both its fundamental aspects and applications. Treatment of uranyl(VI) compounds UO 2 X' 2 (X' = I, OTf, Cl) with Me 3 SiX (X = Cl, Br, I) reagents, in various anhydrous polar organic solvents, has been first considered. In most cases, reduction into tetravalent species with complete de-oxygenation of the uranyl {UO 2 } 2+ ion is observed. The reaction is particularly efficient in acetonitrile where the tetravalent [UX 4 (MeCN) 4 ] complexes, which are useful precursors in uranium chemistry, are isolated. In the course of these reactions, the influence of the solvent, the nature of X' and X in the UO 2 X' 2 precursor and the Me 3 SiX reagent are pointed out. Reaction of the uranyl(VI) UO 2 X 2 (X = I, Cl, OTf, NO 3 ) precursors with the anionic MC 5 R 5 (M = K, R = H, Me; M= Li, R = Me; M= Tl, R = H) reagents did not lead to the organometallic [(η 5 -C 5 R 5 ) n UO 2 X 2-n ] species (n = 1, 2) but to pentavalent uranyl(V) complexes. This method is a facile and rapid route towards the formation of stable pentavalent uranyl which offers promising sources for further U(V) chemical developments and for fundamental and applied interests. Their structure is strongly dependent on the nature of the solvent, the additional ligands X and of the M + cation. In pyridine, the {UO 2 (py) 5 } + ion appears to be an ubiquitous and a quite stable entity. The coordinating properties of the basic oxo groups, which coordinate easily to M + ions (M= Li, K, Tl), favour structural diversity with formation of hetero-polymetallic complexes such as [{UO 2 (py) 5 }{MX(py) 2 }] (M= Li, X I), [{UO 2 (py) 5 }{MX 2 (py) 2 }] ∞ (M= K, Tl, X= OTf; M= K, X= I), [{UO 2 (py) 5 }(M 2 X 3 )]�

Chemistry of sprite discharges through ion-neutral reactions

Directory of Open Access Journals (Sweden)

Y. Hiraki

2008-07-01

Full Text Available We estimate the concentration changes, caused by streamer discharge in sprites, of ozone and related minor species as odd nitrogen (NO_x and hydrogen (HO_x families in the upper stratosphere and mesosphere. The streamer has an intense electric field and high electron density at its head, where a large number of chemically-radical ions and atoms are produced through electron impact on neutral molecules. After its propagation, densities of minor species can be perturbed through ion-neutral chemical reactions initiated by the relaxation of these radical products. We evaluate the production rates of ions and atoms using an electron kinetics model and by assuming that the electric field and electron density are in the head region. We calculate the density variations mainly for NO_x, O_x, and HO_x species using a one-dimensional model of the neutral and ion composition of the middle atmosphere, including the effect of the sprite streamer. Results at the nighttime condition show that the densities of NO, O₃, H, and OH increase suddenly through reactions triggered by the first atomic nitrogen and oxygen product, and electrons just after streamer initiation. It is shown that NO and NO₂ still remain for 1 h by a certain order of increase with their source-sink balance, predominantly around 60 km; for other species, increases in O₃, OH, HO₂, and H₂O₂ still remain in the range of 40–70 km. From this affirmative result of long-time behavior previously not presented, we emphasize that sprites would have the power to impact local chemistry at night. We also discuss the consistency with previous theoretical and observational studies, along with future suggestions.

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

Science.gov (United States)

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.

Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes

KAUST Repository

Chan, Candace K.; Ruffo, Riccardo; Hong, Seung Sae; Cui, Yi

2009-01-01

Silicon nanowires (SiNWs) have the potential to perform as anodes for lithium-ion batteries with a much higher energy density than graphite. However, there has been little work in understanding the surface chemistry of the solid electrolyte

Interface chemistry of nanostructured materials: ion adsorption on mesoporous alumina.

Science.gov (United States)

Wang, Yifeng; Bryan, Charles; Xu, Huifang; Pohl, Phil; Yang, Yi; Brinker, C Jeffrey

2002-10-01

This paper presents a part of our work on understanding the effect of nanoscale pore space confinement on ion sorption by mesoporous materials. Acid-base titration experiments were performed on both mesoporous alumina and alumina particles under various ionic strengths. The point of zero charge (PZC) for mesoporous alumina was measured to be approximately 9.1, similar to that for nonmesoporous alumina materials, indicating that nanoscale pore space confinement does not have a significant effect on the PZC of pore surfaces. However, for a given pH deviation from the PZC, (pH-PZC), the surface charge per mass on mesoporous alumina was as much as 45 times higher than that on alumina particles. This difference cannot be fully explained by the surface area difference between the two materials. Our titration data have demonstrated that nanoscale confinement has a significant effect, most likely via the overlap of the electric double layer (EDL), on ion sorption onto mesopore surfaces. This effect cannot be adequately modeled by existing surface complexation models, which were developed mostly for an unconfined solid-water interface. Our titration data have also indicated that the rate of ion uptake by mesoporous alumina is relatively slow, probably due to diffusion into mesopores, and complete equilibration for sorption could take 4-5 min. A molecular simulation using a density functional theory was performed to calculate ion adsorption coefficients as a function of pore size. The calculation has shown that as pore size is reduced to nanoscales (<10 nm), the adsorption coefficients of ions can vary by more than two orders of magnitude relative to those for unconfined interfaces. The prediction is supported by our experimental data on Zn sorption onto mesoporous alumina. Owing to their unique surface chemistry, mesoporous materials can potentially be used as effective ion adsorbents for separation processes and environmental cleanup.

Radical Rearrangement Chemistry in Ultraviolet Photodissociation of Iodotyrosine Systems: Insights from Metastable Dissociation, Infrared Ion Spectroscopy, and Reaction Pathway Calculations.

Science.gov (United States)

Ranka, Karnamohit; Zhao, Ning; Yu, Long; Stanton, John F; Polfer, Nicolas C

2018-05-29

We report on the ultraviolet photodissociation (UVPD) chemistry of protonated tyrosine, iodotyrosine, and diiodotyrosine. Distonic loss of the iodine creates a high-energy radical at the aromatic ring that engages in hydrogen/proton rearrangement chemistry. Based on UVPD kinetics measurements, the appearance of this radical is coincident with the UV irradiation pulse (8 ns). Conversely, sequential UVPD product ions exhibit metastable decay on ca. 100 ns timescales. Infrared ion spectroscopy is capable of confirming putative structures of the rearrangement products as proton transfers from the imine and β-carbon hydrogens. Potential energy surfaces for the various reaction pathways indicate that the rearrangement chemistry is highly complex, compatible with a cascade of rearrangements, and that there is no preferred rearrangement pathway even in small molecular systems like these. Graphical Abstract.

From hot atom chemistry to epithermal chemistry

International Nuclear Information System (INIS)

Roessler, K.

2004-01-01

The rise and fall of hot atom chemistry (HAC) over the years from 1934 to 2004 is reviewed. Several applications are discussed, in particular to astrophysics and the interaction of energetic ions and atoms in space. Epithermal chemistry (ETC) is proposed to substitute the old name, since it better fits the energy range as well as the non-thermal and non-equilibrium character of the reactions. ETC also avoids the strong connexion of HAC to nuclear chemistry and stands for the opening of the field to physical chemistry and astrophysics. (orig.)

Mass spectrometry. [in organic chemistry

Science.gov (United States)

Burlingame, A. L.; Shackleton, C. H. L.; Howe, I.; Chizhov, O. S.

1978-01-01

A review of mass spectrometry in organic chemistry is given, dealing with advances in instrumentation and computer techniques, selected topics in gas-phase ion chemistry, and applications in such fields as biomedicine, natural-product studies, and environmental pollution analysis. Innovative techniques and instrumentation are discussed, along with chromatographic-mass spectrometric on-line computer techniques, mass spectral interpretation and management techniques, and such topics in gas-phase ion chemistry as electron-impact ionization and decomposition, photoionization, field ionization and desorption, high-pressure mass spectrometry, ion cyclotron resonance, and isomerization reactions of organic ions. Applications of mass spectrometry are examined with respect to bio-oligomers and their constituents, biomedically important substances, microbiology, environmental organic analysis, and organic geochemistry.

Derivatization chemistry of the double-decker dicobalt sandwich ion targeted to design biologically active substances

Czech Academy of Sciences Publication Activity Database

Grüner, Bohumír; Švec, Petr; Hájková, Zuzana; Císařová, I.; Pokorná, Jana; Konvalinka, Jan

2012-01-01

Roč. 84, č. 11 (2012), s. 2243-2262 ISSN 0033-4545 R&D Projects: GA AV ČR IAAX00320901 Institutional support: RVO:61388980 ; RVO:61388963 Keywords : AIDS treatment * boranes * canastide ion * carboranes * dicarbollides * HIV -protease Subject RIV: CA - Inorganic Chemistry Impact factor: 3.386, year: 2012

SIFT-MS quantification of several breath biomarkers of inflammatory bowel disease, IBD: A detailed study of the ion chemistry

Czech Academy of Sciences Publication Activity Database

Brůhová Michalčíková, R.; Dryahina, Kseniya; Španěl, Patrik

2016-01-01

Roč. 396, FEB 2016 (2016), s. 35-41 ISSN 1387-3806 R&D Projects: GA ČR GA13-28882S Institutional support: RVO:61388955 Keywords : Selected ion flow tube mass spectrometry * Ion molecule reactions * Three body association Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.702, year: 2016

Gas-phase reaction rate constants for atmospheric pressure ionization in ion-mobility spectrometry

International Nuclear Information System (INIS)

Vandiver, V.J.

1987-01-01

Ion-mobility spectrometry (IMS) is an instrumental technique in which gaseous ions are formed from neutral molecules by proton and charge transfer from reactant ions through collisional ionization. An abbreviated rate theory has been proposed for atmospheric pressure ionization (API) in IMS, but supporting experimental measurements have not been reported. The objectives of this thesis were (1) assessment of existing API rate theory using positive and negative product ions in IMS, (2) measurement of API equilibria and kinetics for binary mixtures, and (3) investigating of cross-ionizations with multiple-product ions in API reactions. Although IMS measurements and predictions from rate theory were comparable, shapes and slopes of response curves for both proton transfer and electron capture were not described exactly by existing theory. In particular, terms that are needed for calculation of absolute rate constants were unsuitable in the existing theory. These included recombination coefficients,initial number of reactant ions, and opposing ion densities

Low temperature synthesis of Mo2C/W2C superlattices via ultra-thin modulated reactants

International Nuclear Information System (INIS)

Johnson, C.D.; Johnson, D.C.

1996-01-01

The authors report here a synthesis method of preparing carbide superlattices using ultra-thin modulated reactants. Initial investigations into the synthesis of the binary systems, Mo 2 C and W 2 C using ultra-thin modulated reactants revealed that both can be formed at relatively low temperatures (500 and 600 C respectively). DSC and XRD data suggested a two step reaction pathway involving interdiffusion of the initial modulated reactant followed by crystallization of the final product, if the modulation length is on the order of 10 angstrom. This information was used to form Mo 2 C/W 2 C superlattices using the structure of the ultra-thin modulated reactant to control the final superlattice period. Relatively large superlattice modulations were kinetically trapped by having several repeat units of each binary within the total repeat of the initial reactant. DSC and XRD data again are consistent with a two step reaction pathway leading to the formation of carbide superlattices

A SIFT study of the reactions of H2ONO+ ions with several types of organic molecules

Science.gov (United States)

Smith, David; Wang, Tianshu; Spanel, Patrik

2003-11-01

A selected ion flow tube (SIFT) study has been carried out of the reactions of hydrated nitrosonium ions, NO+H2O, which theory has equated to protonated nitrous acid ions, H2ONO+. One objective of this study was to investigate if this ion exhibits the properties of both a cluster ion and a protonated acid in their reactions with a variety of organic molecules. The chosen reactant molecules comprise two each of the following types--amines, terpenes, aromatic hydrocarbons, esters, carboxylic acids, ketones, aldehydes and alcohols. The reactant H2ONO+ (NO+H2O) ions are formed in a discharge ion source and injected into helium carrier gas where they are partially vibrationally excited and partially dissociated to NO+ ions. Hence, the reactions of the H2ONO+ ions had to be studies simultaneously with NO+ ions, the reactions of the latter ions readily being studied by selectively injecting NO+ ions into the carrier gas. The results of this study indicate that the H2ONO+ ions undergo a wide variety of reaction processes that depend on the properties of the reactant molecules such as their ionisation energies and proton affinities. These processes include charge transfer with compounds, M, that have low ionisation energies (producing M+), proton transfer with compounds possessing large proton affinities (MH+), hydride ion transfer (M---H+), alkyl radical (M---R+), alkoxide radical transfer (M---OR+), ion-molecule association (NO+H2OM) and ligand switching (NO+M), producing the ions given in parentheses.

Green chemistry by nano-catalysis

KAUST Repository

Polshettiwar, Vivek

2010-01-01

Nano-materials are important in many diverse areas, from basic research to various applications in electronics, biochemical sensors, catalysis and energy. They have emerged as sustainable alternatives to conventional materials, as robust high surface area heterogeneous catalysts and catalyst supports. The nano-sized particles increase the exposed surface area of the active component of the catalyst, thereby enhancing the contact between reactants and catalyst dramatically and mimicking the homogeneous catalysts. This review focuses on the use of nano-catalysis for green chemistry development including the strategy of using microwave heating with nano-catalysis in benign aqueous reaction media which offers an extraordinary synergistic effect with greater potential than these three components in isolation. To illustrate the proof-of-concept of this "green and sustainable" approach, representative examples are discussed in this article. © 2010 The Royal Society of Chemistry.

GAS-PHASE CHEMISTRY OF THE CYANATE ION, OCN{sup −}

Energy Technology Data Exchange (ETDEWEB)

Cole, Callie A.; Wang, Zhe-Chen; Bierbaum, Veronica M. [Department of Chemistry and Biochemistry, 215 UCB, University of Colorado, Boulder, CO 80309 (United States); Snow, Theodore P. [Center for Astrophysics and Space Astronomy, 389 UCB, University of Colorado, Boulder, CO 80309 (United States)

2015-10-10

Cyanate (OCN{sup −}) is the only ion to date whose presence has been confirmed in the icy mantles that coat interstellar dust grains. Understanding the chemical behavior of cyanate at a fundamental level is therefore integral to the advancement of astrochemistry. We seek to unravel the chemistry of this intriguing anion through a combination of gas-phase experiments and theoretical explorations. Our approach is twofold: first, employing a flowing afterglow-selected ion flow tube apparatus, the reactions between OCN{sup −} and three of the most abundant atomic species in the interstellar medium, hydrogen, nitrogen, and oxygen, are examined. Hydrogen atoms readily react by associative detachment, but the remarkable stability of OCN{sup −} does not give rise to an observable reaction with either nitrogen or oxygen atoms. To explain these results, the potential energy surfaces of several reactions are investigated at the B3LYP/6-311++G(d,p) level of theory. Second, collision induced dissociation experiments involving deprotonated uracil, thymine, and cytosine in an ion trap mass spectrometer reveal an interesting connection between these pyrimidine nucleobase anions and OCN{sup −}. Theoretical calculations at the B3LYP/6-311++G(d,p) level of theory are performed to delineate the mechanisms of dissociation and explore the possible role of OCN{sup −} as a biomolecule precursor.

A rechargeable iodine-carbon battery that exploits ion intercalation and iodine redox chemistry.

Science.gov (United States)

Lu, Ke; Hu, Ziyu; Ma, Jizhen; Ma, Houyi; Dai, Liming; Zhang, Jintao

2017-09-13

Graphitic carbons have been used as conductive supports for developing rechargeable batteries. However, the classic ion intercalation in graphitic carbon has yet to be coupled with extrinsic redox reactions to develop rechargeable batteries. Herein, we demonstrate the preparation of a free-standing, flexible nitrogen and phosphorus co-doped hierarchically porous graphitic carbon for iodine loading by pyrolysis of polyaniline coated cellulose wiper. We find that heteroatoms could provide additional defect sites for encapsulating iodine while the porous carbon skeleton facilitates redox reactions of iodine and ion intercalation. The combination of ion intercalation with redox reactions of iodine allows for developing rechargeable iodine-carbon batteries free from the unsafe lithium/sodium metals, and hence eliminates the long-standing safety issue. The unique architecture of the hierarchically porous graphitic carbon with heteroatom doping not only provides suitable spaces for both iodine encapsulation and cation intercalation but also generates efficient electronic and ionic transport pathways, thus leading to enhanced performance.Carbon-based electrodes able to intercalate Li + and Na + ions have been exploited for high performing energy storage devices. Here, the authors combine the ion intercalation properties of porous graphitic carbons with the redox chemistry of iodine to produce iodine-carbon batteries with high reversible capacities.

Synthesis of new thermoelectrics using modulated elemental reactants

Energy Technology Data Exchange (ETDEWEB)

Hornbostel, M D; Sellinschegg, H; Johnson, D C

1997-07-01

A series of new, metastable ternary crystalline compounds with the skutterudite crystal structure have been synthesized using modulated elemental reactants. The initial reactants are made up of multiple repeats of a {approximately}25 {angstrom} thick unit containing elemental layers of the desired ternary metal, iron and antimony. Low temperature annealing (150 C) results in interdiffusion of the elemental layers to form amorphous reaction intermediates. Annealing these intermediates at temperatures between 200 C and 250 C results in exothermic crystallization of the desired skutterudite crystal structure. Most of the new compounds prepared are only kinetically stable, decomposing exothermically to form thermodynamically more stable mixtures of binary compounds and elements. Low angle x-ray diffraction studies show that the resulting films are exceedingly smooth. These films have an ideal geometry for measuring properties of importance for thermoelectric devices--the Seebeck coefficient and the electrical conductivity. Thermal conductivity can be measured using a modification of the 3{omega} technique of Cahill. Samples can be produced rapidly, allowing for systematic screening and subsequent optimization as a function of composition and doping levels.

Application of Ion Mobility Spectrometry (IMS) in forensic chemistry and toxicology with focus on biological matrices

Science.gov (United States)

Bernhard, Werner; Keller, Thomas; Regenscheit, Priska

1995-01-01

The IMS (Ion Mobility Spectroscopy) instrument 'Ionscan' takes advantage of the fact that trace quantities of illicit drugs are adsorbed on dust particles on clothes, in cars and on other items of evidence. The dust particles are collected on a membrane filter by a special attachment on a vacuum cleaner. The sample is then directly inserted into the spectrometer and can be analyzed immediately. We show casework applications of a forensic chemistry and toxicology laboratory. One new application of IMS in forensic chemistry is the detection of psilocybin in dried mushrooms without any further sample preparation.

On the mechanism of effective chemical reactions with turbulent mixing of reactants and finite rate of molecular reactions

Energy Technology Data Exchange (ETDEWEB)

Vorotilin, V. P., E-mail: VPVorotilin@yandex.ru [Russian Academy of Sciences, Institute of Applied Mechanics (Russian Federation)

2017-01-15

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

Ions and light

CERN Document Server

Bowers, Michael T

2013-01-01

Gas Phase Ion Chemistry, Volume 3: Ions and Light discusses how ions are formed by electron impact, ion-molecule reactions, or electrical discharge. This book discusses the use of light emitted by excited molecules to characterize either the chemistry that formed the excited ion, the structure of the excited ion, or both.Organized into 10 chapters, this volume begins with an overview of the extension of the classical flowing afterglow technique to include infrared and chemiluminescence and laser-induced fluorescence detection. This text then examines the experiments involving molecules that ar

Heavy ion fusion- Using heavy ions to make electricity

International Nuclear Information System (INIS)

Celata, C.M.

2004-01-01

The idea of using nuclear fusion as a source of commercial electrical power has been pursued worldwide since the 1950s. Two approaches, using magnetic and inertial confinement of the reactants, are under study. This paper describes the difference between the two approaches, and discusses in more detail the heavy-ion-driven inertial fusion concept. A multibeam induction linear accelerator would be used to bring ∼100 heavy ion beams to a few GeV. The beams would then heat and compress a target of solid D-T. This approach is unique among fusion concepts in its ability to protect the reaction chamber wall from neutrons and debris

Role of the H bond network in the radiation chemistry of hydrated systems

International Nuclear Information System (INIS)

Pommeret, S.; Renault, J.P.; Caeer, S.Le; Vigneron, G.; Vuilleumier, R.; Bratos, S.; Leicknam, J.Cl.

2006-01-01

In the present contribution a review of the recent work on the H bond dynamics, in absence of any reactant and a new theory that unambiguously establishes a new link between spectroscopic observation and geometric properties is presented, along with results on the radiation chemistry of nanoporous media and its influence on the H bond network of an interface

Atom-at-a-time chemistry

International Nuclear Information System (INIS)

Nagame, Yuichiro

2009-01-01

Several techniques of the analytical chemistry in 'Atom-at-a-time chemistry' for transactinide elements have been developed. In this report a representative example in these techniques is introduced with the results. The contents are the single-atom chemistry, the chemical experiments on transactinide elements, liquid phase chemistry (the ion exchange behavior of Rutherfordium), gas phase chemistry (the chemistry of atomic No.112 element), and future development. (M.H.)

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

Science.gov (United States)

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

2014-01-01

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

ON THE CHEMISTRY OF HYDRIDES OF N ATOMS AND O{sup +} IONS

Energy Technology Data Exchange (ETDEWEB)

Awad, Zainab [Astronomy, Space Science, and Meteorology Department, Faculty of Science, Cairo University, Giza (Egypt); Viti, Serena; Williams, David A., E-mail: zma@sci.cu.edu.eg [Physics and Astronomy Department, University College London, Gower Street, London WC1E 6BT (United Kingdom)

2016-08-01

Previous work by various authors has suggested that the detection by Herschel /HIFI of nitrogen hydrides along the low-density lines of sight toward G10.6-0.4 (W31C) cannot be accounted for by gas-phase chemical models. In this paper we investigate the role of surface reactions on dust grains in diffuse regions, and we find that formation of the hydrides by surface reactions on dust grains with efficiency comparable to that for H{sub 2} formation reconciles models with observations of nitrogen hydrides. However, similar surface reactions do not contribute significantly to the hydrides of O{sup +} ions detected by Herschel /HIFI that are present along many sight lines in the Galaxy. The O{sup +} hydrides can be accounted for by conventional gas-phase chemistry either in diffuse clouds of very low density with normal cosmic-ray fluxes or in somewhat denser diffuse clouds with high cosmic-ray fluxes. Hydride chemistry in dense dark clouds appears to be dominated by gas-phase ion–molecule reactions.

Effect of surface chemistries and characteristics of Ti6Al4V on the Ca and P adsorption and ion dissolution in Hank's ethylene diamine tetra-acetic acid solution.

Science.gov (United States)

Chang, E; Lee, T M

2002-07-01

This study examined the influence of chemistries and surface characteristics of Ti6Al4V on the adsorption of Ca and P species and ion dissolution behavior of the material exposed in Hank's solution with 8.0 mM ethylene diamine tetra-acetic acid at 37 degrees C. The variation of chemistries of the alloy and nano-surface characteristics (chemistries of nano-surface oxides, amphoteric OH group adsorbed on oxides, and oxide thickness) was effected by surface modification and three passivation methods (34% nitric acid passivation. 400 degrees C heated in air, and aged in 100 degrees C water). X-ray photoelectron spectroscopy and Auger electron spectroscopy were used for surface analyses. The chemistries of nano-surface oxides in a range studied should not change the capability of Ca and P adsorption. Nor is the capability affected significantly by amphoteric OH group and oxide thickness. However, passivations influence the surface oxide thickness and the early stage ion dissolution rate of the alloy. The rate-limiting step of the rate can be best explained by metal-ion transport through the oxide film, rather than hydrolysis of the film. Variation of the chemistries of titanium alloy alters the electromotive force potential of the metal, thereby affecting the corrosion and ion dissolution rate.

The effects of combined therapy of rheumatoid arthritis on the acute phase reactants.

Science.gov (United States)

Rexhepi, Sylejman; Rexhepi, Mjellma; Sahatçiu-Meka, Vjollca; Pllana, Ejup; Dragusha, Gani; Gashi, Masar; Rexhepi, Blerta

2009-01-01

The paper presents the results of studies of acute phase reactants in the 60 treated patients with rheumatoid arthritis. Patients were divided into two groups, depending on the applied treatment: group I (n = 30) was treated with methotrexate, sulfasalazine and hydroxychloroquine, and group II (n = 30) with methotrexate. The results of our study shows that there is a statistically significant reduction in the value of acute phase reactants and clinical parameters after treatment in both investigated groups of patients, and also a significant statistical difference between the first and second group of treated patients.

F- and H-Area Seepage Basins Water Treatment System Process Optimization and Alternative Chemistry Ion Exchange/Sorbent Material Screening Clearwell Overflow Study

Energy Technology Data Exchange (ETDEWEB)

Serkiz, S.M.

2000-08-30

This study investigated alternative ion exchange/sorbent materials and polishing chemistries designed to remove specific radionuclides not removed during the neutralization/precipitation/clarification process.

The behavior of exciplex decay processes and interplay of radiationless transition and preliminary reorganization mechanisms of electron transfer in loose and tight pairs of reactants.

Science.gov (United States)

Kuzmin, Michael G; Soboleva, Irina V; Dolotova, Elena V

2007-01-18

Exciplex emission spectra and rate constants of their decay via internal conversion and intersystem crossing are studied and discussed in terms of conventional radiationless transition approach. Exciplexes of 9-cyanophenanthrene with 1,2,3-trimethoxybenzene and 1,3,5-trimethoxybenzene were studied in heptane, toluene, butyl acetate, dichloromethane, butyronitrile, and acetonitrile. A better description of spectra and rate constants is obtained using 0-0 transition energy and Gauss broadening of vibrational bands rather than the free energy of electron transfer and reorganization energy. The coincidence of parameters describing exciplex emission spectra and dependence of exciplex decay rate constants on energy gap gives the evidence of radiationless quantum transition mechanism rather than thermally activated medium reorganization mechanism of charge recombination in exciplexes and excited charge transfer complexes (contact radical ion pairs) as well as in solvent separated radical ion pairs. Radiationless quantum transition mechanism is shown to provide an appropriate description also for the main features of exergonic excited-state charge separation reactions if fast mutual transformations of loose and tight pairs of reactants are considered. In particular, very fast electron transfer (ET) in tight pairs of reactants with strong electronic coupling of locally excited and charge transfer states can prevent the observation of an inverted region in bimolecular excited-state charge separation even for highly exergonic reactions.

Reactions of POxCly- ions with O2(a 1[Delta]g), H2O, and Cl2 at 298 K

Science.gov (United States)

Midey, Anthony J.; Dotan, Itzhak; Viggiano, A. A.

2008-06-01

The rate constants and product branching ratios for the reactions of phosphorus oxychloride anions, POxCly- for x = 1-2 and y = 1-3, with O2(a 1[Delta]g), Cl2, and H2O have been measured in a selected ion flow tube (SIFT) at 298 K. A mixture of O2(a 1[Delta]g) in O2 has been produced using a recently designed chemical singlet oxygen generator (sparger) with an emission detection scheme adopted previously in our laboratory. The experiments continue a series of investigations into the oxidation reactions of POxCly- ions, searching for pathways to the terminal PO2- and PO3- ions observed in combustion chemistry with POCl3 present. None of the POxCly- ions react with H2O or O2(a 1[Delta]g). The O2(a 1[Delta]g) rate constants have a limit of <1 × 10-11 cm3 s-1, except for PO2Cl- where a limit of <5 × 10-11 cm3 s-1 has been determined. The H2O rate constants have limits of <1 × 10-11 cm3 s-1. All of the POxCly- ions react with Cl2, excluding PO3- and PO2Cl2-. Depending on the reactant ion, Cl-, Cl2- or PO2Cl2- product ions form.

Homogeneous Media Milling: Reactant-Assisted Mechanochemical Synthesis of Functionalized Nanoparticles from Malleable and Ductile Metals

Science.gov (United States)

2014-01-01

equipped with valves ( McMaster -Carr part number 4912K96) that serve several purposes. The jars are loaded and sealed inside a N2-filled glove box...Temperature and Solvent Effects on Viscosity B Coefficients . Monovalent Ions in Acetonitrile at 15, 25, and 35 °C. Journal of Physical Chemistry 1990, 94

DOE fundamentals handbook: Chemistry

International Nuclear Information System (INIS)

1993-01-01

This handbook was developed to assist nuclear facility operating contractors in providing operators, maintenance personnel, and the technical staff with the necessary fundamentals training to ensure a basic understanding of chemistry. This volume contains the following modules: reactor water chemistry (effects of radiation on water chemistry, chemistry parameters), principles of water treatment (purpose; treatment processes [ion exchange]; dissolved gases, suspended solids, and pH control; water purity), and hazards of chemicals and gases (corrosives [acids, alkalies], toxic compounds, compressed gases, flammable/combustible liquids)

Molecular beam studies of ion-molecule reactions

International Nuclear Information System (INIS)

Gentry, W.R.

1978-01-01

A review is presented in which an attempt is made to highlight some of the areas in which molecular beam techniques contribute to the understanding of ion--molecule reaction dynamics. Included are reactant kinetic energy range and resolution, internal state selection and analysis, and new chemical systems and phenomena. 35 references

Uncertainty quantification of ion chemistry in lean and stoichiometric homogenous mixtures of methane, oxygen, and argon

KAUST Repository

Kim, Daesang

2015-07-01

Uncertainty quantification (UQ) methods are implemented to obtain a quantitative characterization of the evolution of electrons and ions during the ignition of methane-oxygen mixtures under lean and stoichiometric conditions. The GRI-Mech 3.0 mechanism is combined with an extensive set of ion chemistry pathways and the forward propagation of uncertainty from model parameters to observables is performed using response surfaces. The UQ analysis considers 22 uncertain rate parameters, which include both chemi-ionization, proton transfer, and electron attachment reactions as well as neutral reactions pertaining to the chemistry of the CH radical. The uncertainty ranges for each rate parameter are discussed. Our results indicate that the uncertainty in the time evolution of the electron number density is due mostly to the chemi-ionization reaction CH+O⇌HCO+ +E- and to the main CH consumption reaction CH+O2 ⇌O+HCO. Similar conclusions hold for the hydronium ion H3O+, since electrons and H3O+ account for more than 99% of the total negative and positive charge density, respectively. Surprisingly, the statistics of the number density of charged species show very little sensitivity to the uncertainty in the rate of the recombination reaction H3O+ +E- →products, until very late in the decay process, when the electron number density has fallen below 20% of its peak value. Finally, uncertainties in the secondary reactions within networks leading to the formation of minor ions (e.g., C2H3O+, HCO+, OH-, and O-) do not play any role in controlling the mean and variance of electrons and H3O+, but do affect the statistics of the minor ions significantly. The observed trends point to the role of key neutral reactions in controlling the mean and variance of the charged species number density in an indirect fashion. Furthermore, total sensitivity indices provide quantitative metrics to focus future efforts aiming at improving the rates of key reactions responsible for the

Uncertainty quantification of ion chemistry in lean and stoichiometric homogenous mixtures of methane, oxygen, and argon

KAUST Repository

Kim, Daesang; Rizzi, Francesco; Cheng, Kwok Wah; Han, Jie; Bisetti, Fabrizio; Knio, Omar Mohamad

2015-01-01

Uncertainty quantification (UQ) methods are implemented to obtain a quantitative characterization of the evolution of electrons and ions during the ignition of methane-oxygen mixtures under lean and stoichiometric conditions. The GRI-Mech 3.0 mechanism is combined with an extensive set of ion chemistry pathways and the forward propagation of uncertainty from model parameters to observables is performed using response surfaces. The UQ analysis considers 22 uncertain rate parameters, which include both chemi-ionization, proton transfer, and electron attachment reactions as well as neutral reactions pertaining to the chemistry of the CH radical. The uncertainty ranges for each rate parameter are discussed. Our results indicate that the uncertainty in the time evolution of the electron number density is due mostly to the chemi-ionization reaction CH+O⇌HCO+ +E- and to the main CH consumption reaction CH+O2 ⇌O+HCO. Similar conclusions hold for the hydronium ion H3O+, since electrons and H3O+ account for more than 99% of the total negative and positive charge density, respectively. Surprisingly, the statistics of the number density of charged species show very little sensitivity to the uncertainty in the rate of the recombination reaction H3O+ +E- →products, until very late in the decay process, when the electron number density has fallen below 20% of its peak value. Finally, uncertainties in the secondary reactions within networks leading to the formation of minor ions (e.g., C2H3O+, HCO+, OH-, and O-) do not play any role in controlling the mean and variance of electrons and H3O+, but do affect the statistics of the minor ions significantly. The observed trends point to the role of key neutral reactions in controlling the mean and variance of the charged species number density in an indirect fashion. Furthermore, total sensitivity indices provide quantitative metrics to focus future efforts aiming at improving the rates of key reactions responsible for the

Acute-phase reactants in periodontal disease: current concepts and future implications.

Science.gov (United States)

Archana, Vilasan; Ambili, Ranjith; Nisha, Krishnavilasam Jayakumary; Seba, Abraham; Preeja, Chandran

2015-05-01

Periodontal disease has been linked to adverse cardiovascular events by unknown mechanisms. C-reactive protein is a systemic marker released during the acute phase of an inflammatory response and is a prognostic marker for cardiovascular disease, with elevated serum levels being reported during periodontal disease. Studies also reported elevated levels of various other acute-phase reactants in periodontal disease. It has been reported extensively in the literature that treatment of periodontal infections can significantly lower serum levels of C-reactive protein. Therefore, an understanding of the relationship between acute-phase response and the progression of periodontal disease and other systemic health complications would have a profound effect on the periodontal treatment strategies. In view of this fact, the present review highlights an overview of acute-phase reactants and their role in periodontal disease. © 2014 Wiley Publishing Asia Pty Ltd.

Organic chemistry of graphene: the Diels-Alder reaction.

Science.gov (United States)

Denis, Pablo A

2013-11-11

Herein, by using dispersion-corrected density functional theory, we investigated the Diels-Alder chemistry of pristine and defective graphene. Three dienes were considered, namely 2,3-dimethoxy-1,3-butadiene (DMBD), 9-methylanthracene (9MA), and 9,10-dimethylanthracene (910DMA). The dienophiles that were assayed were tetracyanoethylene (TCNE) and maleic anhydride (MA). When pristine graphene acted as the dienophile, we found that the cycloaddition products were 47-63 kcal mol(-1) less stable than the reactants, thus making the reaction very difficult. The presence of Stone-Wales translocations, 585 double vacancies, or 555-777 reconstructed double vacancies did not significantly improve the reactivity because the cycloaddition products were still located at higher energy than the reactants. However, for the addition of 910DMA to single vacancies, the product showed comparable stability to the separated reactants, whereas for unsaturated armchair edges the reaction was extremely favorable. With regards the reactions with dienophiles, for TCNE, the cycloaddition product was metastable. In the case of MA, we observed a reaction product that was less stable than the reactants by 50 kcal mol(-1) . For the reactions between graphene as a diene and the dienophiles, we found that the most-promising defects were single vacancies and unsaturated armchair edges, because the other three defects were much-less reactive. Thus, we conclude that the reactions with these above-mentioned dienes may proceed on pristine or defective sheets with heating, despite being endergonic. The same statement also applies to the dienophile maleic anhydride. However, for TCNE, the reaction is only likely to occur onto single vacancies or unsaturated armchair edges. We conclude that the dienophile character of graphene is slightly stronger than its behavior as a diene. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion measurements in premixed methane-oxygen flames

KAUST Repository

Alquaity, Awad

2014-07-25

Ions are formed as a result of chemi-ionization processes in combustion systems. Recently, there has been an increasing interest in understanding flame ion chemistry due to the possible application of external electric fields to reduce emissions and improve combustion efficiency by active control of combustion process. In order to predict the effect of external electric fields on combustion plasma, it is critical to gain a good understanding of the flame ion chemistry. In this work, a Molecular Beam Mass Spectrometer (MBMS) is utilized to measure ion concentration profiles in premixed methane-oxygen-argon burner-stabilized flames. Lean, stoichiometric and rich flames at atmospheric pressure are used to study the dependence of ion chemistry on equivalence ratio of premixed flames. The relative ion concentration profiles are compared qualitatively with previous methane-oxygen studies and show good agreement. The relative ion concentration data obtained in the present study can be used to validate and improve ion chemistry models for methane-oxygen flames.

Synchrotron-based XPS studies of AlGaN and GaN surface chemistry and its relationship to ion sensor behaviour

Energy Technology Data Exchange (ETDEWEB)

Khir, Farah Liyana Muhammad, E-mail: 21001899@student.uwa.edu.au [School of Electrical, Electronic and Computer Engineering, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia); Myers, Matthew, E-mail: Matt.Myers@csiro.au [School of Chemistry and Biochemistry, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia); CSIRO Earth Science and Resource Engineering, Kensington, Western Australia 6151 (Australia); Podolska, Anna [School of Electrical, Electronic and Computer Engineering, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia); Department of Exploration Geophysics, Curtin University of Technology, 26 Dick Perry Avenue, ARRC, Kensington, Western Australia 6151 (Australia); Sanders, Tarun Maruthi [School of Electrical, Electronic and Computer Engineering, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia); Baker, Murray V., E-mail: murray.baker@uwa.edu.au [School of Chemistry and Biochemistry, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia); Nener, Brett D., E-mail: brett.nener@uwa.edu.au [School of Electrical, Electronic and Computer Engineering, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia); Parish, Giacinta, E-mail: giacinta.parish@uwa.edu.au [School of Electrical, Electronic and Computer Engineering, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia)

2014-09-30

Highlights: • Soft X-ray was used to study the surface chemistry of GaN and AlGaN. • The surface chemistry and sensor behaviour were investigated. • The oxide of aluminum is significantly more reactive than gallium. • The Cl{sup −} ions are greater in GaN samples compared to AlGaN samples. - Abstract: Soft X-ray photoelectron spectroscopy was used to investigate the fundamental surface chemistry of both AlGaN and GaN surfaces in the context of understanding the behaviour of AlGaN/GaN heterostructures as chemical field-effect transistor (CHEMFET) ion sensors. AlGaN and GaN samples were subjected to different methods of oxide growth (native oxide and thermally grown oxide) and chemical treatment conditions. Our investigations indicate that the etching of the oxide layer is more pronounced with AlGaN compared to GaN. Also, we observed that chloride ions have a greater tendency to attach to the GaN surface relative to the AlGaN surface. Furthermore, chloride ions are comparatively more prevalent on surfaces treated with 5% HCl acid solution. The concentration of chloride ions is even higher on the HCl treated native oxide surface resulting in a very clear deconvolution of the Cl 2p{sub 1/2} and Cl 2p{sub 3/2} peaks. For GaN and AlGaN surfaces, a linear response (e.g. source-drain current) is typically seen with variation in pH of buffered solutions with constant reference electrode voltage at the surface gate; however, an inverted bath-tub type response (e.g. a maximum at neutral pH and lower values at pH values away from neutral) and a general tendency to negative charge selectivity has been also widely reported. We have shown that our XPS investigations are consistent with the different sensor response reported in the literature for these CHEMFET devices and may help to explain the differing response of these materials.

Advances in quantum chemistry

CERN Document Server

Sabin, John R

2013-01-01

Advances in Quantum Chemistry presents surveys of current topics in this rapidly developing field that has emerged at the cross section of the historically established areas of mathematics, physics, chemistry, and biology. It features detailed reviews written by leading international researchers. This volume focuses on the theory of heavy ion physics in medicine.Advances in Quantum Chemistry presents surveys of current topics in this rapidly developing field that has emerged at the cross section of the historically established areas of mathematics, physics, chemistry, and biology. It features

Bioorthogonal chemistry: strategies and recent development

Science.gov (United States)

Ramil, Carlo P.; Lin, Qing

2013-01-01

The use of covalent chemistry to track biomolecules in their native environment—a focus of bioorthogonal chemistry—has received considerable interests recently among chemical biologists and organic chemists alike. To facilitate wider adoption of bioorthogonal chemistry in biomedical research, a central effort in the last few years has been focused on the optimization of a few known bioorthogonal reactions, particularly with respective to reaction kinetics improvement, novel genetic encoding systems, and fluorogenic reactions for bioimaging. During these optimizations, three strategies have emerged, including the use of ring strain for substrate activation in the cycloaddition reactions, the discovery of new ligands and privileged substrates for accelerated metal-catalysed reactions, and the design of substrates with pre-fluorophore structures for rapid “turn-on” fluorescence after selective bioorthogonal reactions. In addition, new bioorthogonal reactions based on either modified or completely unprecedented reactant pairs have been reported. Finally, increasing attention has been directed toward the development of mutually exclusive bioorthogonal reactions and their applications in multiple labeling of a biomolecule in cell culture. In this feature article, we wish to present the recent progress in bioorthogonal reactions through the selected examples that highlight the above-mentioned strategies. Considering increasing sophistication in bioorthogonal chemistry development, we strive to project several exciting opportunities where bioorthogonal chemistry can make a unique contribution to biology in near future. PMID:24145483

Modeling of the reactant conversion rate in a turbulent shear flow

Science.gov (United States)

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

1992-01-01

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

Spatial atomic layer deposition for coating flexible porous Li-ion battery electrodes

Energy Technology Data Exchange (ETDEWEB)

Yersak, Alexander S.; Sharma, Kashish; Wallas, Jasmine M.; Dameron, Arrelaine A.; Li, Xuemin; Yang, Yongan; Hurst, Katherine E.; Ban, Chunmei; Tenent, Robert C.; George, Steven M. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309 and Department of Mechanical Engineering, University of Colorado, Boulder, Colorado 80309

2018-01-01

Ultrathin atomic layer deposition (ALD) coatings on the electrodes of Li-ion batteries can enhance the capacity stability of the Li-ion batteries. To commercialize ALD for Li-ion battery production, spatial ALD is needed to decrease coating times and provide a coating process compatible with continuous roll-to-roll (R2R) processing. The porous electrodes of Li-ion batteries provide a special challenge because higher reactant exposures are needed for spatial ALD in porous substrates. This work utilized a modular rotating cylinder spatial ALD reactor operating at rotation speeds up to 200 revolutions/min (RPM) and substrate speeds up to 200 m/min. The conditions for spatial ALD were adjusted to coat flexible porous substrates. The reactor was initially used to characterize spatial Al2O3 and ZnO ALD on flat, flexible metalized polyethylene terephthalate foils. These studies showed that slower rotation speeds and spacers between the precursor module and the two adjacent pumping modules could significantly increase the reactant exposure. The modular rotating cylinder reactor was then used to coat flexible, model porous anodic aluminum oxide (AAO) membranes. The uniformity of the ZnO ALD coatings on the porous AAO membranes was dependent on the aspect ratio of the pores and the reactant exposures. Larger reactant exposures led to better uniformity in the pores with higher aspect ratios. The reactant exposures were increased by adding spacers between the precursor module and the two adjacent pumping modules. The modular rotating cylinder reactor was also employed for Al2O3 ALD on porous LiCoO2 (LCO) battery electrodes. Uniform Al coverages were obtained using spacers between the precursor module and the two adjacent pumping modules at rotation speeds of 25 and 50 RPM. The LCO electrodes had a thickness of ~49 um and pores with aspect ratios of ~12-25. Coin cells were then constructed using the ALD-coated LCO electrodes and were tested to determine their battery

The Quantitative Resolution of a Mixture of Group II Metal Ions by Thermometric Titration with EDTA. An Analytical Chemistry Experiment.

Science.gov (United States)

Smith, Robert L.; Popham, Ronald E.

1983-01-01

Presents an experiment in thermometric titration used in an analytic chemistry-chemical instrumentation course, consisting of two titrations, one a mixture of calcium and magnesium, the other of calcium, magnesium, and barium ions. Provides equipment and solutions list/specifications, graphs, and discussion of results. (JM)

Higher-capacity lithium ion battery chemistries for improved residential energy storage with micro-cogeneration

International Nuclear Information System (INIS)

Darcovich, K.; Henquin, E.R.; Kenney, B.; Davidson, I.J.; Saldanha, N.; Beausoleil-Morrison, I.

2013-01-01

Highlights: • Characterized two novel high capacity electrode materials for Li-ion batteries. • A numerical discharge model was run to characterize Li-ion cell behavior. • Engineering model of Li-ion battery pack developed from cell fundamentals. • ESP-r model integrated micro-cogeneration and high capacity Li-ion storage. • Higher capacity batteries shown to improve micro-cogeneration systems. - Abstract: Combined heat and power on a residential scale, also known as micro-cogeneration, is currently gaining traction as an energy savings practice. The configuration of micro-cogeneration systems is highly variable, as local climate, energy supply, energy market and the feasibility of including renewable type components such as wind turbines or photovoltaic panels are all factors. Large-scale lithium ion batteries for electrical storage in this context can provide cost savings, operational flexibility, and reduced stress on the distribution grid as well as a degree of contingency for installations relying upon unsteady renewables. Concurrently, significant advances in component materials used to make lithium ion cells offer performance improvements in terms of power output, energy capacity, robustness and longevity, thereby enhancing their prospective utility in residential micro-cogeneration installations. The present study evaluates annual residential energy use for a typical Canadian home connected to the electrical grid, equipped with a micro-cogeneration system consisting of a Stirling engine for supplying heat and power, coupled with a nominal 2 kW/6 kW h lithium ion battery. Two novel battery cathode chemistries, one a new Li–NCA material, the other a high voltage Ni-doped lithium manganate, are compared in the residential micro-cogeneration context with a system equipped with the presently conventional LiMn 2 O 4 spinel-type battery

Polymer chemistry (revised edition)

International Nuclear Information System (INIS)

Kim, Jae Mum

1987-02-01

This book deals with polymer chemistry, which is divided into fourteen chapters. The contents of this book are development of polymer chemistry, conception of polymer, measurement of polymer chemistry, conception of polymer, measurement of polymer, molecule structure of polymer, thermal prosperities of solid polymer, basic theory of polymerization, radical polymerization, ion polymerization, radical polymerization, copolymerization, polymerization by step-reaction, polymer reaction, crown polymer and inorganic polymer on classification and process of creation such as polymeric sulfur and carbon fiber.

Self-assembly of a superparamagnetic raspberry-like silica/iron oxide nanocomposite using epoxy-amine coupling chemistry.

Science.gov (United States)

Cano, Manuel; de la Cueva-Méndez, Guillermo

2015-02-28

The fabrication of colloidal nanocomposites would benefit from controlled hetero-assembly of ready-made particles through covalent bonding. Here we used epoxy-amine coupling chemistry to promote the self-assembly of superparamagnetic raspberry-like nanocomposites. This adaptable method induced the covalent attachment of iron oxide nanoparticles sparsely coated with amine groups onto epoxylated silica cores in the absence of other reactants.

Chemistry of Technetium

International Nuclear Information System (INIS)

Omori, Takashi

2001-01-01

Since the late 1970's the coordination chemistry of technetium has been developed remarkably. The background of the development is obviously related to the use of technetium radiopharmaceuticals for diagnosis in nuclear medicine. Much attention has also been denoted to the chemical behavior of environmental 99 Tc released from reprocessing plants. This review covers the several aspects of technetium chemistry, including production of radioisotopes, analytical chemistry and coordination chemistry. In the analytical chemistry, separation of technetium, emphasizing chromatography and solvent extraction, is described together with spectrophotometric determination of technetium. In the coordination chemistry of technetium, a characteristic feature of the chemistry of Tc(V) complexes is referred from the view point of the formation of a wide variety of highly stable complexes containing the Tc=O or Tc≡N bond. Kinetic studies of the preparation of Tc(III) complexes using hexakis (thiourea) technetium(III) ion as a starting material are summarized, together with the base hydrolysis reactions of Tc(III), Tc(IV) and Tc(V) complexes. (author)

A flame particle tracking analysis of turbulence–chemistry interaction in hydrogen–air premixed flames

KAUST Repository

Uranakara, Harshavardhana A.; Chaudhuri, Swetaprovo; Dave, Himanshu L.; Arias, Paul G.; Im, Hong G.

2015-01-01

Interactions of turbulence, molecular transport, and energy transport, coupled with chemistry play a crucial role in the evolution of flame surface geometry, propagation, annihilation, and local extinction/re-ignition characteristics of intensely turbulent premixed flames. This study seeks to understand how these interactions affect flame surface annihilation of lean hydrogen–air premixed turbulent flames. Direct numerical simulations (DNSs) are conducted at different parametric conditions with a detailed reaction mechanism and transport properties for hydrogen–air flames. Flame particle tracking (FPT) technique is used to follow specific flame surface segments. An analytical expression for the local displacement flame speed (Sd) of a temperature isosurface is considered, and the contributions of transport, chemistry, and kinematics on the displacement flame speed at different turbulence-flame interaction conditions are identified. In general, the displacement flame speed for the flame particles is found to increase with time for all conditions considered. This is because, eventually all flame surfaces and their resident flame particles approach annihilation by reactant island formation at the end of stretching and folding processes induced by turbulence. Statistics of principal curvature evolving in time, obtained using FPT, suggest that these islands are ellipsoidal on average enclosing fresh reactants. Further examinations show that the increase in Sd is caused by the increased negative curvature of the flame surface and eventual homogenization of temperature gradients as these reactant islands shrink due to flame propagation and turbulent mixing. Finally, the evolution of the normalized, averaged, displacement flame speed vs. stretch Karlovitz number are found to collapse on a narrow band, suggesting that a unified description of flame speed dependence on stretch rate may be possible in the Lagrangian description.

A flame particle tracking analysis of turbulence–chemistry interaction in hydrogen–air premixed flames

KAUST Repository

Uranakara, Harshavardhana A.

2015-11-21

Interactions of turbulence, molecular transport, and energy transport, coupled with chemistry play a crucial role in the evolution of flame surface geometry, propagation, annihilation, and local extinction/re-ignition characteristics of intensely turbulent premixed flames. This study seeks to understand how these interactions affect flame surface annihilation of lean hydrogen–air premixed turbulent flames. Direct numerical simulations (DNSs) are conducted at different parametric conditions with a detailed reaction mechanism and transport properties for hydrogen–air flames. Flame particle tracking (FPT) technique is used to follow specific flame surface segments. An analytical expression for the local displacement flame speed (Sd) of a temperature isosurface is considered, and the contributions of transport, chemistry, and kinematics on the displacement flame speed at different turbulence-flame interaction conditions are identified. In general, the displacement flame speed for the flame particles is found to increase with time for all conditions considered. This is because, eventually all flame surfaces and their resident flame particles approach annihilation by reactant island formation at the end of stretching and folding processes induced by turbulence. Statistics of principal curvature evolving in time, obtained using FPT, suggest that these islands are ellipsoidal on average enclosing fresh reactants. Further examinations show that the increase in Sd is caused by the increased negative curvature of the flame surface and eventual homogenization of temperature gradients as these reactant islands shrink due to flame propagation and turbulent mixing. Finally, the evolution of the normalized, averaged, displacement flame speed vs. stretch Karlovitz number are found to collapse on a narrow band, suggesting that a unified description of flame speed dependence on stretch rate may be possible in the Lagrangian description.

Amine chemistry. Update on impact on resin

International Nuclear Information System (INIS)

Bachman, Gregory; Kellogg, Douglas; Wilkes, Marty

2012-01-01

Impurity removal in the steam cycle and the associated prevention of corrosion and/or fouling of system components are the goals of ion exchange resins. However, in many instances (such as a switch to amine chemistry or a change in product specifications), resins do not remove, and, in fact, contribute impurities to the steam cycle. This paper reviews recent data compiled to determine the direct and indirect effects of amines on ion exchange resins used in the power industry. Water chemistries have improved in recent years, in large part due to changes in chemistry and resins, but it is necessary to continue to develop products, processes and techniques to reduce impurities and improve overall water chemistry in power plant systems. (orig.)

Amine chemistry. Update on impact on resin

Energy Technology Data Exchange (ETDEWEB)

Bachman, Gregory; Kellogg, Douglas [Siemens Industry, Inc., Rockford, IL (United States). Technology and Lab Services; Wilkes, Marty [Siemens Industry, Inc., Rockford, IL (United States). Water Technologies Div.

2012-03-15

Impurity removal in the steam cycle and the associated prevention of corrosion and/or fouling of system components are the goals of ion exchange resins. However, in many instances (such as a switch to amine chemistry or a change in product specifications), resins do not remove, and, in fact, contribute impurities to the steam cycle. This paper reviews recent data compiled to determine the direct and indirect effects of amines on ion exchange resins used in the power industry. Water chemistries have improved in recent years, in large part due to changes in chemistry and resins, but it is necessary to continue to develop products, processes and techniques to reduce impurities and improve overall water chemistry in power plant systems. (orig.)

Using Gas-Phase Guest-Host Chemistry to Probe the Structures of b Ions of Peptides

Science.gov (United States)

Somogyi, Árpád; Harrison, Alex G.; Paizs, Béla

2012-12-01

Middle-sized b n ( n ≥ 5) fragments of protonated peptides undergo selective complex formation with ammonia under experimental conditions typically used to probe hydrogen-deuterium exchange in Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Other usual peptide fragments like y, a, a*, etc., and small b n ( n ≤ 4) fragments do not form stable ammonia adducts. We propose that complex formation of b n ions with ammonia is characteristic to macrocyclic isomers of these fragments. Experiments on a protonated cyclic peptide and N-terminal acetylated peptides fully support this hypothesis; the protonated cyclic peptide does form ammonia adducts while linear b n ions of acetylated peptides do not undergo complexation. Density functional theory (DFT) calculations on the proton-bound dimers of all-Ala b 4 , b 5 , and b 7 ions and ammonia indicate that the ionizing proton initially located on the peptide fragment transfers to ammonia upon adduct formation. The ammonium ion is then solvated by N+-H…O H-bonds; this stabilization is much stronger for macrocyclic b n isomers due to the stable cage-like structure formed and entropy effects. The present study demonstrates that gas-phase guest-host chemistry can be used to selectively probe structural features (i.e., macrocyclic or linear) of fragments of protonated peptides. Stable ammonia adducts of b 9 , b 9 -A, and b 9 -2A of A8YA, and b 13 of A20YVFL are observed indicating that even these large b-type ions form macrocyclic structures.

Transesterification of castor oil usingMgO/SiO2 catalyst and coconutoilas co-reactant

OpenAIRE

Kamisah D. Pandiangan; Novesar Jamarun; Syukri Arief; Wasinton Simanjuntak

2016-01-01

This paper describes the transesterification of castor oil with the use of coconut oil as co-reactant and MgO/SiO2as heterogeneous base catalyst. The catalyst was preparedfrom rice husk silica and magnesium nitrate by sol-gel method, with MgO load of 20% relative to silica, and then subjected to sintering treatment at 600 oC for 6 hours. A series of experiments was carried out, indicating that the use of coconut oil as co-reactant significantly promoted the conversion of castor oil into b...

Radiation chemistry

International Nuclear Information System (INIS)

Swallow, A.J.

1983-01-01

The subject is covered in chapters, entitled: introduction (defines scope of article as dealing with the chemistry of reactive species, (e.g. excess electrons, excited states, free radicals and inorganic ions in unusual valency states) as studied using radiation with radiation chemistry in its traditional sense and with biological and industrial applications); gases; water and simple inorganic systems; aqueous metallo-organic compounds and metalloproteins; small organic molecules in aqueous solution; microheterogeneous systems; non-aqueous liquids and solutions; solids; biological macromolecules; synthetic polymers. (U.K.)

Current developments in radiation chemistry

International Nuclear Information System (INIS)

Cooper, R.

2000-01-01

Full text: The theme of the 2000 Gordon Conference on Radiation Chemistry was 'diversity'. The range of topics covered was heralded by the opening presentations which went from the galactic to molecular biology, radiation chemistry and non thermal surface processes in the outer solar system to achievements and open challenges in DNA research. The rest of the conference reflected the extended usage of radiation chemistry -its processes and techniques - applied to a panorama of topics. The ability to generate either oxidising or reducing free radicals in known quantities has been the foundation stone on which all applications are based. In particular it is noticeable that biological systems have been attempted by an increasing number of workers, such as studies of biological ageing and also reactions of nitric oxide in biological environments. Electron transfer processes in proteins are straightforward applications of solvated electron chemistry even if the results are not straightforward in their interpretation. Other topics presented include, radiation chemical processes induced in: supercritical CO 2 , treatment of contaminated materials, 3-dimensional Fullerenes, zeolites and radiation catalysis. In material science, aspects of ions and excited states in polymers, conducting polymers, donor acceptor processes in photo curing, enhancement of photo-electron yields in doped silver halides- improvement of the photographic process, radiation chemistry in cages and bubbles are discussed. The fundamental aspects of radiation chemistry are not yet all worked out. Subpicosecond pulsed electron beam sources, some of them 'tabletop', are still being planned to probe the early events in radiation chemistry both in water and in organic solvents. There is still an interest in the chemistry produced by pre-solvated electrons and the processes induced by heavy ion radiolysis. The description of the relaxation of an irradiated system which contains uneven distributions of ions

A plant-wide aqueous phase chemistry module describing pH variations and ion speciation/pairing in wastewater treatment process models.

Science.gov (United States)

Flores-Alsina, Xavier; Kazadi Mbamba, Christian; Solon, Kimberly; Vrecko, Darko; Tait, Stephan; Batstone, Damien J; Jeppsson, Ulf; Gernaey, Krist V

2015-11-15

There is a growing interest within the Wastewater Treatment Plant (WWTP) modelling community to correctly describe physico-chemical processes after many years of mainly focusing on biokinetics. Indeed, future modelling needs, such as a plant-wide phosphorus (P) description, require a major, but unavoidable, additional degree of complexity when representing cationic/anionic behaviour in Activated Sludge (AS)/Anaerobic Digestion (AD) systems. In this paper, a plant-wide aqueous phase chemistry module describing pH variations plus ion speciation/pairing is presented and interfaced with industry standard models. The module accounts for extensive consideration of non-ideality, including ion activities instead of molar concentrations and complex ion pairing. The general equilibria are formulated as a set of Differential Algebraic Equations (DAEs) instead of Ordinary Differential Equations (ODEs) in order to reduce the overall stiffness of the system, thereby enhancing simulation speed. Additionally, a multi-dimensional version of the Newton-Raphson algorithm is applied to handle the existing multiple algebraic inter-dependencies. The latter is reinforced with the Simulated Annealing method to increase the robustness of the solver making the system not so dependent of the initial conditions. Simulation results show pH predictions when describing Biological Nutrient Removal (BNR) by the activated sludge models (ASM) 1, 2d and 3 comparing the performance of a nitrogen removal (WWTP1) and a combined nitrogen and phosphorus removal (WWTP2) treatment plant configuration under different anaerobic/anoxic/aerobic conditions. The same framework is implemented in the Benchmark Simulation Model No. 2 (BSM2) version of the Anaerobic Digestion Model No. 1 (ADM1) (WWTP3) as well, predicting pH values at different cationic/anionic loads. In this way, the general applicability/flexibility of the proposed approach is demonstrated, by implementing the aqueous phase chemistry module in some

The chemistry of the actinide elements. Volume I

International Nuclear Information System (INIS)

Katz, J.J.; Seaborg, G.T.; Morss, L.R.

1986-01-01

The Chemistry of the Actinide Elements is a comprehensive, contemporary and authoritative exposition of the chemistry and related properties of the 5f series of elements: actinium, thorium, protactinium, uranium and the first eleven. This second edition has been completely restructured and rewritten to incorporate current research in all areas of actinide chemistry and chemical physics. The descriptions of each element include accounts of their history, separation, metallurgy, solid-state chemistry, solution chemistry, thermo-dynamics and kinetics. Additionally, separate chapters on spectroscopy, magnetochemistry, thermodynamics, solids, the metallic state, complex ions and organometallic compounds emphasize the comparative chemistry and unique properties of the actinide series of elements. Comprehensive lists of properties of all actinide compounds and ions in solution are given, and there are special sections on such topics as biochemistry, superconductivity, radioisotope safety, and waste management, as well as discussion of the transactinides and future elements

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

Science.gov (United States)

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

2014-11-26

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

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

Science.gov (United States)

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

2015-06-21

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

A Simple Analytical Model for Predicting the Detectable Ion Current in Ion Mobility Spectrometry Using Corona Discharge Ionization Sources

Science.gov (United States)

Kirk, Ansgar Thomas; Kobelt, Tim; Spehlbrink, Hauke; Zimmermann, Stefan

2018-05-01

Corona discharge ionization sources are often used in ion mobility spectrometers (IMS) when a non-radioactive ion source with high ion currents is required. Typically, the corona discharge is followed by a reaction region where analyte ions are formed from the reactant ions. In this work, we present a simple yet sufficiently accurate model for predicting the ion current available at the end of this reaction region when operating at reduced pressure as in High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) or most IMS-MS instruments. It yields excellent qualitative agreement with measurement results and is even able to calculate the ion current within an error of 15%. Additional interesting findings of this model are the ion current at the end of the reaction region being independent from the ion current generated by the corona discharge and the ion current in High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) growing quadratically when scaling down the length of the reaction region. [Figure not available: see fulltext.

Distributed scaffolding: Wiki collaboration among Latino high school chemistry students

Science.gov (United States)

O'Sullivan, Edwin Duncan, Jr.

The primary purpose of this study was to evaluate if wiki collaboration among Latino high school chemistry students can help reduce the science achievement gap between Latino and White students. The study was a quasi-experimental pre/post control group mixed-methods design. It used three intact sections of a high school chemistry course. The first research question asked if there is a difference in academic achievement between a treatment and control group on selected concepts from the topics of bonding, physical changes, and chemical changes, when Latino high school chemistry students collaborate on a quasi-natural wiki project. Overall results for all three activities (Bonding, Physical Changes, and Chemical Changes) indicated no significant difference between the wiki and control group. However, students performing the chemical changes activity did significantly better than their respective control group. Furthermore, there was a significant association, with large effect size, between group membership and ability to overcome the misconception that aqueous ionic reactants in precipitation reactions exist as molecular pairs of ions. Qualitative analysis of classroom and computer lab dialogue, discussion board communication, student focus groups, teacher interviews, and wiki content attributes the better performance of the chemical changes wiki group to favorable differences in intersubjectivity and calibrated assistance, as well as learning about submicroscopic representations of precipitation reactions in multiple contexts. Furthermore, the nonsignificant result overall points to an aversion to peer editing as a possible cause. Drawing considerably on Vygotsky and Piaget, the results are discussed within the context of how distributed scaffolding facilitated medium levels of cognitive conflict. The second research question asked what the characteristics of distributed metacognitive scaffolding are when Latino high school chemistry students collaborate on a quasi

Structure And Chemistry Of Ion Masses ≤ 40 Amu In The Inner Coma Of Comet HalleyStructure And Chemistry Of Ion Masses ≤ 40 Amu In The Inner Coma Of Comet Halley

Science.gov (United States)

Haider, S. A.; Bhardwaj, A.

In this paper, we have developed a chemical model to study the chemistry of 46 ions (CH5+, SH+, S+, H2S+, NH3OH+, CH3+, HCO+, H2CO+, C2H3+, C3H3+, H3CO+, H2CN+, H3S+, NH3+, CH3OH2+, CH3OH+, NH4+, H3O+, N+, NH+, NH2+, N2+, C2H+, C+, CH2+, CH+, C2N+, C3H+, C2H4+, C2H5+, CO+, O+, H+, C2+, HCN+, OH+, O2+, CHOH2+, HNO+, N2H+, H2O+, CH4+, C2H2+, (H2O)2+, H5O2+ and C3H+) corresponding to masses ≤ 40 amu in the inner coma of comet Halley. The ionization sources included in the model are solar EUV photon, photoelectron and auroral electron of solar wind origin. The production rates, loss rates and mass densities of these ions are calculated using Analytical Yield Spectrum approach and coupled continuity equation controlled by steady state photochemical model, which involves over 600 chemical reactions between ions, neutrals, photons and electrons in the coma. The calculated mass densities are compared with Giotto Ion Mass Spectrometer (IMS) and Neutral Mass Spectrometer (NMS) data at radial distances 1500 km, 3500 km and 6000 km. The nine major peaks at 12, 15, 19, 26, 28, 31, 33, 35, and 39 amu observed in IMS/NMS spectra are reproduced well by model calculation. ^

Chemistry in Titan

Science.gov (United States)

Plessis, S.; Carrasco, N.; Pernot, P.

2009-04-01

Modelling the chemical composition of Titan's ionosphere is a very challenging issue. Latest works perform either inversion of CASSINI's INMS mass spectra (neutral[1] or ion[2]), or design coupled ion-neutral chemistry models[3]. Coupling ionic and neutral chemistry has been reported to be an essential feature of accurate modelling[3]. Electron Dissociative Recombination (EDR), where free electrons recombine with positive ions to produce neutral species, is a key component of ion-neutral coupling. There is a major difficulty in EDR modelling: for heavy ions, the distribution of neutral products is incompletely characterized by experiments. For instance, for some hydrocarbon ions only the carbon repartition is measured, leaving the hydrogen repartition and thus the exact neutral species identity unknown[4]. This precludes reliable deterministic modelling of this process and of ion-neutral coupling. We propose a novel stochastic description of the EDR chemical reactions which enables efficient representation and simulation of the partial experimental knowledge. The description of products distribution in multi-pathways reactions is based on branching ratios, which should sum to unity. The keystone of our approach is the design of a probability density function accounting for all available informations and physical constrains. This is done by Dirichlet modelling which enables one to sample random variables whose sum is constant[5]. The specifics of EDR partial uncertainty call for a hierarchiral Dirichlet representation, which generalizes our previous work[5]. We present results on the importance of ion-neutral coupling based on our stochastic model. C repartition H repartition (measured) (unknown ) → C4H2 + 3H2 + H .. -→ C4 . → C4H2 + 7H → C3H8. + CH C4H+9 + e- -→ C3 + C .. → C3H3 + CH2 + 2H2 → C2H6 + C2H2 + H .. -→ C2 + C2 . → 2C2H2 + 2H2 + H (1) References [1] J. Cui, R.V. Yelle, V. Vuitton, J.H. Waite Jr., W.T. Kasprzak

Chemistry Notes

Science.gov (United States)

School Science Review, 1972

1972-01-01

Short articles on the kinetics of the hydrogen peroxide-iodide ion reaction, simulation of fluidization catalysis, the use of Newman projection diagrams to represent steric relationships in organic chemistry, the use of synthetic substrates for proteolytic enzyme reactions, and two simple clock reactions"--hydrolysis of halogenoalkanes and…

Molecular Studies of Complex Soil Organic Matter Interactions with Metal Ions and Mineral Surfaces using Classical Molecular Dynamics and Quantum Chemistry Methods

Science.gov (United States)

Andersen, A.; Govind, N.; Laskin, A.

2017-12-01

Mineral surfaces have been implicated as potential protectors of soil organic matter (SOM) against decomposition and ultimate mineralization to small molecules which can provide nutrients for plants and soil microbes and can also contribute to the Earth's elemental cycles. SOM is a complex mixture of organic molecules of biological origin at varying degrees of decomposition and can, itself, self-assemble in such a way as to expose some biomolecule types to biotic and abiotic attack while protecting other biomolecule types. The organization of SOM and SOM with mineral surfaces and solvated metal ions is driven by an interplay of van der Waals and electrostatic interactions leading to partitioning of hydrophilic (e.g. sugars) and hydrophobic (e.g., lipids) SOM components that can be bridged with amphiphilic molecules (e.g., proteins). Classical molecular dynamics simulations can shed light on assemblies of organic molecules alone or complexation with mineral surfaces. The role of chemical reactions is also an important consideration in potential chemical changes of the organic species such as oxidation/reduction, degradation, chemisorption to mineral surfaces, and complexation with solvated metal ions to form organometallic systems. For the study of chemical reactivity, quantum chemistry methods can be employed and combined with structural insight provided by classical MD simulations. Moreover, quantum chemistry can also simulate spectroscopic signatures based on chemical structure and is a valuable tool in interpreting spectra from, notably, x-ray absorption spectroscopy (XAS). In this presentation, we will discuss our classical MD and quantum chemistry findings on a model SOM system interacting with mineral surfaces and solvated metal ions.

Model Titan atmospheric hydrocarbon analysis by Ion Mobility Spectrometry in dry helium

International Nuclear Information System (INIS)

Kojiro, D.R.; Stimac, R.M.; Wernlund, R.F.; Cohen, M.J.

1990-01-01

Ion Mobility Spectrometry (IMS) is one analytical technique being investigated for the in situ analysis of the atmosphere of Titan. Any hydrocarbon ions that may form react immediately, in microseconds, with the high concentration of water vapor normally present in conventional IMS. By reducing the water concentration to the parts-per-billion range, the lifetime of the hydrocarbon ions may be increased to the milliseconds required for measurement. At low water level concentrations, other species may become the reactant ion. This study focuses on IMS analysis of expected Titan atmospheric hydrocarbons under very dry, low water concentration conditions

Design, fabrication and performance of a mixed-reactant membraneless micro direct methanol fuel cell stack

Science.gov (United States)

Abrego-Martínez, J. C.; Moreno-Zuria, A.; Cuevas-Muñiz, F. M.; Arriaga, L. G.; Sun, Shuhui; Mohamedi, Mohamed

2017-12-01

In the present work, we report the design, fabrication and evaluation of a membraneless mixed-reactant and air-breathing microfluidic direct methanol fuel cell (ML-μDMFC) stack operated in passive mode. The operation under mixed-reactant conditions was achieved by using a highly methanol-tolerant Ag/Pt/CP cathode with ultra-low Pt loading in alkaline medium. Prior to the fabrication of the stack, a flow simulation was made in order to study the behavior of the reactants stream in the microchannel through the 2 cells. Subsequently, the device was tested in passive mode using a mixture of 5 M MeOH +0.5 M KOH. The results showed that by connecting the 2 cells in series, it is possible to effectively double the voltage of a single ML-μDMFC, as well as increasing the absolute power by 75% with practically no cost increase. The stack was capable of operate continuously for more than 2 h with a single charge of 40 μL, producing an OCV of 0.89 V and a maximum power density of 3.33 mW mgPt-1. Additionally, the device exhibited good stability throughout a 10 h test.

Ion binding by humic and fulvic acids: A computational procedure based on functional site heterogeneity and the physical chemistry of polyelectrolyte solutions

International Nuclear Information System (INIS)

Marinsky, J.A.; Reddy, M.M.; Ephraim, J.; Mathuthu, A.

1988-04-01

Ion binding equilibria for humic and fulvic acids are examined from the point of view of functional site heterogeneity and the physical chemistry of polyelectrolyte solutions. A detailed explanation of the potentiometric properties of synthetic polyelectrolytes and ion-exchange gels is presented first to provide the basis for a parallel consideration of the potentiometric properties exhibited by humic and fulvic acids. The treatment is then extended to account for functional site heterogeneity. Sample results are presented for analysis of the ion-binding reactions of a standard soil fulvic acid (Armadale Horizons Bh) with this approach to test its capability for anticipation of metal ion removal from solution. The ultimate refined model is shown to be adaptable, after appropriate consideration of the heterogeneity and polyelectrolyte factors, to programming already available for the consideration of ion binding by inorganics in natural waters. (orig.)

Low temperature nitrogen chemistry. Final report

Energy Technology Data Exchange (ETDEWEB)

Glarborg, P.; Dam-Johansen, K.; Kristensen, P.G.; Alzueta, M.; Roejel, H.

1997-04-01

The results of a two tasks program on Natural Gas Reburning are reported. The work involved an experimental and theoretical study of the reburning and hybrid reburning/SNCR chemistry in the 1000-1500 K range. The interactions between hydrocarbon and nitrogen chemistry under fuel-rich conditions were investigated in order to assess the NO{sub x} reduction potential of low temperature reburning. The effect of reburn fuel(carbon monoxide, methane, acetylene, ethylene, ethane, and methane/ethane mixture), temperature, stoichiometry, reactant dilution, reaction time, and inlet NO level were studied. The results indicate a significant NO reduction potential even below 1400 K, but extrapolation to practical conditions are complicated by inadequate knowledge of the detailed chemistry as well as of the effect of mixing. The possibilities of enhancing the conversion to N{sub 2} instead of NO by adding selective reducing agents (hybrid reburning/SNCR) were evaluated. Our results indicate little synergistic effect between reburn and SNCR. The most simple configuration, where the selective reducing agent is injected together with the burnout air, is not expected to be effective, unless the N-agent is injected in form of an aqueous solution. A chemical kinetic model for reburning and reburn/SNCR is listed and can be obtained by e-mail from pgl(commerical at)kt.dtu.dk.(au) 145 refs.

BWR chromium chemistry

International Nuclear Information System (INIS)

Baston, V.F.; Indig, M.E.; Skarpelos, J.M.

1992-10-01

This report addresses the concern about higher total specific conductivity in the reactor recirculation loop water due to the chromate ion. This concern is particularly high at plants where all other ionic species have been reduced through careful attention to makeup and condensate polisher operations. An EPRI Chromate Workshop was held in November 1990 to consider the issues raised by observed levels of chromate ion (generally 5 to 50 ppB). While BWRs on normal water chemistry were the only ones observing chromate, even plants on hydrogen water chemistry (HWC) observe sharp spikes of conductivity due to chromate whenever the hydrogen supply was interrupted after a reasonably long HWC operational period. The consensus of the workshop attendees was that chromate was not a concern as an agent causing pipe cracking compared to the more common species such as chloride and sulfate. However, the data are somewhat ambiguous for levels of chromate above 50 ppB. Adjustments to the weighing factors for the various ionic species in the industry chemistry performance index are suggested to allow for the known relative higher aggressiveness of other species relative to that of chromate

Negative ion detachment cross sections: Progress report, March 1, 1985--February 29, 1988

International Nuclear Information System (INIS)

Champion, R.L.; Doverspike, L.D.

1987-08-01

The purpose of the experimental investigations undertaken during the past three years was to perform an extensive and comprehensive study of the collisional dynamics of reactants which involve collisions of negative ions and neutral atomic and molecular targets. The (laboratory) collision energies for these studies ranged from about 1 eV up to 500 eV and the experiments involved measurements of both absolute total cross sections and doubly-differential cross sections. The various processes investigated included electron detachment, charge transfer, dissociative charge transfer and reactive (or rearrangement) scattering. Reactants which were the subject of these investigations included the negative ions O/sup minus/, S/sup minus/, Na/sup minus /, K/sup minus/, Cs/sup minus/, H/sup minus/, D/sup minus/ in collisions with H 2 , D 2 , O 2 , N 2 , CO, CO 2 , CH 4 and the alkali atoms Na, K and Cs

General chemistry

International Nuclear Information System (INIS)

Kwon, Yeong Sik; Lee, Dong Seop; Ryu, Haung Ryong; Jang, Cheol Hyeon; Choi, Bong Jong; Choi, Sang Won

1993-07-01

The book concentrates on the latest general chemistry, which is divided int twenty-three chapters. It deals with basic conception and stoichiometry, nature of gas, structure of atoms, quantum mechanics, symbol and structure of an electron of ion and molecule, chemical thermodynamics, nature of solid, change of state and liquid, properties of solution, chemical equilibrium, solution and acid-base, equilibrium of aqueous solution, electrochemistry, chemical reaction speed, molecule spectroscopy, hydrogen, oxygen and water, metallic atom; 1A, IIA, IIIA, carbon and atom IVA, nonmetal atom and an inert gas, transition metals, lanthanons, and actinoids, nuclear properties and radioactivity, biochemistry and environment chemistry.

Chemistry WebBook

Science.gov (United States)

SRD 69 NIST Chemistry WebBook (Web, free access)   The NIST Chemistry WebBook contains: Thermochemical data for over 7000 organic and small inorganic compounds; thermochemistry data for over 8000 reactions; IR spectra for over 16,000 compounds; mass spectra for over 33,000 compounds; UV/Vis spectra for over 1600 compounds; electronic and vibrational spectra for over 5000 compounds; constants of diatomic molecules(spectroscopic data) for over 600 compounds; ion energetics data for over 16,000 compounds; thermophysical property data for 74 fluids.

Platinum- and membrane-free swiss-roll mixed-reactant alkaline fuel cell.

Science.gov (United States)

Aziznia, Amin; Oloman, Colin W; Gyenge, Előd L

2013-05-01

Eliminating the expensive and failure-prone proton exchange membrane (PEM) together with the platinum-based anode and cathode catalysts would significantly reduce the high capital and operating costs of low-temperature (<373 K) fuel cells. We recently introduced the Swiss-roll mixed-reactant fuel cell (SR-MRFC) concept for borohydride-oxygen alkaline fuel cells. We now present advances in anode electrocatalysis for borohydride electrooxidation through the development of osmium nanoparticulate catalysts supported on porous monolithic carbon fiber materials (referred to as an osmium 3D anode). The borohydride-oxygen SR-MRFC operates at 323 K and near atmospheric pressure, generating a peak power density of 1880 W m(-2) in a single-cell configuration by using an osmium-based anode (with an osmium loading of 0.32 mg cm(-2)) and a manganese dioxide gas-diffusion cathode. To the best of our knowledge, 1880 W m(-2) is the highest power density ever reported for a mixed-reactant fuel cell operating under similar conditions. Furthermore, the performance matches the highest reported power densities for conventional dual chamber PEM direct borohydride fuel cells. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bibliographies on radiation chemistry

International Nuclear Information System (INIS)

Hoffman, M.Z.; Ross, A.B.

1986-01-01

The one-electron oxidation and reduction of metal ions and complexes can yield species in unusual oxidation states, and ligand-radicals coordinated to the central metal. These often unstable species can be mechanistically important intermediates in thermal, photochemical, and electrochemical reactions involving metal-containing substances. Their generation via radiolysis provides an alternate means of characterizing them using kinetic and spectroscopic techniques. We hope these bibliographies on the radiation chemistry of metal ions and complexes, presented according to periodic groups, will prove useful to researchers in metallo-redox chemistry. These bibliographies contain only primary literature sources; reviews are not included. However, a list of general review articles on the radiation chemistry of metal ions and complexes is presented here in the first section which covers cobalt, rhodium and iridium, Group 9 in the new IUPAC notation. Additional parts of the bibliography are planned, covering other periodic groups. Part A of the bibliography was prepared by a search of the Radiation Chemistry Data Center Bibliographic Data Base (RCDCbib) through January 1986 for papers on rhodium, iridium and cobalt compounds, and radiolysis (both continuous and pulsed). Papers in which the use of metal compounds was incidental to the primary objective of the study were excluded. Excluded also were publications in unrefereed and obscure sources such as meeting proceedings, internal reports, dissertations, and patents. The majority of the studies in the resultant compilation deal with experiments performed on solutions, mainly aqueous, although a substantial fraction is devoted to solid-state esr measurements. The references are listed in separate sections for each of the metals, and are presented in approximate chronological order. (author)

Basic chemistry for radioactive waste management

International Nuclear Information System (INIS)

Park, Kyong Kyun; Kim, Won Ho; Jee, Kwang Yong; Kim, Jong Goo; Park, Yeong Jae; Yu, Mahn Su; Jee, Choun Suk; Song, Byoung Chul; Choi, Ke Chon; Eom, Tae Yoon

1991-03-01

The complex formation between uranium(VI) ion and chloride ion in aqueous solution can be confirmed by UV-Vis absorption spectroscopy and differential pulse polarography. Absorption spectra and differential pulse polarograms of uranyl ion in hypochlorite/chloride media shows for its interaction with hypochlorite ion. Although the spectral changes for its interaction are ambiguous, new half-wave potential due to the interaction of uranium(VI)-hypochlorite ion appears in the differential pulse polarogram. Kinetic studies on the electron transfer reaction between U(IV) ion and Fe(III)(phen)3 complex in the solution containing dipicolinic acid or phosphoric acid show that the reaction rate slows down in low ligands concentration and speeds up in high ligands concentration. This result indicates that free functional group of multidentate ligands coordinated to U(IV) ion interacts at the 2 or 9 position carbon atom of phenanthroline ring in iron(III) complex. The presence of 5-sulfosalicylic acid slows down the electron transfer reaction between U(IV) ion and Fe(III) ion through the complex formation with two reactants. More information about the complex formation between U(IV) ion and 5-sulfosalicylic acid is needed for accurate explanation of the reaction mechanism. Both plutonium and uranium are extracted by TBP/dodecane from the aqueous solution, in which the post-irradiated nuclear fuel pellet is dissolved. They are back-extracted into 2M HCl solution after reducing plutonium(IV) ion to plutonium(III) ion by added U(IV) ion. Removing uranium on the DOWEX A-l anion exchange column, plutonium is eluted later for its purification. Gamma and alpha spectroscopic measurements shows the high decontamination factor and 95% recovery for the initial amounts of plutonium. (Author)

Ion sorption onto hydrous ferric oxides: Effect on major element fluid chemistry at Aespoe, Sweden

International Nuclear Information System (INIS)

Bruton, C.J.; Viani, B.E.

1996-06-01

The observed variability of fluid chemistry at the Aespoe Hard Rock Laboratory is not fully described by conservative fluid mixing models. Ion exchange may account for some of the observed discrepancies. It is also possible that variably charged solids such as oxyhydroxides of Fe can serve as sources and sinks of anions and cations through surface complexation. Surface complexation reactions on hydrous ferric oxides involve sorption of both cations and anions. Geochemical modeling of the surface chemistry of hydrous ferric oxides (HFOs) in equilibrium with shallow HBH02 and deep KA0483A waters shows that HFOs can serve as significant, pH-sensitive sources and sinks for cations and anions. Carbonate sorption is favored especially at below-neutral pH. A greater mass of carbonate is sorbed onto HFO surfaces than is contained in the fluid when 10 g goethite, used as a proxy for HFOs, is in contact with 1 kg H 2 O. The masses of sorbent required to significantly impact fluid chemistry through sorption/desorption reactions seem to be reasonable when compared to the occurrences of HFOs at Aespoe. Thus, it is possible that small changes in fluid chemistry can cause significant releases of cations or anions from HFOs into the fluid phase or, alternately, result in uptake of aqueous species onto HFO surfaces. Simulations of the mixing of shallow HBH02 and native KA0483A waters in the presence of a fixed mass of goethite show that surface complexation does not cause the concentrations of Ca, Sr, and SO 4 to deviate from those that are predicted using conservative mixing models. Results for HCO 3 are more difficult to interpret and cannot be addressed adequately at this time

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

Energy Technology Data Exchange (ETDEWEB)

Kipriyanov, Alexey A.; Kipriyanov, Alexander A.; Doktorov, Alexander B. [Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Novosibirsk 630090, Russia and Novosibirsk State University, Novosibirsk 630090 (Russian Federation)

2016-04-14

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

Ion exchange phenomena

Energy Technology Data Exchange (ETDEWEB)

Bourg, I.C.; Sposito, G.

2011-05-01

Ion exchange phenomena involve the population of readily exchangeable ions, the subset of adsorbed solutes that balance the intrinsic surface charge and can be readily replaced by major background electrolyte ions (Sposito, 2008). These phenomena have occupied a central place in soil chemistry research since Way (1850) first showed that potassium uptake by soils resulted in the release of an equal quantity of moles of charge of calcium and magnesium. Ion exchange phenomena are now routinely modeled in studies of soil formation (White et al., 2005), soil reclamation (Kopittke et al., 2006), soil fertilitization (Agbenin and Yakubu, 2006), colloidal dispersion/flocculation (Charlet and Tournassat, 2005), the mechanics of argillaceous media (Gajo and Loret, 2007), aquitard pore water chemistry (Tournassat et al., 2008), and groundwater (Timms and Hendry, 2007; McNab et al., 2009) and contaminant hydrology (Chatterjee et al., 2008; van Oploo et al., 2008; Serrano et al., 2009).

High pressure chemistry of red phosphorus by photoactivated simple molecules

Science.gov (United States)

Ceppatelli, Matteo; Bini, Roberto; Fanetti, Samuele; Caporali, Maria; Peruzzini, Maurizio

2013-06-01

High pressure (HP) is very effective in reducing intermolecular distances and inducing unexpected chemical reactions. In particular the photoactivation of the reactants in HP conditions can lead to very efficient and selective processes. The chemistry of phosphorus is currently based on the white molecular form. The red polymeric allotrope, despite more stable and much less toxic, has not attracted much attention so far. However, switching from the white to the red form would benefit any industrial procedure, especially from an environmental point of view. On the other side, water and ethanol are renewable, environmental friendly and largely available molecules, usable as reactants and photoactivators in HP conditions. Here we report a study on the HP photoinduced reactivity of red phosphorus with water and ethanol, showing the possibility of very efficient and selective processes, leading to molecular hydrogen and valuable phosphorus compounds. The reactions have been studied by means of FTIR and Raman spectroscopy and pressure has been generated using DAC and SAC. HP reactivity has been activated by the two-photon absorption of near-UV wavelengths and occured in total absence of solvents, catalysts and radical initiators, at room T and mild pressure conditions (0.2-1.5 GPa).

Experimental investigation of laminar LPG-H{sub 2} jet diffusion flame with preheated reactants

Energy Technology Data Exchange (ETDEWEB)

D.P. Mishra; P. Kumar [Indian Institute of Technology, Kanpur (India). Combustion Laboratory, Department of Aerospace Engineering

2008-10-15

This paper presents an experimental investigation of the effect of H{sub 2} addition on flame length, soot free length fraction (SFLF), flame radiant fraction, gas temperature and emission level in LPG-H{sub 2} composite fuel jet diffusion flame for two preheated cases namely, (i) preheated air and (ii) preheated air and fuel. Results show that the H{sub 2} addition leads to a reduction in flame length which may be caused due to an increased gas temperature. Besides this, the flame length is also observed to be reduced with increasing reactants temperature. The soot free length fraction (SFLF) increases as H{sub 2} is added to fuel stream. This might have been caused by decrease in the C/H ratio in the flame and is favorable to attenuate PAH formation rate. Interestingly, the SFLF is observed to be reduced with increasing reactants temperature that may be due to reduction in induction period of soot formation caused by enhanced flame temperature. Moreover, the decreased radiant heat fraction with hydrogen addition is pertinent with the reduction in soot concentration level. The reduction in NOx emission level with H{sub 2} addition to the fuel stream is also observed. On the contrary, NOx emission level is found to be enhanced significantly with reactant temperature that can be attributed to the increase in thermal NOx through Zeldovich mechanism. 31 refs., 4 figs., 2 tabs.

Premixed flame chemistry of a gasoline primary reference fuel surrogate

KAUST Repository

Selim, Hatem

2017-03-10

Investigating the combustion chemistry of gasoline surrogate fuels promises to improve detailed reaction mechanisms used for simulating their combustion. In this work, the combustion chemistry of one of the simplest, but most frequently used gasoline surrogates – primary reference fuel 84 (PRF 84, 84 vol% iso-octane and 16 vol% n-heptane), has been examined in a stoichiometric premixed laminar flame. Time-of-flight mass spectrometry coupled with a vacuum ultraviolet (VUV) synchrotron light source for species photoionization was used. Reactants, major end-products, stable intermediates, free radicals, and isomeric species were detected and quantified. Numerical simulations were conducted using a detailed chemical kinetic model with the most recently available high temperature sub-mechanisms for iso-octane and heptane, built on the top of an updated pentane isomers model and AramcoMech 2.0 (C0C4) base chemistry. A detailed interpretation of the major differences between the mechanistic pathways of both fuel components is given. A comparison between the experimental and numerical results is depicted and rate of production and sensitivity analyses are shown for the species with considerable disagreement between the experimental and numerical findings.

Ninth international symposium on hot atom chemistry. Abstracts

International Nuclear Information System (INIS)

1977-01-01

Abstracts of the papers presented at the Symposium are compiled. The topics considered were chemical dynamics of high energy reactions, hot atom chemistry in organic compounds of tritium, nitrogen, oxygen, and halogens, theory and chemical dynamics of hot atom reactions as determined by beam studies, solid state reactions of recoil atoms and implanted ions, hot atom chemistry in energy-related research, hot atom chemistry in inorganic compounds of oxygen and tritium, hot positronium chemistry, applied hot atom chemistry in labelling, chemical effects of radioactive decay, decay-induced reactions and excitation labelling, physical methods in hot atom chemistry, and hot atom reactions in radiation and stratospheric chemistry

Vibrational-state-selected ion--molecule reaction cross sections at thermal energies

NARCIS (Netherlands)

Pijkeren, D. van; Boltjes, E.; Eck, J. van; Niehaus, A.

1984-01-01

A method designed to measure relative ion—molecule reaction rates at thermal collision energies for selected reactant ion vibrational states is described. Relative reaction rates are determined for the three endothermic reactions: H2+ (υ)(He,H)HeH+, H2+ (υ)(Ne,H)NeH+, D2+(υ)(Ne, D)NeD+, and for the

Enhancing Capacity Performance by Utilizing the Redox Chemistry of the Electrolyte in a Dual-Electrolyte Sodium-Ion Battery.

Science.gov (United States)

Senthilkumar, Sirugaloor Thangavel; Bae, Hyuntae; Han, Jinhyup; Kim, Youngsik

2018-05-04

A strategy is described to increase charge storage in a dual electrolyte Na-ion battery (DESIB) by combining the redox chemistry of the electrolyte with a Na + ion de-insertion/insertion cathode. Conventional electrolytes do not contribute to charge storage in battery systems, but redox-active electrolytes augment this property via charge transfer reactions at the electrode-electrolyte interface. The capacity of the cathode combined with that provided by the electrolyte redox reaction thus increases overall charge storage. An aqueous sodium hexacyanoferrate (Na 4 Fe(CN) 6 ) solution is employed as the redox-active electrolyte (Na-FC) and sodium nickel Prussian blue (Na x -NiBP) as the Na + ion insertion/de-insertion cathode. The capacity of DESIB with Na-FC electrolyte is twice that of a battery using a conventional (Na 2 SO 4 ) electrolyte. The use of redox-active electrolytes in batteries of any kind is an efficient and scalable approach to develop advanced high-energy-density storage systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of layer thickness and composition on the kinetics of solid state reactions in the niobium-selenium system studied using superlattice reactants

International Nuclear Information System (INIS)

Fukuto, M.; Kevan, S.D.

1997-01-01

The ability to form an amorphous reaction intermediate by the low temperature interdiffusion of a modulated elemental reactant is shown to be a function of the overall composition as well as elemental layer thicknesses in the niobium-selenium system. For niobium-rich reactants, an amorphous reaction intermediate was observed to form upon low temperature annealing of reactants with modulation thicknesses less than 60 A. Further annealing of the amorphous intermediates led to the crystallization of Nb 2 Se, Nb 5 Se 4 or Nb 3 Se 4 depending upon the overall composition of the amorphous intermediate. Modulated elemental reactants with overall compositions containing more than two-thirds selenium were found to heterogeneously nucleate NbSe 2 at the reacting interfaces. The formation of the thermodynamically expected compounds Nb 2 Se 3 , NbSe 3 , and Nb 2 Se 9 at their respective compositions required extended high temperature annealing to react the dichalcogenide with the remaining elemental reactants. A striking difference between the evolution of the low angle diffraction patterns in these two composition regimes suggests the differences in the reaction kinetics result from a composition dependence of the diffusion coefficients. (orig.)

Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2.

Science.gov (United States)

Maitra, Urmimala; House, Robert A; Somerville, James W; Tapia-Ruiz, Nuria; Lozano, Juan G; Guerrini, Niccoló; Hao, Rong; Luo, Kun; Jin, Liyu; Pérez-Osorio, Miguel A; Massel, Felix; Pickup, David M; Ramos, Silvia; Lu, Xingye; McNally, Daniel E; Chadwick, Alan V; Giustino, Feliciano; Schmitt, Thorsten; Duda, Laurent C; Roberts, Matthew R; Bruce, Peter G

2018-03-01

The search for improved energy-storage materials has revealed Li- and Na-rich intercalation compounds as promising high-capacity cathodes. They exhibit capacities in excess of what would be expected from alkali-ion removal/reinsertion and charge compensation by transition-metal (TM) ions. The additional capacity is provided through charge compensation by oxygen redox chemistry and some oxygen loss. It has been reported previously that oxygen redox occurs in O 2p orbitals that interact with alkali ions in the TM and alkali-ion layers (that is, oxygen redox occurs in compounds containing Li + -O(2p)-Li + interactions). Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 exhibits an excess capacity and here we show that this is caused by oxygen redox, even though Mg 2+ resides in the TM layers rather than alkali-metal (AM) ions, which demonstrates that excess AM ions are not required to activate oxygen redox. We also show that, unlike the alkali-rich compounds, Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 does not lose oxygen. The extraction of alkali ions from the alkali and TM layers in the alkali-rich compounds results in severely underbonded oxygen, which promotes oxygen loss, whereas Mg 2+ remains in Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 , which stabilizes oxygen.

Ion mobility spectrometry

CERN Document Server

Eiceman, GA

2005-01-01

Key Developments for Faster, More Precise Detection Capabilities Driven by the demand for the rapid and advanced detection of explosives, chemical and biological warfare agents, and narcotics, ion mobility spectrometry (IMS) undergone significant refinements in technology, computational capabilities, and understanding of the principles of gas phase ion chemistry and mobility. Beginning with a thorough discussion of the fundamental theories and physics of ion mobility, Ion Mobility Spectrometry, Second Edition describes the recent advances in instrumentation and newly

Automation of a battery of ion exchange columns for the determination of Pu in biological samples

International Nuclear Information System (INIS)

Jeanmaire, L.; Ballada, J.; Rigaudiere, R.; Patti, F.; Clanet, F.

1967-01-01

The document describes an apparatus allowing ten automatic and simultaneous determination of plutonium by ion exchange resins in urine. The constant flow rate reactants supply is realized by plastic siphons. The different determination phases are controlled by a programmer. (A.L.B.) [fr

Electrostatics in Chemistry

Indian Academy of Sciences (India)

Electrostatics in Chemistry. 3. Molecular Electrostatic Potential: Visualization and Topography. Shridhar R Gadre and Pravin K Bhadane. 1 1. Basic Principles, Resona- nce, Vol.4, No.2, 11-19, 1999. 2. Electrostatic Potentials of. Atoms, Ions and Molecules,. Resonance, Vol.4, No.5, 40-51,. 1999. Topographical features of the ...

Laccase Immobilization by Chelated Metal Ion Coordination Chemistry

Directory of Open Access Journals (Sweden)

Qingqing Wang

2014-09-01

Full Text Available In this work, amidoxime polyacrylonitrile (AOPAN nanofibrous membrane was prepared by a reaction between PAN nanofibers and hydroxylamine hydrochloride. The AOPAN nanofibrous membranes were used for four metal ions (Fe3+, Cu2+, Ni2+, Cd2+ chelation under different conditions. Further, the competition of different metal ions coordinating with AOPAN nanofibrous membrane was also studied. The AOPAN chelated with individual metal ion (Fe3+, Cu2+, Ni2+, Cd2+ and also the four mixed metal ions were further used for laccase (Lac immobilization. Compared with free laccase, the immobilized laccase showed better resistance to pH and temperature changes as well as improved storage stability. Among the four individual metal ion chelated membranes, the stability of the immobilized enzymes generally followed the order as Fe–AOPAN–Lac > Cu–AOPAN–Lac > Ni–AOPAN–Lac > Cd–AOPAN–Lac. In addition, the immobilized enzyme on the carrier of AOPAN chelated with four mixed metal ions showed the best properties.

Progress report, Chemistry and Materials Division, October 1 to December 31, 1975

International Nuclear Information System (INIS)

1976-01-01

Interim research results are reported in solid state science (ion penetration, electron microscopy, radiation damage and metal physics, nuclear methods of analysis), general chemistry (analytical chemistry, hydrogen-water exchange, radioactivity measurements, electrochemistry), physical chemistry (radiation and isotope chemistry), materials science (surface chemistry and metal physics), and university research (deuterium exchange and zirconium alloy properties). (E.C.B.)

A plant wide aqueous phase chemistry model describing pH variations and ion speciation/pairing in wastewater treatment process models

DEFF Research Database (Denmark)

Flores-Alsina, X.; Mbamba, C. Kazadi; Solon, K.

cationic/anionic loads. In this way, the general applicability/flexibility of the proposed approach is demonstrated by implementing the aqueous phase chemistry module in some of the most frequently used WWTP process simulation models. Finally, it is shown how traditional wastewater modelling studies can......, require a major, but unavoidable, additional degree of complexity when representing cationic/anionic behaviour in Activated Sludge (AS)/Anaerobic Digestion (AD) systems (Ikumi et al., 2014). In this paper, a plant-wide aqueous phase chemistry module describing pH variations plus ion speciation...... of Ordinary Differential Equations (ODEs) in order to reduce the overall stiffness of the system, thereby enhancing simulation speed. Additionally, a multi-dimensional version of the Newton-Raphson algorithm is applied to handle the existing multiple algebraic inter-dependencies (Solon et al., 2015...

A plant-wide aqueous phase chemistry module describing pH variations and ion speciation/pairing in wastewater treatment process models

DEFF Research Database (Denmark)

Flores Alsina, Xavier; Kazadi Mbamba, Christian; Solon, Kimberly

2015-01-01

at different cationic/anionic loads. In this way, the general applicability/flexibility of the proposed approach is demonstrated, by implementing the aqueous phase chemistry module in some of the most frequently used WWTP process simulation models. Finally, it is shown how traditional wastewater modelling......, but unavoidable, additional degree of complexity when representing cationic/anionic behaviour in Activated Sludge (AS)/Anaerobic Digestion (AD) systems. In this paper, a plant-wide aqueous phase chemistry module describing pH variations plus ion speciation/pairing is presented and interfaced with industry......) in order to reduce the overall stiffness of the system, thereby enhancing simulation speed. Additionally, a multi-dimensional version of the Newton-Raphson algorithm is applied to handle the existing multiple algebraic inter-dependencies. The latter is reinforced with the Simulated Annealing method...

Serum levels of chicken mannan-binding lectin (MBL) during virus infections; indication that chicken MBL is an acute phase reactant

DEFF Research Database (Denmark)

Nielsen, O.L.; Jensenius, J. C.; Jørgensen, Poul Henrik

1999-01-01

Mannan-binding lectin (MBL) is a serum collectin which is believed to be an opsonin of the innate immune defence against various microorganisms. MBL is a minor acute phase reactant in man. We investigated the concentration of serum MBL in chickens infected with infectious bronchitis virus (IBV...... levels returned to normal values 6-10 days after infection. The results indicated that MBL is a minor acute phase reactant in chickens....

Uranium chemistry research unit

International Nuclear Information System (INIS)

Anon.

1978-01-01

The initial field of research of this Unit, established in 1973, was the basic co-ordination chemistry of uranium, thorium, copper, cobalt and nickel. Subsequently the interest of the Unit extended to extractive metallurgy relating to these metals. Under the term 'co-ordination chemistry' is understood the interaction of the central transition metal ion with surrounding atoms in its immediate vicinity (within bonding distance) and the influence they have on each other - for example, structural studies for determining the number and arrangement of co-ordinated atoms and spectrophotometric studies to establish how the f electron energy levels of uranium are influenced by the environment. New types of uranium compounds have been synthesized and studied, and the behaviour of uranium ions in non-aqueous systems has also received attention. This work can be applied to the development and study of extractants and new extractive processes for uranium

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

Science.gov (United States)

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

2016-04-14

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

Hadron chemistry in heavy ion collisions

International Nuclear Information System (INIS)

Montvay, I.; Zimanyi, J.

1978-06-01

In the models for energetic heavy ion reactions it is assumed that during the reaction a hot and dense nuclear matter, a fireball is formed from all or a part of nucleons of the target and projectile nuclei. The process is similar to the chemical processes leading to dynamical equilibrium. The relaxation times necessary to establish ''chemical'' equilibrium among different hadrons in hot, dense hadronic matter is deducted in a statistical model. Consequences for heavy ion collisions are discussed. The possibility of Bose-Einstein pion condensation around the break-up time of the nuclear fireball is pointed out. (D.P.)

Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement VIII, halogen species evaluation for atmospheric chemistry

International Nuclear Information System (INIS)

Atkinson, R.; Baulch, D.L.; Cox, R.A.; Hampson, R.F. Jr.; Kerr, J.A.; Rossi, M.J.; Troe, J.

2000-01-01

This paper updates and extends part of the previous data base of critical evaluations of the kinetics and photochemistry of gas-phase chemical reactions of neutral species involved in atmospheric chemistry [J. Phys. Chem. Ref. Data 9, 295 (1980); 11, 327 (1982); 13, 1259 (1984); 18, 881 (1989); 21, 1125 (1992); 26, 521 (1997); 26, 1329 (1997); 28, 191 (1999)]. The present evaluation is limited to the inorganic halogen family of atmospherically important reactions. The work has been carried out by the authors under the auspices of the IUPAC Subcommittee on Gas Phase Kinetic Data Evaluation for Atmospheric Chemistry. Data sheets have been prepared for 102 thermal and photochemical reactions, containing summaries of the available experimental data with notes giving details of the experimental procedures. For each thermal reaction, a preferred value of the rate coefficient at 298 K is given together with a temperature dependence where possible. The selection of the preferred value is discussed and estimates of the accuracies of the rate coefficients and temperature coefficients have been made for each reaction. For each photochemical reaction the data sheets list the preferred values of the photoabsorption cross sections and the quantum yields of the photochemical reactions together with comments on how they were selected. The data sheets are intended to provide the basic physical chemical data needed as input for calculations that model atmospheric chemistry. A table summarizing the preferred rate data is provided, together with an appendix listing the available values of enthalpies of formation of the reactant and product species

The impact of reactants composition and temperature on the flow structure in a wake stabilized laminar lean premixed CH4/H2/air flames; mechanism and scaling

KAUST Repository

Michaels, D.

2016-11-11

In this paper we investigate the role of reactants composition and temperature in defining the steady flow structure in bluff body stabilized premixed flames. The study was motivated by experiments which showed that the flow structure and stability map for different fuels and inlet conditions collapse using the extinction strain rate as the chemical time scale. The investigation is conducted using a laminar lean premixed flame stabilized on a heat conducting bluff-body. Calculations are performed for a wide range of mixtures of CH4/H2/air (0.35 ≤ ϕ ≤ 0.75, 0 ≤ %H2 ≤ 40, 300 ≤ Tin [K] ≤ 500) in order to systematically vary the burning velocity (2.0–35.6 cm/s), dilatation ratio (2.7–6.4), and extinction strain rate (106–2924 1/s). The model is based on a fully resolved unsteady two-dimensional flow with detailed chemistry and species transport, and with no artificial flame anchoring boundary conditions. Calculations reveal that the recirculation zone length correlates with a chemical time scale based on the flame extinction strain rate corresponding to the inlet fuel composition, stoichiometry, pressure and temperature; and are consistent with experimental data in literature. It was found that in the wake region the flame is highly stretched and its location and interaction with the flow is governed by the reactants combustion characteristics under high strain.

Ion Chromatography Applications in Wastewater Analysis

Directory of Open Access Journals (Sweden)

Rajmund Michalski

2018-02-01

Full Text Available Wastewater analysis is an important area in analytical and environmental chemistry. It can be performed with both the classic wet methods and instrumental techniques. The development of new methods, and modification of the existing ones, constitute a major task for researchers. Ion chromatography plays a predominant role in ion determinations with the instrumental methods. It offers several advantages over the conventional methods, such as simultaneous determinations of alkali and alkaline earth cations and ammonia. Ammonium ions cannot be determined by spectroscopic methods. Ion chromatography has been accepted world-wide as a reference method for analyzing anions and cations in water and wastewater due to the fact that it enables the replacement of several individual wet chemistry methods for common ions with one instrumental technique. The following article describes the principles of ion chromatography, such as stationary phases, eluents, detectors, and sample preparation methods. Moreover, the applications of ion chromatography in wastewater analyses and international standards are presented.

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

Science.gov (United States)

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

2015-11-07

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

Uranium chemistry: significant advances

International Nuclear Information System (INIS)

Mazzanti, M.

2011-01-01

The author reviews recent progress in uranium chemistry achieved in CEA laboratories. Like its neighbors in the Mendeleev chart uranium undergoes hydrolysis, oxidation and disproportionation reactions which make the chemistry of these species in water highly complex. The study of the chemistry of uranium in an anhydrous medium has led to correlate the structural and electronic differences observed in the interaction of uranium(III) and the lanthanides(III) with nitrogen or sulfur molecules and the effectiveness of these molecules in An(III)/Ln(III) separation via liquid-liquid extraction. Recent work on the redox reactivity of trivalent uranium U(III) in an organic medium with molecules such as water or an azide ion (N 3 - ) in stoichiometric quantities, led to extremely interesting uranium aggregates particular those involved in actinide migration in the environment or in aggregation problems in the fuel processing cycle. Another significant advance was the discovery of a compound containing the uranyl ion with a degree of oxidation (V) UO 2 + , obtained by oxidation of uranium(III). Recently chemists have succeeded in blocking the disproportionation reaction of uranyl(V) and in stabilizing polymetallic complexes of uranyl(V), opening the way to to a systematic study of the reactivity and the electronic and magnetic properties of uranyl(V) compounds. (A.C.)

Negative Ion Chemistry in the Coma of Comet 1P/Halley

Science.gov (United States)

Cordiner, M. A.; Charnley, S. B.

2012-01-01

Negative ions (anions) were identified in the coma of comet 1P/Halley from in-situ measurements performed by the Giotto spacecraft in 1986. These anions were detected with masses in the range 7-110 amu, but with insufficient mass resolution to permit unambiguous identification. We present details of a new chemical-hydrodynamic model for the coma of comet Halley that includes - for the first time - atomic and molecular anions, in addition to a comprehensive hydrocarbon chemistry. Anion number densities arc calculated as a function of radius in the coma, and compared with the Giotto results. Important anion production mechanisms arc found to include radiative electron attachment, polar photodissociation, dissociative electron attachment, and proton transfer. The polyyne anions C4H(-) and C6H(-) arc found to be likely candidates to explain the Giotto anion mass spectrum in the range 49-73 amu. Thc CN(-) anion probably makes a significant contribution to the mass spectrum at 26 amu. Larger carbon-chain anions such as C8H(1) can explain the peak near 100 amu provided there is a source of large carbon-chain-bearing molecules from the cometary nucleus.

Mobility and molecular ions of dimethyl methyl phosphonate, methyl salicylate and acetone

Science.gov (United States)

Nowak, D. M.

1983-06-01

The mobilities of positive and negative reactant ions are reported for (H2O)nH(+); (H2O)2O2 and (H2O)2CO3(-) ion clusters. The formation of positive DMMP monomer and dimer is reported, and equilbria molecular reactions are reported. Acetone is reported as forming a dimer at 81 ppb with a reduced mobility (K sub o) of 1.82, Methyl salicylate is shown to form a protonated and hydrated positive monomer. Mixtures of DMMP and methyl salicylate with acetone showed a substantial change in DMMP ion clustering and little or no change in the methyl salicylate mobility spectra. Negative ions were not observed for DMMP, methyl salicylate, acetone and the mixtures under the conditions reported.

Mendeleev-2013. VII All-Russian conference of young scientists, postgraduate students and students with international participation on chemistry and nanomaterials. Book of abstracts. Section 4. Organic chemistry

International Nuclear Information System (INIS)

2013-01-01

VII All-Russian conference of young scientists, postgraduate students and students with international participation on chemistry and nanomaterials was conducted on the Chemistry department of Saint-Petersburg University on April, 2-5, 2013. In the conference participants from 14 countries took part. There were five sections: Nanochemistry and nanomaterials, Analytic chemistry, Inorganic chemistry, Organic chemistry, Physical chemistry. In the collection (Section 2 - Organic chemistry) there are the abstracts concerning different aspects of organic chemistry: synthesis and study of properties of heterocyclic, organometallic, biologically active, medicinal compounds, new ion exchange materials, reagents for analytic chemistry, etc [ru

Fiscal 1999 survey report. Part 2. Research study on restraint of carbon dioxide generation by green chemistry; 1999 nendo green chemistry ni yoru CO{sub 2} hassei yokusei ni kakawaru chosa kenkyu. 2

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-01

In connection with green chemistry, a concept of bringing paradigm shift to chemical technologies as something that makes reduction in environmental load compatible with economic activities; surveys were made this year on the developments of fine chemicals from renewable resources such as cellulose among the cases of developing chemical substances/products to be called 'green chemicals' reducing environmental load; developments of surfactants produced by certain microorganism, plastic additives with reduced pollutant loads, particularly fire retardants and environmentally benign reactant solvents; concept of green chemistry in the development of chlorofluorocarbon-alternatives; and up-to-date technological level concerning a design method of chemical materials and an estimation method for chemical safety using quantum chemistry calculation. In regard to the chemical materials and products intrinsically containing a certain level of risk, R and D should be reinforced and accelerated in the future on the alternative materials/products reducing their toxicity. In this case, along with the importance of discussing compatibility of technological possibility with economical adaptability, sociological study seems to be necessary in incorporating environmental load reduction into economic evaluation. (NEDO)

Research on the actinide chemistry in Nuclear Fuel Cycle

Energy Technology Data Exchange (ETDEWEB)

Song, Kyseok; Park, Yong Joon; Cho, Young Hwan; and others

2012-04-15

Fundamental technique to measure chemical behaviors and properties of lanthanide and actinide in radioactive waste is necessary for the development of pryochemical process. First stage, the electrochemical/spectroscopic integrated measurement system was designed and set up for spectro-electrochemical measurements of lanthanide and actinide ions in high temperature molten salt media. A compact electrochemical cell and electrode system was also developed for the minimization of reactants, and consequently minimization of radioactive waste generation. By applying these equipments, oxidation and reduction behavior of lanthanide and actinide ions in molten salt media have been made. Also, thermodynamic parameter values are determined by interpreting the results obtained from electrochemical measurements. Several lanthanide ions exhibited fluorescence properties in molten salt. Also, UV-VIS measurement provided the detailed information regarding the oxidation states of lanthanide and actinide ions in high temperature molten salt media. In the second stage, measurement system for physical properties at pyrochemical process such as viscosity, melting point and conductivity is established, and property database at different compositions of lanthanide and actinide is collected. And, both interactions between elements and properties with different potential are measured at binary composition of actinide-lanthanide in molten salt using electrochemical/spectroscopic integrated measurement system.

Analytical chemistry

International Nuclear Information System (INIS)

Anon.

1985-01-01

The division for Analytical Chemistry continued to try and develope an accurate method for the separation of trace amounts from mixtures which, contain various other elements. Ion exchange chromatography is of special importance in this regard. New separation techniques were tried on certain trace amounts in South African standard rock materials and special ceramics. Methods were also tested for the separation of carrier-free radioisotopes from irradiated cyclotron discs

Electron capture by multicharged ions at eV energies

International Nuclear Information System (INIS)

Havener, C.C.; Huq, M.S.; Meyer, F.W.; Phaneuf, R.A.

1988-01-01

A multicharged ion-atom merged-beams apparatus has been used in conjunction with the ORNL-ECR ion source to measure accurate absolute electron-capture cross sections in the energy range from below 1 eV/amu to 1500 eV/amu. Measurements for N/sup 3+,4+,5+/ /plus/ H(D) collisions indicate good agreement with available theoretical calculations. However, measurements with O 5+ /plus/ H(D) show an unexpected low-energy behavior which may be attributable to the ion-induced-dipole attraction between the reactants. Scaled Landau-Zener calculations presented here identify a transfer plus excitation channel which has the correct energy dependence at low energies. This finding suggest the need for a comprehensive coupled channel calculation which would include such product states. 25 refs., 8 figs

Negative ion molecule reactions of WF6: evidence for a pressure dependent branching ratio

International Nuclear Information System (INIS)

Viggiano, A.A.; Paulson, J.F.

1984-01-01

Rate coefficients have been measured in a selected ion flow tube (SIFT) for reactions of several negative ions with WF 6 . With the exception of SF - 5 , all the reactant ions studied having an electron detachment energy less than 3.36 eV reacted rapidly by charge exchange. SF - 5 transferred a fluoride ion producing WF - 7 . Ions with detachment energies greater than 3.36 eV associated rapidly with WF - 6 . Br - , with a detachment energy of 3.36 eV, reacted with WF 6 both by ion-neutral association and by charge exchange. The branching ratio for these two channels was found to depend on temperature and pressure. All these data indicate that the electron affinity of WF 6 is nearly equal to that of Br

Chemistry and kinetics of size-selected cobalt cluster cations at thermal energies. I. Reactions with CO

Science.gov (United States)

Guo, B. C.; Kerns, K. P.; Castleman, A. W., Jr.

1992-06-01

The chemistry and kinetics of size-selected Co+n cluster-ion (n=2-8) reactions with CO are studied using a selected ion drift tube affixed with a laser vaporization source operated under well-defined thermal conditions. All reactions studied in the present work are found to be association reactions. Their absolute rate constants, which are determined quantitatively, are found to have a strong dependence on cluster size. Similar to the cases of reactions with many other reactants such as H2 and CH4, Co+4 and Co+5 display a higher reactivity toward the CO molecule than do clusters of neighboring size. The multiple-collision conditions employed in the present work have enabled a determination of the maximum coordination number of CO molecules bound onto each Co+n cluster. It is found that the tetramer tends to bond 12 CO molecules, the pentamer 14 CO, hexamer 16 CO, and so on. The results are interpreted in terms of Lauher's calculation and the polyhedral skeletal electron pair theory. All the measured maximum coordination numbers correlate extremely well with the predictions of these theories, except for the trimer where the measured number is one CO less than the predicted value. The good agreement between experiment and theory enables one to gain some insight into the geometric structure of the clusters. Based on the present findings, the cobalt tetramer cation is interpreted to have a tetrahedral structure, the pentamer a trigonal bipyramid, and the hexamer an octahedral structure. Other cluster structures are also discussed.

Method of detecting defects in ion exchange membranes of electrochemical cells by chemochromic sensors

Science.gov (United States)

Brooker, Robert Paul; Mohajeri, Nahid

2016-01-05

A method of detecting defects in membranes such as ion exchange membranes of electrochemical cells. The electrochemical cell includes an assembly having an anode side and a cathode side with the ion exchange membrane in between. In a configuration step a chemochromic sensor is placed above the cathode and flow isolation hardware lateral to the ion exchange membrane which prevents a flow of hydrogen (H.sub.2) between the cathode and anode side. The anode side is exposed to a first reactant fluid including hydrogen. The chemochromic sensor is examined after the exposing for a color change. A color change evidences the ion exchange membrane has at least one defect that permits H.sub.2 transmission therethrough.

Ion transport membrane reactor systems and methods for producing synthesis gas

Science.gov (United States)

Repasky, John Michael

2015-05-12

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

Progress report, Chemistry and Materials Division, July 1 to September 30, 1976

International Nuclear Information System (INIS)

Preliminary results are reported on research into ion penetration, electron microscopy, radiation damage and metal physics, analytical chemistry, radiation chemistry, basic corrosion studies and isotope separation techniques. (O.T.)

Progress report, Chemistry and Materials Division, April 1 to June 30, 1977

International Nuclear Information System (INIS)

1977-07-01

Research results are reported in such areas as ion penetration, electron microscopy, metal physics and radiation damage, nuclear methods of analysis, fuel analysis, and general analytical chemistry, electrochemistry, radiation chemistry, hydrogen-deuterium exchange, and surface chemistry of nuclear materials like zirconium base alloys. (E.C.B.)

Progress report, Chemistry and Materials Division, January 1 to March 31, 1976

International Nuclear Information System (INIS)

1976-05-01

Interim results are reported in research fields roughly classified as ion penetration, electron microscopy, radiation damage and metal physics, nuclear methods of analysis, analytical chemistry, deuterium separation, radioactivity measurement, radiation and isotope chemistry, and surface chemistry and metal physics, primarily of zirconium alloys. (E.C.B.)

Progress report, Chemistry and Materials Division, January 1 to March 31, 1977

International Nuclear Information System (INIS)

1977-04-01

Results are described of research on ion penetration, electron microscopy, radiation damage and metal physics, nuclear methods of analysis, computer calculating methods, analytical chemistry, deuterium exchange, radioactivity measurement, electrochemistry, mass spectrometry and fuel analysis, radiation chemistry, surface chemistry, and properties of zirconium base alloys. (E.C.B.)

Photoionization and ion cyclotron resonance studies of the ion chemistry of ethylene oxide

Science.gov (United States)

Corderman, R. R.; Williamson, A. D.; Lebreton, P. R.; Buttrill, S. E., Jr.; Beauchamp, J. L.

1976-01-01

The formation of the ethylene oxide molecular ion and its subsequent ion-molecule reactions leading to the products C2H5O(+) and C3H5O(+) have been studied using time-resolved photoionization mass spectroscopy, ion cyclotron resonance spectroscopy, and photoelectron spectroscopy. An examination of the effects of internal energy on reactivity shows that the ratio of C3H5O(+) to C2H5O(+) increases by an order of magnitude with a single quantum of vibrational energy. The formation of (C2H4O/+/)-asterisk in a collision-induced isomerization is found which yields a ring-opened structure by C-C bond cleavage. The relaxed ring-opened C2H4O(+) ion reacts with neutral ethylene oxide by CH2(+) transfer to yield an intermediate product ion C3H6O(+) which gives C3H5O(+) by loss of H.

Negative chlorine ion chemistry in the upper stratosphere and its application to an artificially created dense electron cloud

Directory of Open Access Journals (Sweden)

S. S. Prasad

1995-03-01

Full Text Available This paper discusses new potential reactions of chlorine-bearing anions (negative ions in the upper stratosphere. These reactions are then applied to the negative-ion chemistry following the injection of an electron cloud of very high density, of the order of 106-107 e- cm-3, in the 40-45-km region. The idea is to evaluate the recently proposed scheme to mitigate ozone depletion by converting the reactive chlorine atoms at these altitudes into Cl- ions which are unreactive towards ozone, i.e., electron scavenging of Cl. We find that the previously neglected photodetachment from Cl- is fast. For an overhead sun, this process may have a rate coefficient of 0.08 s-1 when multiple scattering is included. The rate could be even higher, depending on the ground albedo. Switching reaction between Cl-·H2O and HCl might lead to the formation of Cl-·HCl anion. Possible reactions of Cl-·H2O and Cl-·HCl with O atoms could produce ClO- and Cl-2. The production of ClO- in this manner is significant because Cl- having a high photodetachment rate constant would be regenerated in the very likely reactions of ClO- with O. When these possibilities are considered, then it is found that the chlorine anions may not be the major ions inside the electron cloud due to the rapid photodetachment from Cl-. Furthermore, in such a cloud, there may be the hazard that the Cl--Cl-·H2O-ClO--Cl- cycle amounts to catalytic destruction of two O atoms. Thus, the scheme could be risky if practised in the altitude region where atomic oxygen is an important constituent. Similar conclusions apply even if the ClO- species forms ClO-3 by three-body association with O2, instead of reacting with O. It must be emphasized that the present study is speculative at this time, because none of the relevant reactions have been investigated in the laboratory as yet. Nevertheless, it is very safe to say that the scheme of ozone preservation by electron scavenging of the upper stratospheric Cl is

Progress report, Chemistry and Materials Division, April 1 to June 30, 1978

International Nuclear Information System (INIS)

1978-07-01

Provisional research results are reported in the general areas of ion beam-radiation interactions with metals, radiation chemistry, hydrogen isotope exchange, analytical chemistry, and zirconium alloy properties. (E.C.B.)

Effects of ion concentration on the hydrogen bonded structure of ...

Indian Academy of Sciences (India)

WINTEC

Effects of ion concentration on the hydrogen bonded structure of water in the vicinity of ions in aqueous NaCl solutions. A NAG. 1. , D CHAKRABORTY and A CHANDRA*. Department of Chemistry, Indian Institute of Technology, Kanpur 208 016. 1. Present address: Department of Chemistry and Chemical Engineering,.

Progress report, Chemistry and Materials Division, 1 April to 30 June, 1979

International Nuclear Information System (INIS)

1979-07-01

Research results are reported by groups investigating ion penetration, nuclear methods of analysis, accelerator operation, general analytical chemistry, radoactivity measurement, deuterium analysis, electrochemistry, mass spectrometry and fuel analysis, radiation chemistry and laser photochemistry, hydrogen-water exchange, isotope chemistry, surface chemistry, and electron microscopy. Work in an associated laboratory at the University of Toronto on isotopic changes in reaction rates is reported. (L.L.)

Organic chemistry in Titan's upper atmosphere and its astrobiological consequences: I. Views towards Cassini plasma spectrometer (CAPS) and ion neutral mass spectrometer (INMS) experiments in space

Science.gov (United States)

Ali, A.; Sittler, E. C.; Chornay, D.; Rowe, B. R.; Puzzarini, C.

2015-05-01

The discovery of carbocations and carbanions by Ion Neutral Mass Spectrometer (INMS) and the Cassini Plasma Spectrometer (CAPS) instruments onboard the Cassini spacecraft in Titan's upper atmosphere is truly amazing for astrochemists and astrobiologists. In this paper we identify the reaction mechanisms for the growth of the complex macromolecules observed by the CAPS Ion Beam Spectrometer (IBS) and Electron Spectrometer (ELS). This identification is based on a recently published paper (Ali et al., 2013. Planet. Space Sci. 87, 96) which emphasizes the role of Olah's nonclassical carbonium ion chemistry in the synthesis of the organic molecules observed in Titan's thermosphere and ionosphere by INMS. The main conclusion of that work was the demonstration of the presence of the cyclopropenyl cation - the simplest Huckel's aromatic molecule - and its cyclic methyl derivatives in Titan's atmosphere at high altitudes. In this study, we present the transition from simple aromatic molecules to the complex ortho-bridged bi- and tri-cyclic hydrocarbons, e.g., CH2+ mono-substituted naphthalene and phenanthrene, as well as the ortho- and peri-bridged tri-cyclic aromatic ring, e.g., perinaphthenyl cation. These rings could further grow into tetra-cyclic and the higher order ring polymers in Titan's upper atmosphere. Contrary to the pre-Cassini observations, the nitrogen chemistry of Titan's upper atmosphere is found to be extremely rich. A variety of N-containing hydrocarbons including the N-heterocycles where a CH group in the polycyclic rings mentioned above is replaced by an N atom, e.g., CH2+ substituted derivative of quinoline (benzopyridine), are found to be dominant in Titan's upper atmosphere. The mechanisms for the formation of complex molecular anions are discussed as well. It is proposed that many closed-shell complex carbocations after their formation first, in Titan's upper atmosphere, undergo the kinetics of electron recombination to form open-shell neutral

Ejection of Coulomb Crystals from a Linear Paul Ion Trap for Ion-Molecule Reaction Studies.

Science.gov (United States)

Meyer, K A E; Pollum, L L; Petralia, L S; Tauschinsky, A; Rennick, C J; Softley, T P; Heazlewood, B R

2015-12-17

Coulomb crystals are being increasingly employed as a highly localized source of cold ions for the study of ion-molecule chemical reactions. To extend the scope of reactions that can be studied in Coulomb crystals-from simple reactions involving laser-cooled atomic ions, to more complex systems where molecular reactants give rise to multiple product channels-sensitive product detection methodologies are required. The use of a digital ion trap (DIT) and a new damped cosine trap (DCT) are described, which facilitate the ejection of Coulomb-crystallized ions onto an external detector for the recording of time-of-flight (TOF) mass spectra. This enables the examination of reaction dynamics and kinetics between Coulomb-crystallized ions and neutral molecules: ionic products are typically cotrapped, thus ejecting the crystal onto an external detector reveals the masses, identities, and quantities of all ionic species at a selected point in the reaction. Two reaction systems are examined: the reaction of Ca(+) with deuterated isotopologues of water, and the charge exchange between cotrapped Xe(+) with deuterated isotopologues of ammonia. These reactions are examples of two distinct types of experiment, the first involving direct reaction of the laser-cooled ions, and the second involving reaction of sympathetically-cooled heavy ions to form a mixture of light product ions. Extensive simulations are conducted to interpret experimental results and calculate optimal operating parameters, facilitating a comparison between the DIT and DCT approaches. The simulations also demonstrate a correlation between crystal shape and image shape on the detector, suggesting a possible means for determining crystal geometry for nonfluorescing ions.

Progress report, Chemistry and Materials Division, October 1 to December 31, 1977

International Nuclear Information System (INIS)

1978-01-01

Research results are reported on the interaction of ion beams with solids, radiation chemistry, hydrogen isotope exchange, surface science, analytical chemistry, and properties of zirconium and its alloys. (E.C.B.)

Proton-bound cluster ions in ion mobility spectrometry

Science.gov (United States)

Ewing, R. G.; Eiceman, G. A.; Stone, J. A.

1999-01-01

Gaseous oxygen and nitrogen bases, both singly and as binary mixtures, have been introduced into ion mobility spectrometers to study the appearance of protonated molecules, and proton-bound dimers and trimers. At ambient temperature it was possible to simultaneously observe, following the introduction of molecule A, comparable intensities of peaks ascribable to the reactant ion (H2O)nH+, the protonated molecule AH+ and AH+ H2O, and the symmetrical proton bound dimer A2H+. Mass spectral identification confirmed the identifications and also showed that the majority of the protonated molecules were hydrated and that the proton-bound dimers were hydrated to a much lesser extent. No significant peaks ascribable to proton-bound trimers were obtained no matter how high the sample concentration. Binary mixtures containing molecules A and B, in some cases gave not only the peaks unique to the individual compounds but also peaks due to asymmetrical proton bound dimers AHB+. Such ions were always present in the spectra of mixtures of oxygen bases but were not observed for several mixtures of oxygen and nitrogen bases. The dimers, which were not observable, notable for their low hydrogen bond strengths, must have decomposed in their passage from the ion source to the detector, i.e. in a time less than approximately 5 ms. When the temperature was lowered to -20 degrees C, trimers, both homogeneous and mixed, were observed with mixtures of alcohols. The importance of hydrogen bond energy, and hence operating temperature, in determining the degree of solvation of the ions that will be observed in an ion mobility spectrometer is stressed. The possibility is discussed that a displacement reaction involving ambient water plays a role in the dissociation.

Transition metal chemistry of hydroxy(–OH)-rich molecules ...

Indian Academy of Sciences (India)

Administrator

Appropriately designed hydroxy(–OH) containing Schiff's base and Mannich base molecules have been recently found to be important for development of the coordination chemistry of a number of metal ions in the biomimetic chemistry of metalloenzymes. In this context, our group has studied the coordination role of these ...

High pressure chemistry of red phosphorus by photo-activated simple molecules

Science.gov (United States)

Ceppatelli, M.; Fanetti, S.; Bini, R.; Caporali, M.; Peruzzini, M.

2014-05-01

High pressure (HP) is very effective in reducing intermolecular distances and inducing unexpected chemical reactions. In addition the photo-activation of the reactants in HP conditions can lead to very efficient and selective processes. The chemistry of phosphorus is currently based on the white molecular form. The red polymeric allotrope, despite more stable and much less toxic, has not attracted much attention so far. However, switching from the white to the red form would benefit any industrial procedure, especially from an environmental point of view. On the other side, water and ethanol are renewable, environmental friendly and largely available molecules, usable as reactants and photo-activators in HP conditions. Here we report a study on the HP photo-induced reactivity of red phosphorus with water and ethanol, showing the possibility of very efficient and selective processes, leading to molecular hydrogen and valuable phosphorus compounds. The reactions have been studied by means of FTIR and Raman spectroscopy and pressure has been generated using membrane Diamond (DAC) and Sapphire (SAC) anvil cells. HP reactivity has been activated by the two-photon absorption of near-UV wavelengths and occurred in total absence of solvents, catalysts and radical initiators, at room T and mild pressure conditions (0.2-1.5 GPa).

High pressure chemistry of red phosphorus by photo-activated simple molecules

International Nuclear Information System (INIS)

Ceppatelli, M; Bini, R; Caporali, M; Peruzzini, M; Fanetti, S

2014-01-01

High pressure (HP) is very effective in reducing intermolecular distances and inducing unexpected chemical reactions. In addition the photo-activation of the reactants in HP conditions can lead to very efficient and selective processes. The chemistry of phosphorus is currently based on the white molecular form. The red polymeric allotrope, despite more stable and much less toxic, has not attracted much attention so far. However, switching from the white to the red form would benefit any industrial procedure, especially from an environmental point of view. On the other side, water and ethanol are renewable, environmental friendly and largely available molecules, usable as reactants and photo-activators in HP conditions. Here we report a study on the HP photo-induced reactivity of red phosphorus with water and ethanol, showing the possibility of very efficient and selective processes, leading to molecular hydrogen and valuable phosphorus compounds. The reactions have been studied by means of FTIR and Raman spectroscopy and pressure has been generated using membrane Diamond (DAC) and Sapphire (SAC) anvil cells. HP reactivity has been activated by the two-photon absorption of near-UV wavelengths and occurred in total absence of solvents, catalysts and radical initiators, at room T and mild pressure conditions (0.2–1.5 GPa).

Chemistry--The Big Picture

Science.gov (United States)

Cassell, Anne

2011-01-01

Chemistry produces materials and releases energy by ionic or electronic rearrangements. Three structure types affect the ease with which a reaction occurs. In the Earth's crust, "solid crystals" change chemically only with extreme heat and pressure, unless their fixed ions touch moving fluids. On the other hand, in living things, "liquid crystals"…

Collections for terminology in chemistry

International Nuclear Information System (INIS)

1974-08-01

This book describes terminology in chemistry, which is divided into seven chapters. The contents of this book are element name, names of an inorganic compound such as ion and radical and polyacid, an organic compound on general principle and names, general terminology 1 and 2, unit and description method on summary, unit and the symbol for unit, number and pH, Korean mark for people's name in chemistry, names of JUPAC organic compound of summary, hydrocarbons, fused polycyclic hydrocarbons, bridged hydrocarbons, cyclic hydrocarbons with side chains, terpenes hydrocarbons, fundamental heterocyclic systems and heterocyclic spiro compounds.

Formation and decomposition of ammoniated ammonium ions

International Nuclear Information System (INIS)

Ikezoe, Yasumasa; Suzuki, Kazuya; Nakashima, Mikio; Yokoyama, Atsushi; Shiraishi, Hirotsugu; Ohno, Shin-ichi

1998-09-01

Structures, frequencies, and chemical reactions of ammoniated ammonium ions (NH 4 + .nNH 3 ) were investigated theoretically by ab initio molecular orbital calculations and experimentally by observing their formation and decomposition in a corona discharge-jet expansion process. The ab initio calculations were carried out using a Gaussian 94 program, which gave optimized structures, binding energies and harmonic vibrational frequencies of NH 4 + .nNH 3 . Effects of discharge current, the reactant gas and the diameter of the gas expanding pinhole were examined on the size n distribution of NH 4 + .nNH 3 . The results indicated that the cluster ion, in the jet expansion process, grew in size mostly equal to or less than one unit under experimental conditions employed. Effects of discharge current, pinhole diameter, flight time in vacuum and cluster size were examined on the decomposition rate of cluster ions formed. In our experimental conditions, the internal energies of cluster ions were mainly determined through exo- and/or endo-thermic reactions involved in the cluster formation process. (author)

Charles J. Pedersen's legacy to chemistry.

Science.gov (United States)

Izatt, Reed M

2017-05-09

The serendipitous discovery in 1961 of dibenzo-18-crown-6 by Charles J. Pedersen marked the beginning of research on cyclic polyether macrocyclic compounds. These compounds have a remarkably selective affinity for certain metal ions and provide a framework for studying molecular recognition processes. Pedersen's work excited much interest in the scientific community and fueled important advances in macrocyclic and supramolecular chemistry. Born in Korea of a Japanese mother and a Norwegian engineer father, he was educated in Japan and later graduated from the University of Dayton (BS, chemical engineering) and Massachusetts Institute of Technology (MS, chemistry). He worked at du Pont for 42 years as a research chemist. His research talent at du Pont earned him an appointment as a Research Associate allowing him to pursue research as he chose. This freedom served him well making it possible for him to devote all his efforts following his discovery of dibenzo-18-crown-6 until his retirement to synthesis of cyclic polyethers and evaluation of their metal ion complexation properties. His influence on macrocyclic and supramolecular chemistry has been pervasive. He was co-recipient of the 1987 Nobel Prize in chemistry for development and use of molecules with structure-specific interactions of high selectivity. The year 2017 marks the fiftieth anniversary of the publication of his first paper describing his synthesis of over 50 crown ethers.

Chemistry of groundwater discharge inferred from longitudinal river sampling

Science.gov (United States)

Batlle-Aguilar, J.; Harrington, G. A.; Leblanc, M.; Welch, C.; Cook, P. G.

2014-02-01

We present an approach for identifying groundwater discharge chemistry and quantifying spatially distributed groundwater discharge into rivers based on longitudinal synoptic sampling and flow gauging of a river. The method is demonstrated using a 450 km reach of a tropical river in Australia. Results obtained from sampling for environmental tracers, major ions, and selected trace element chemistry were used to calibrate a steady state one-dimensional advective transport model of tracer distribution along the river. The model closely reproduced river discharge and environmental tracer and chemistry composition along the study length. It provided a detailed longitudinal profile of groundwater inflow chemistry and discharge rates, revealing that regional fractured mudstones in the central part of the catchment contributed up to 40% of all groundwater discharge. Detailed analysis of model calibration errors and modeled/measured groundwater ion ratios elucidated that groundwater discharging in the top of the catchment is a mixture of local groundwater and bank storage return flow, making the method potentially useful to differentiate between local and regional sourced groundwater discharge. As the error in tracer concentration induced by a flow event applies equally to any conservative tracer, we show that major ion ratios can still be resolved with minimal error when river samples are collected during transient flow conditions. The ability of the method to infer groundwater inflow chemistry from longitudinal river sampling is particularly attractive in remote areas where access to groundwater is limited or not possible, and for identification of actual fluxes of salts and/or specific contaminant sources.

Teachers' Misconceptions about the Effects of Addition of More Reactants or Products on Chemical Equilibrium

Science.gov (United States)

Cheung, Derek; Ma, Hong-jia; Yang, Jie

2009-01-01

The importance of research on misconceptions about chemical equilibrium is well recognized by educators, but in the past, researchers' interest has centered on student misconceptions and has neglected teacher misconceptions. Focusing on the effects of adding more reactants or products on chemical equilibrium, this article discusses the various…

Summary Report for April, May and June, 1951, Chemistry Division, Section C-1

Energy Technology Data Exchange (ETDEWEB)

Manning, W. M. [Argonne National Lab. (ANL), Argonne, IL (United States). Chemistry Division; Osborne, D. W. [Argonne National Lab. (ANL), Argonne, IL (United States). Chemistry Division

1951-08-01

This is a summary report for April, May and June, 1951, in the Chemistry Division, Section C-1 of Argonne National Laboratory. Topics include Nuclear Chemistry and Radiochemistry with specifics about the following: 1) U²³⁸ (n,2n) Cross Section WIthin a Uranium Slug, and 2) Possible Occurrence of Si³² in Nature. Basic Chemistry is also covered, going into the following subjects: 1) Heats of Solution of Salts in Organic Solvents, 2) Effect of Coordination on Absorption Spectra of Anions, 3) Entropy, Enthalpy, and Heat Capacity of Thorium Dioxide from 10 to 300°K, 4) The Thermodynamics of Neptunium Ions, 5) Migration of Ions in Ion-Exchange Resins During Electrolysis, and 5) Mutual Separation of Lanthanides and Actinides by Solvent Extraction Techniques.

Studies of gas phase ion/molecule reactions by Fourier transform ion cyclotron resonance mass spectrometry

International Nuclear Information System (INIS)

Kleingeld, J.C.

1984-01-01

An important field in which Fourier-transform ion cyclotron resonance has useful applications is that of gas phase ion chemistry, the subject of this thesis. First, the general picture of ion-molecule reactions in the gas phase is discussed. Next, some positive ion-molecule reactions are described, whereas the remaining chapters deal with negative ion-molecule reactions. Most of these studies have been performed using the FT-ICR method. Reactions involving H 3 O - and NH 4 - ions are described whereas the other chapters deal with larger organic complexes. (Auth.)

Ion chemistry of 1H-1,2,3-triazole.

Science.gov (United States)

Ichino, Takatoshi; Andrews, Django H; Rathbone, G Jeffery; Misaizu, Fuminori; Calvi, Ryan M D; Wren, Scott W; Kato, Shuji; Bierbaum, Veronica M; Lineberger, W Carl

2008-01-17

A combination of experimental methods, photoelectron-imaging spectroscopy, flowing afterglow-photoelectron spectroscopy and the flowing afterglow-selected ion flow tube technique, and electronic structure calculations at the B3LYP/6-311++G(d,p) level of density functional theory (DFT) have been employed to study the mechanism of the reaction of the hydroxide ion (HO-) with 1H-1,2,3-triazole. Four different product ion species have been identified experimentally, and the DFT calculations suggest that deprotonation by HO- at all sites of the triazole takes place to yield these products. Deprotonation of 1H-1,2,3-triazole at the N1-H site gives the major product ion, the 1,2,3-triazolide ion. The 335 nm photoelectron-imaging spectrum of the ion has been measured. The electron affinity (EA) of the 1,2,3-triazolyl radical has been determined to be 3.447 +/- 0.004 eV. This EA and the gas-phase acidity of 2H-1,2,3-triazole are combined in a negative ion thermochemical cycle to determine the N-H bond dissociation energy of 2H-1,2,3-triazole to be 112.2 +/- 0.6 kcal mol-1. The 363.8 nm photoelectron spectroscopic measurements have identified the other three product ions. Deprotonation of 1H-1,2,3-triazole at the C5 position initiates fragmentation of the ring structure to yield a minor product, the ketenimine anion. Another minor product, the iminodiazomethyl anion, is generated by deprotonation of 1H-1,2,3-triazole at the C4 position, followed by N1-N2 bond fission. Formation of the other minor product, the 2H-1,2,3-triazol-4-ide ion, can be rationalized by initial deprotonation of 1H-1,2,3-triazole at the N1-H site and subsequent proton exchanges within the ion-molecule complex. The EA of the 2H-1,2,3-triazol-4-yl radical is 1.865 +/- 0.004 eV.

The Effect of Non-equilibrium Kinetics on Oxygen Chemistry in the Interstellar Medium

Science.gov (United States)

Naduvalath, Balakrishnan

2006-01-01

It has been suggested that in photon-dominated regions, oxygen chemistry is initiated by the O+H2 yields OH+H reaction. The reaction has an energy barrier of about 0.4 eV with ground state reactants and it is slow at low temperatures. There is strong experimental evidence that vibrational excitation of the H2 molecule increases the reactivity significantly. We present extensive quantum calculations of cross sections and rate coefficients for the O+H2(v) reaction for v = 0 - 3 of the H2 molecule and show that the vibrational excitation of the molecule has a significant effect on reactivity, especially at low temperatures.

Toward a Rational Design of Highly Folded Peptide Cation Conformations. 3D Gas-Phase Ion Structures and Ion Mobility Characterization

Czech Academy of Sciences Publication Activity Database

Pepin, R.; Laszlo, K. J.; Marek, Aleš; Peng, B.; Bush, M. F.; Lavanant, H.; Afonso, C.; Tureček, F.

2016-01-01

Roč. 27, č. 10 (2016), s. 1647-1660 ISSN 1044-0305 Institutional support: RVO:61388963 Keywords : peptide ions * ion mobility * collisional cross sections * density functional theory calculations * ion structures * polar effects Subject RIV: CC - Organic Chemistry Impact factor: 2.786, year: 2016

Water chemistry in Kuji river. Its spatial and seasonal variations in major ions and organic substances

International Nuclear Information System (INIS)

Niina, Toshiaki; Matsunaga, Takeshi; Amano, Hikaru

1996-02-01

As a basic research with a aim to clarify the migration behavior of radionuclides in rivers, the characteristics of dissolved ions and organic substances in river water, which characteristics may affect the behavior, was investigated. The investigation was carried out for the Kuji river in the northern Kanto district (Japan) comprising four sampling campaigns in 1994 for 10 locations from the upstream to the downstream. Concentrations of major ions, iron and manganese species and organic substances were analyzed in laboratory. Values of temperature of the water, pH, conductivity, dissolved oxygen were measured in the field. This investigation was conducted mainly under low water flow conditions of the river, while a limited number of campaigns were under high flow conditions due to precipitation events. The concentrations of major inorganic ions increased steadily toward the down-stream, resulting in approximately two times increase for the traveling distance of 100 km. They showed a seasonal variation that they were highest in the spring and lowest in the autumn when there were most concentrated precipitation events in a year. The constituents were mainly Na + , Ca 2+ , SO 4 2- and HCO 3 - , and were similar for every sampling locations and seasons. Concentrations of dissolved organic substances (carbon compounds) were lowest in the upstream and increased about twice in the downstream as well as major inorganic ions. Their level was 1-3 mg/l, which can be ranked as relatively lower in general values for fresh water environments. They were highest in the spring (average over the locations: 2.2 mg/l) and lowest in the autumn (1.3 mg/l) and also in the winter (1.3 mg/l). These results will be useful as a basic understanding of spatial and seasonal variations of river water chemistry, especially related to the organic substances which can bind with radionuclides to make a mobile complex. (author)

Magnetic resonance imaging of chemistry.

Science.gov (United States)

Britton, Melanie M

2010-11-01

Magnetic resonance imaging (MRI) has long been recognized as one of the most important tools in medical diagnosis and research. However, MRI is also well placed to image chemical reactions and processes, determine the concentration of chemical species, and look at how chemistry couples with environmental factors, such as flow and heterogeneous media. This tutorial review will explain how magnetic resonance imaging works, reviewing its application in chemistry and its ability to directly visualise chemical processes. It will give information on what resolution and contrast are possible, and what chemical and physical parameters can be measured. It will provide examples of the use of MRI to study chemical systems, its application in chemical engineering and the identification of contrast agents for non-clinical applications. A number of studies are presented including investigation of chemical conversion and selectivity in fixed-bed reactors, temperature probes for catalyst pellets, ion mobility during tablet dissolution, solvent dynamics and ion transport in Nafion polymers and the formation of chemical waves and patterns.

Negative chlorine ion chemistry in the upper stratosphere and its application to an artificially created dense electron cloud

Directory of Open Access Journals (Sweden)

S. S. Prasad

Full Text Available This paper discusses new potential reactions of chlorine-bearing anions (negative ions in the upper stratosphere. These reactions are then applied to the negative-ion chemistry following the injection of an electron cloud of very high density, of the order of 10^6-10⁷ e^- cm^-3, in the 40-45-km region. The idea is to evaluate the recently proposed scheme to mitigate ozone depletion by converting the reactive chlorine atoms at these altitudes into Cl^- ions which are unreactive towards ozone, i.e., electron scavenging of Cl. We find that the previously neglected photodetachment from Cl^- is fast. For an overhead sun, this process may have a rate coefficient of 0.08 s^-1 when multiple scattering is included. The rate could be even higher, depending on the ground albedo. Switching reaction between Cl^-·H₂O and HCl might lead to the formation of Cl^-·HCl anion. Possible reactions of Cl^-·H₂O and Cl^-·HCl with O atoms could produce ClO^- and Cl^-₂. The production of ClO^- in this manner is significant because Cl^- having a high photodetachment rate constant would be regenerated in the very likely reactions of ClO^- with O. When these possibilities are considered, then it is found that the chlorine anions may not be the major ions inside the electron cloud due to the rapid photodetachment from Cl^-. Furthermore, in such a cloud, there may be the hazard that the Cl^--Cl^-·H₂O-ClO^--Cl^- cycle amounts to catalytic destruction of two O atoms. Thus, the scheme could be risky if practised in the altitude region where atomic oxygen is an important constituent. Similar conclusions apply even if the ClO^- species forms ClO^-₃ by three-body association with O₂

Polyimide resin composites via in situ polymerization of monomeric reactants

Science.gov (United States)

Cavano, P. J.

1974-01-01

Thermo-oxidatively stable polyimide/graphite-fiber composites were prepared using a unique in situ polymerization of monomeric reactants directly on reinforcing fibers. This was accomplished by using an aromatic diamine and two ester-acids in a methyl alcohol solvent, rather than a previously synthesized prepolymer varnish, as with other A-type polyimides. A die molding procedure was developed and a composite property characterization conducted with high modulus graphite fiber tow. Flexure, tensile, compressive, and shear tests were conducted at temperatures from 72 to 650 F on laminates before and after exposures at the given temperatures in an air environment for times up to 1000 hours. The composite material was determined to be oxidatively, thermally, and hydrolytically stable.

Assessing toxicity of varying major ion concentrations to marine organisms

International Nuclear Information System (INIS)

Mount, D.R.; Quast, W.

1993-01-01

Recent regulatory developments have required that produced waters discharged in the Gulf of Mexico be monitored for toxicity to marine organisms. While produced water may contain a variety of indigenous and introduced chemicals, virtually all have moderate to high concentrations of major ions. Although seawater is also rich in these ions, excessive salinity can cause toxicity to marine organisms. Perhaps more importantly, toxicity to marine organisms can be caused by deviations from normal ion ratios even if the total salinity is within organism tolerances. To provide a better understanding of marine organism responses to variations in major ion concentrations, the authors conducted a series of laboratory experiments to quantify the responses of mysid shrimp (Mysidopsis bahia) and sheepshead minnows (Cyprinodon variegatus) to modifications of normal seawater chemistry. Acute testing included both increasing and decreasing the concentrations of individual ions relative to seawater, as well as altering total salinity. Results show these organisms can be adversely affected by this altered chemistry and their sensitivity is dependent upon the individual ions that are manipulated. Results from these studies are being incorporated into an overall strategy for evaluating the influence of major ion chemistry on produced water toxicity tests

The Generation of Dehydroalanine Residues in Protonated Polypeptides: Ion/Ion Reactions for Introducing Selective Cleavages

Science.gov (United States)

Peng, Zhou; Bu, Jiexun; McLuckey, Scott A.

2017-09-01

We examine a gas-phase approach for converting a subset of amino acid residues in polypeptide cations to dehydroalanine (Dha). Subsequent activation of the modified polypeptide ions gives rise to specific cleavage N-terminal to the Dha residue. This process allows for the incorporation of selective cleavages in the structural characterization of polypeptide ions. An ion/ion reaction within the mass spectrometer between a multiply protonated polypeptide and the sulfate radical anion introduces a radical site into the multiply protonated polypeptide reactant. Subsequent collisional activation of the polypeptide radical cation gives rise to radical side chain loss from one of several particular amino acid side chains (e.g., leucine, asparagine, lysine, glutamine, and glutamic acid) to yield a Dha residue. The Dha residues facilitate preferential backbone cleavages to produce signature c- and z-ions, demonstrated with cations derived from melittin, mechano growth factor (MGF), and ubiquitin. The efficiencies for radical side chain loss and for subsequent generation of specific c- and z-ions have been examined as functions of precursor ion charge state and activation conditions using cations of ubiquitin as a model for a small protein. It is noted that these efficiencies are not strongly dependent on ion trap collisional activation conditions but are sensitive to precursor ion charge state. Moderate to low charge states show the greatest overall yields for the specific Dha cleavages, whereas small molecule losses (e.g., water/ammonia) dominate at the lowest charge states and proton catalyzed amide bond cleavages that give rise to b- and y-ions tend to dominate at high charge states. [Figure not available: see fulltext.

Multitracers in chemistry and biochemistry

International Nuclear Information System (INIS)

Ambe, F.

2000-01-01

The multitracer technique using heavy-ion reactions has successfully developed in the last decade and is expected to widen its application in chemistry, biochemistry and other fields with technical improvement in future. Several examples of recent application are reviewed and development in the coming century is forecast. (author)

Visualizing Chemistry: Investigations for Teachers.

Science.gov (United States)

Ealy, Julie B.; Ealy, James L., Jr.

This book contains 101 investigations for chemistry classrooms. Topics include: (1) Physical Properties; (2) Reactions of Some Elements; (3) Reactions Involving Gases; (4) Energy Changes; (5) Solutions and Solubility; (6) Transition Metals and Complex Ions; (7) Kinetics and Equilibrium; (8) Acids and Bases; (9) Oxidation-Reduction; (10)…

Reactions of metal ions and their clusters in the gas phase using laser ionization: ion cyclotron resonance spectroscopy

International Nuclear Information System (INIS)

Freiser, B.S.

1981-04-01

Two subjects are discussed in this report: advances in proposed studies on metal ion chemistry and expansion of laboratory facilities. The development of a combined pulsed laser source-ion cyclotron resonance spectrometer has proven to be a convenient and powerful method for generating metal ions and for studying their subsequent chemistry in the gas phase. The main emphasis of this research has been on the application of metal ions as a selective chemical ionization reagents and progress in this area are discussed. The goal is to identify trends in reactivity i.e. mechanisms useful in interpreting the chemical ionization spectra of unknown compounds and to test for the functional group selectivity of the various metal ions. The feasibility of these goals have been demonstrated in extensive studies on Cu + with esters and ketones, on Fe + with ethers, ketones, and hydrocarbons, and on Ti + with hydrocarbons. In addition, preliminary results on sulfur containing compounds and on a variety of other metallic ions have been obtained. Laboratory facilities were expanded from one ion cyclotron resonance (ICR) spectrometer to two, plus a third instrument the Fourier Transform Ion Cyclotron Resonance (FTICR) spectrometer

Analysis of abused drugs by selected ion monitoring: quantitative comparison of electron impact and chemical ionization

International Nuclear Information System (INIS)

Foltz, R.L.; Knowlton, D.A.; Lin, D.C.K.; Fentiman, A.F. Jr.

1975-01-01

A comparison was made of the relative sensitivities of electron impact and chemical ionization when used for selected ion monitoring analysis of commonly abused drugs. For most of the drugs examined chemical ionization using ammonia as the reactant gas gave the largest single m/e ion current response per unit weight of sample. However, if maximum sensitivity is desired it is important to evaluate electron impact and chemical ionization with respect to both maximum response and degree of interference from background and endogenous materials

Ion measurements in premixed methane-oxygen flames

KAUST Repository

Alquaity, Awad; Hourani, Nadim; Chahine, May; Selim, Hatem; Sarathy, Mani; Farooq, Aamir

2014-01-01

Mass Spectrometer (MBMS) is utilized to measure ion concentration profiles in premixed methane-oxygen-argon burner-stabilized flames. Lean, stoichiometric and rich flames at atmospheric pressure are used to study the dependence of ion chemistry

Spectroscopy and chemistry of uranium IV

International Nuclear Information System (INIS)

Folcher, G.; Rigny, P.

1980-06-01

Different fundamental research papers on uranium IV are presented, some were never edited. Molecular spectroscopy was used for identification and structural study of uranium IV in aqueous or organic solutions. The fields studied are: coordination, stereochemistry, electronic structure and chemical properties. For interpretation of results some studies were made with solid compounds or with thorium compounds or thorium complexes. Knowledge of actinides chemistry is improved, uranium and thorium being models for 5 f ions, extractive chemistry is better understood and new applications are possible [fr

Progress report, Chemistry and Materials Division, April 1 to June 30, 1976

International Nuclear Information System (INIS)

1976-07-01

Preliminary results are reported on research covering such topics as ion penetration, electron microscopy, radiation damage and metal physics, nuclear methods of analysis, analytical chemistry, hydrogen-deuterium exchange, radiation chemistry, and corrosion (primarily of zirconium alloys). (E.C.B.)

The influence of tertiary butyl hydrazine as a co-reactant on the atomic layer deposition of silver

Energy Technology Data Exchange (ETDEWEB)

Golrokhi, Zahra; Marshall, Paul A.; Romani, Simon [Centre for Materials and Structures, School of Engineering,The University of Liverpool, Liverpool L69 3GH (United Kingdom); Rushworth, Simon [EpiValence, The Wilton Centre, Redcar, Cleveland, TS10 4RF (United Kingdom); Chalker, Paul R. [Centre for Materials and Structures, School of Engineering,The University of Liverpool, Liverpool L69 3GH (United Kingdom); Potter, Richard J., E-mail: rjpott@liverpool.ac.uk [Centre for Materials and Structures, School of Engineering,The University of Liverpool, Liverpool L69 3GH (United Kingdom)

2017-03-31

Highlights: • We demonstrate metallic silver growth by direct liquid injection thermal ALD. • A substituted hydrazine is used as a powerful reducing agent for the first time. • The hydrazine extends the ALD temperature window compared with alcohol. • Hydrazine promotes a more planar growth mode compared to alcohol. • Film adhesion is improved using hydrazine compared with alcohol. - Abstract: Ultra-thin conformal silver films are the focus of development for applications such as anti-microbial surfaces, optical components and electronic devices. In this study, metallic silver films have been deposited using direct liquid injection thermal atomic layer deposition (ALD) using (hfac)Ag(1,5-COD) ((hexafluoroacetylacetonato)silver(I)(1,5-cyclooctadiene)) as the metal source and tertiary butyl hydrazine (TBH) as a co-reactant. The process provides a 23 °C wide ‘self-limiting’ ALD temperature window between 105 and 128 °C, which is significantly wider than is achievable using alcohol as a co-reactant. A mass deposition rate of ∼20 ng/cm{sup 2}/cycle (∼0.18 Å/cycle) is observed under self-limiting growth conditions. The resulting films are crystalline metallic silver with a near planar film-like morphology which are electrically conductive. By extending the temperature range of the ALD window by the use of TBH as a co-reactant, it is envisaged that the process will be exploitable in a range of new low temperature applications.

Wet-cleaning of MgO(001): Modification of surface chemistry and effects on thin film growth investigated by x-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy

OpenAIRE

Le Febvrier, Arnaud; Jensen, Jens; Eklund, Per

2017-01-01

The effect of the wet-cleaning process using solvents and detergent on the surface chemistry of MgO(001) substrate for film deposition was investigated. Six different wet-cleaning processes using solvent and detergent were compared. The effect on film growth was studied by the example system ScN. The surface chemistry of the cleaned surface was studied by x-ray photoelectron spectroscopy and the film/substrate interface after film growth was investigated by time-of-flight secondary ion mass s...

Department of Chemistry Progress Report (January 1989 - December 1991)

International Nuclear Information System (INIS)

1992-03-01

The research activities in Department of Chemistry during the last 3 years from 1989 to 1991 were compiled. The researches and works of Department of Chemistry are mainly those concerned with important basic matters and items which are committed to further development of nuclear fuels and materials, to establishment of the nuclear fuel cycle, and to new development of advanced nuclear researches such as laser, ion-beam and photo-chemistry. Intensive efforts were also made on chemical analysis service of various fuels and nuclear materials. (author)

Ion-molecule reactions in the binary mixture of ethylene oxide and trioxane, 1

International Nuclear Information System (INIS)

Kumakura, Minoru; Sugiura, Toshio.

1977-01-01

The formation mechanism of protonated molecular ions by cross-reactions in ethylene oxide-trioxane mixtures has been studied with use of a modified time-of-flight mass spectrometer. The precursors of the product ions were determined by analysis of the fine structure of their ionization efficiency curves using deuterated ethylene oxide. Protonated ethylene oxide is formed by the hydrogen atom transfer reaction of ethylene oxide molecular ion with trioxane, and protonated trioxane by the proton transfer reaction of CHO + (from ethylene oxide) with trioxane. In the ion-molecule reactions of ethylene-d 4 oxide-trioxane mixtures, appreciable isotope effect was observed. The CHO + from ethylene oxide is an important reactant ion as compared with that from trioxane in the proton transfer reaction, and CHO + from ethylene oxide was suggested as a thermal reactive ion. The order of proton affinity could be estimated from the proton transfer reactions involving CHO + . It was found that the proton affinity of trioxane is smaller than that of ethylene oxide. (auth.)

Electron capture by Ne3+ ions from atomic hydrogen

International Nuclear Information System (INIS)

Rejoub, R.; Bannister, M.E.; Havener, C.C.; Savin, D.W.; Verzani, C.J.; Wang, J.G.; Stancil, P.C.

2004-01-01

Using the Oak Ridge National Laboratory ion-atom merged-beam apparatus, absolute total electron-capture cross sections have been measured for collisions of Ne 3+ ions with hydrogen (deuterium) atoms at energies between 0.07 and 826 eV/u. Comparison to previous measurements shows large discrepancies between 50 and 400 eV/u. Previously published molecular-orbital close-coupling (MOCC) calculations were performed over limited energy ranges, but show good agreement with the present measurements. Here MOCC calculations are presented for energies between 0.01 and 1000 eV/u for collisions with both H and D. For energies below ∼1 eV/u, an enhancement in the magnitude of both the experimental and theoretical cross sections is observed which is attributed to the ion-induced dipole attraction between the reactants. Below ∼4 eV/u, the present calculations show a significant target isotope effect

Electron capture by Ne3+ ions from atomic hydrogen

Science.gov (United States)

Rejoub, R.; Bannister, M. E.; Havener, C. C.; Savin, D. W.; Verzani, C. J.; Wang, J. G.; Stancil, P. C.

2004-05-01

Using the Oak Ridge National Laboratory ion-atom merged-beam apparatus, absolute total electron-capture cross sections have been measured for collisions of Ne3+ ions with hydrogen (deuterium) atoms at energies between 0.07 and 826 eV/u . Comparison to previous measurements shows large discrepancies between 50 and 400 eV/u . Previously published molecular-orbital close-coupling (MOCC) calculations were performed over limited energy ranges, but show good agreement with the present measurements. Here MOCC calculations are presented for energies between 0.01 and 1000 eV/u for collisions with both H and D. For energies below ˜1 eV/u , an enhancement in the magnitude of both the experimental and theoretical cross sections is observed which is attributed to the ion-induced dipole attraction between the reactants. Below ˜4 eV/u , the present calculations show a significant target isotope effect.

Single-ion conducting diblock terpolymers for lithium-ion batteries

Science.gov (United States)

Morris, Melody; Epps, Thomas H., III

Block polymer (BP) electrolytes provide an attractive route to overcome the competing constraints of high conductivity and mechanical/thermal stability in lithium-ion batteries through nanoscale self-assembly. For example, macromolecules can be engineered such that one domain conducts lithium ions and the other prevents lithium dendrite formation. Herein, we report on the behavior of a single-ion conducting BP electrolyte that was designed to facilitate the transport of lithium ions. These polymers differ from traditional salt-doped BP electrolytes, which require the addition of a lithium salt to bestow conductivity and typically suffer from substantial counterion motion that reduces efficiency. New single-ion BPs were synthesized, and the nanoscale morphologies were determined using small angle X-ray scattering and transmission electron microscopy. Electrolyte performance was measured using AC impedance spectroscopy and DC polarization, and the results were correlated to nanoscale morphology and ion content. Enhanced physical understanding of single-ion BPs was gained by connecting the ion mobility to the chemistry, chain structure, and ion content of the single-ion BP. These studies can be applied to other charged-neutral block polymers to elucidate the effects of ion content on self-assembly and macroscopic properties.

2016 Nobel Prize in Chemistry1

Indian Academy of Sciences (India)

open-up a new area of chemistry in a paradigm shifting man- ner. .... tives that undergo facile reactions, in the presence of metal-ion chelation with ... shuttle moves from one station to .... ATP hydrolysis and the rotor action of the enzyme. In the ...

Anodic behaviour of the stainless steel AISI 430 in aqueous solutions of chloride and sulphate ions

International Nuclear Information System (INIS)

Sebrao, M.Z.

1982-01-01

The kinetics of the dissolution of stainless steel AISI 430 in the presence of chloride and sulphate ions has been studied in terms of the ion concentration, the pH variation, and the velocity of the working electrode. The experimental method utilized was the potentiostatic anodic polarization, and the reactants used were NaCl and Na 2 SO 4 at room temperature. Atomic Absorption spectrophotometry and Auger Electrons spectroscopy (AES) analyses were made in order to support the interpretation of results obtained by means of the potentiostatic polarization method. (author)

Solution chemistry

Energy Technology Data Exchange (ETDEWEB)

None

1973-07-01

Research progress is reported on studies in heavy element chemistry. Topics considered are: synergistic complexes of plutonyl ion; water uptake in synergistic systems; formation constants of some uranyl BETA -diketone complexes; thermodynamic acid dissociation constants of BETA -diketones; thermodynamic formation constants of uranyl BETA -diketonates; thiocyanate complexes of some trivalent lanthanides and actinides; stability constants of actinide complexes using dinonyl naphthalenesulfonic acid extraction; TBP extraction of actinides; stability constants of complexes of Pu(III) with 5- sulfosalicycllc acid; and solvent extraction behavior of Pu( VII). (DHM)

Staged membrane oxidation reactor system

Science.gov (United States)

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

2012-09-11

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

Use of periodic variations of reactant concentrations in time resolved ftir studies of CO oxidation on Pd/ZrO{sub 2} catalysts

Energy Technology Data Exchange (ETDEWEB)

Ortelli, E; Wokaun, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1999-08-01

Sine wave modulation of feed concentrations was used to induce dynamic variations in the concentrations of products, intermediates and reactants, which were monitored in a diffuse reflectance FTIR (DRIFT) cell. The phase shift {Delta}{phi} between the external perturbation of the feed and the signals of products, intermediates and reactants was examined in dependence on the modulation frequency {omega}. Reaction constants of a simplified model mechanism were estimated for a Pd{sub 25}Zr{sub 75} based catalyst for CO oxidation. (author) 1 fig., 2 refs.

Growing interstellar molecules with ion-molecule reactions

International Nuclear Information System (INIS)

Bohme, D.K.

1989-01-01

Laboratory measurements of gas-phase ion-molecule reactions continue to provide important insights into the chemistry of molecular growth in interstellar environments. It is also true that the measurements are becoming more demanding as larger molecules capture our interest. While some of these measurements are motivated by current developments in chemical models of interstellar environments or by new molecular observations by astronomers, others explore novel chemistry which can lead to predictions of new interstellar molecules. Here the author views the results of some recent measurements, taken in the Ion Chemistry Laboratory at York University with the SIFT technique, which address some of the current needs of modellers and observers and which also provide some new fundamental insight into molecular growth, particularly when it occurs in the presence of large molecules such as PAH molecules which are now thought to have a major influence on the chemistry of interstellar environments in which they are present

Some novel diagnostic techniques for plasma chemistry

International Nuclear Information System (INIS)

Kaufman, M.

1976-01-01

In order to probe the mechanisms of chemical transformations in electric discharges it is most useful to monitor concentrations of reactants, products and reactive intermediates as a function of discharge parameters. Mass spectrometry, a popular technique for observing intermediates in chemical reactions, meets with particular difficulty when applied to discharges, due to the presence of excited molecules as well as free radicals in such systems. Molecular beam analysis, a synthesis of mass spectrometry with molecular beam measurements of electric and magnetic moments and velocity distributions, is a technique developed in the laboratory which offers distinct advantages for the analysis of intermediates in electric discharges. In low pressure discharges, end-product analysis can be facilitated by sample compression. A chromatographic sampling system which employs compression in order to achieve sensitivity has been developed and evaluated. There is some question concerning the appropriate discharge parameters to be employed in correlating measured variations in concentrations. An investigation is being made of the use of discharge 'actinometers' as a means of measuring the intensity of electric discharges. In discharges the intensity (number and energy of the electrons) and the chemistry are strongly coupled. Thus, it is necessary that the actinometer be present in the reactor; it is not permissible to substitute vessels as is customary in photochemical investigations. Since the actinometer is to measure only the discharge intensity, it must not participate in any chemical reactions with molecules and intermediates in the discharge. Finally, the ratio of the rates of the primary interactions of the actinometer and reactant with the discharge must be independent of discharge parameters. (author)

Computational radiation chemistry: the emergence of a new field

International Nuclear Information System (INIS)

Bartczak, W.M.; Kroh, J.

1991-01-01

The role of the computer experiment as an information source, which is complementary to the ''real'' experiment in radiation chemistry, is discussed. The discussion is followed by a brief review of some of the simulation techniques, which have been recently applied to the problems of radiation chemistry: ion recombination in spurs and tracks of ionization, electron tunnelling in low-temperature glasses, electron localization in disordered media. (author)

Modern trends in contemporary chemistry

International Nuclear Information System (INIS)

Javed, H.; Pervez, H.; Qadeer, R.

1993-01-01

This publication contains a collection of papers presented at symposium on M odern Trends in Contemporary Chemistry , that was held in Islamabad, Pakistan, March 6-8, 1990. The symposium was divided into five sections for presentation of about 55 scientific and technical papers and 6 review papers. The contents of these papers were of good quality in the widespread concern in new trends of chemistry. The six reviews papers covered fields of ortho metallation reactions, evaluation of heterogeneous electron transfer rate contents, macro reticular ion-exchange resins, spectrochemical analytical techniques, liquid crystal-high technology materials for practical applications and trends in advanced ceramics. (A.B.)

Mass spectrometry in clinical chemistry

International Nuclear Information System (INIS)

Pettersen, J.E.

1977-01-01

A brief description is given of the functional elements of a mass spectrometer and of some currently employed mass spectrometric techniques, such as combined gas chromatography-mass spectrometry, mass chromatography, and selected ion monitoring. Various areas of application of mass spectrometry in clinical chemistry are discussed, such as inborn errors of metabolism and other metabolic disorders, intoxications, quantitative determinations of drugs, hormones, gases, and trace elements, and the use of isotope dilution mass spectrometry as a definitive method for the establishment of true values for concentrations of various compounds in reference sera. It is concluded that mass spectrometry is of great value in clinical chemistry. (Auth.)

Actinide Sciences at ITN - Basic Studies in Chemistry with Potential Interest for Partitioning, Fuel Fabrication and More

International Nuclear Information System (INIS)

Almeida, M.; Dias, M.; Goncalves, A.P.; Henriques, M.S.; Lopes, E.B.; Pereira, L.C.J.; Santos, I.C.; Verbovytskyy, Y.; Waerenborgh, J.C.; Branco, J.B.; Carretas, J.M.; Cruz, A.; Ferreira, A.C.; Gasche, T.A.; Leal, J.P.; Lopes, G.; Lourenco, C.; Marcalo, J.; Maria, L.; Monteiro, B.; Mora, E.; Pereira, C.C.L.; Paiva, I.

2010-01-01

The current activities in the area of actinide chemistry at ITN, comprising basic research studies in inorganic and organometallic chemistry, catalysis, gas-phase ion chemistry, thermochemistry, and solid state chemistry, are briefly described. Actinide (and lanthanide) chemistry studies at ITN will be pursued connecting basic research with potential applications in nuclear and non-nuclear areas. (authors)

Water chemistry in Kuji river. Its spatial and seasonal variations in major ions and organic substances

Energy Technology Data Exchange (ETDEWEB)

Niina, Toshiaki; Matsunaga, Takeshi; Amano, Hikaru [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

1996-02-01

As a basic research with a aim to clarify the migration behavior of radionuclides in rivers, the characteristics of dissolved ions and organic substances in river water, which characteristics may affect the behavior, was investigated. The investigation was carried out for the Kuji river in the northern Kanto district (Japan) comprising four sampling campaigns in 1994 for 10 locations from the upstream to the downstream. Concentrations of major ions, iron and manganese species and organic substances were analyzed in laboratory. Values of temperature of the water, pH, conductivity, dissolved oxygen were measured in the field. This investigation was conducted mainly under low water flow conditions of the river, while a limited number of campaigns were under high flow conditions due to precipitation events. The concentrations of major inorganic ions increased steadily toward the down-stream, resulting in approximately two times increase for the traveling distance of 100 km. They showed a seasonal variation that they were highest in the spring and lowest in the autumn when there were most concentrated precipitation events in a year. The constituents were mainly Na{sup +}, Ca{sup 2+}, SO{sub 4}{sup 2-} and HCO{sub 3}{sup -}, and were similar for every sampling locations and seasons. Concentrations of dissolved organic substances (carbon compounds) were lowest in the upstream and increased about twice in the downstream as well as major inorganic ions. Their level was 1-3 mg/l, which can be ranked as relatively lower in general values for fresh water environments. They were highest in the spring (average over the locations: 2.2 mg/l) and lowest in the autumn (1.3 mg/l) and also in the winter (1.3 mg/l). These results will be useful as a basic understanding of spatial and seasonal variations of river water chemistry, especially related to the organic substances which can bind with radionuclides to make a mobile complex. (author).

Primary processes and ionic reactions in the chemistry of recoiling silicon atoms

International Nuclear Information System (INIS)

Gaspar, P.P.; Garmestani, K.; Boo, B.H.; Stewart, G.W.

1993-01-01

Hot atom chemistry has permitted the elucidation of the chemistry of free atoms, and these include the polyvalent atoms of refractory group 14 elements, that is, carbon, silicon and germanium. Since no more than two bonds are formed normally in a single reactive collision of free atoms, the study on the chemistry of atoms like C, Si and Ge that require the formation of more than two bonds to saturate their chemical valence necessarily involves the study of reactive intermediates. By the studies on the chemistry of recoiling 31 Si atoms, the mechanistic conclusions reached are reported. The most important unanswered questions concerning the reaction of recoiling 31 Si atoms in the systems are shown, and progress has been made toward the answering. By using tetramethyl silane as a trapping agent for silicon ions, it has been established that the reaction of 31 Si ions contributes significantly to the formation of products in recoil systems. The studies by various researchers on this theme are reported. (K.I.)

Redox Chemistry of Molybdenum Trioxide for Ultrafast Hydrogen-Ion Storage.

Science.gov (United States)

Wang, Xianfu; Xie, Yiming; Tang, Kai; Wang, Chao; Yan, Chenglin

2018-05-11

Hydrogen ions are ideal charge carriers for rechargeable batteries due to their small ionic radius and wide availability. However, little attention has been paid to hydrogen-ion storage devices because they generally deliver relatively low Coulombic efficiency as a result of the hydrogen evolution reaction that occurs in an aqueous electrolyte. Herein, we successfully demonstrate that hydrogen ions can be electrochemically stored in an inorganic molybdenum trioxide (MoO 3 ) electrode with high Coulombic efficiency and stability. The as-obtained electrode exhibits ultrafast hydrogen-ion storage properties with a specific capacity of 88 mA hg -1 at an ultrahigh rate of 100 C. The redox reaction mechanism of the MoO 3 electrode in the hydrogen-ion cell was investigated in detail. The results reveal a conversion reaction of the MoO 3 electrode into H 0.88 MoO 3 during the first hydrogen-ion insertion process and reversible intercalation/deintercalation of hydrogen ions between H 0.88 MoO 3 and H 0.12 MoO 3 during the following cycles. This study reveals new opportunities for the development of high-power energy storage devices with lightweight elements. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Major ion chemistry of surface water in the Xilin River Basin and the possible controls].

Science.gov (United States)

Tang, Xi-Wen; Wu, Jin-Kui

2014-01-01

Under the increasing pressure of water shortage and steppe degradation, information on the hydrological cycle in the steppe region in Inner Mongolia is urgently needed. Major ions are widely used to identify the hydrological processes in a river basin. Based on the analysis results of 239 river water samples collected in 13 sections along the Xilin River system during 2006 to 2008, combined with data from groundwater and precipitation samples collected in the same period and the meteorological and hydrological data in the Xilin River Basin, hydrochemical characteristics and the chemistry of major ions of the Xilin River water have been studied by means of Piper triangle plots and Gibbs diagrams. The results showed that: (1) the total dissolved solid (TDS) in river water mainly ranged between 136.7 mg x L(-1) and 376.5 mg x L(-1), and (2) it had an increasing trend along the river flow path. (3) The major cations and anions of river water were Ca2+ and HCO3-, respectively, and the chemical type of the river water varied from HCO3- -Ca2+ in the headwater area to HCO(3-)-Ca2+ Mg2+ in the lower part. (4) The variation in the concentration of major irons in surface water was not significant at the temporal scale. Usually, the concentration values of major irons were much higher in May than those in other months during the runoff season, while the values were a bit lower in 2007 than those in 2006 and 2008. Except for SO4(2-), the concentrations of other ions such as Ca2+, Na+, Mg2+, K+, Cl- and HCO3- showed a upward trend along the river flow path. Comparing major ion concentrations of the river water with those of local groundwater and precipitation, the concentration in river water was between those of precipitation and groundwater but was much closer to the concentration of groundwater. This indicated that the surface water was recharged by a mixture of precipitation and groundwater, and groundwater showed a larger impact. The Gibbs plot revealed that the chemical

Multicomponent Reactions in Ligation and Bioconjugation Chemistry.

Science.gov (United States)

Reguera, Leslie; Méndez, Yanira; Humpierre, Ana R; Valdés, Oscar; Rivera, Daniel G

2018-05-25

Multicomponent reactions (MCRs) encompass an exciting class of chemical transformations that have proven success in almost all fields of synthetic organic chemistry. These convergent procedures incorporate three or more reactants into a final product in one pot, thus combining high levels of complexity and diversity generation with low synthetic cost. Striking applications of these processes are found in heterocycle, peptidomimetic, and natural product syntheses. However, their potential in the preparation of large macro- and biomolecular constructs has been realized just recently. This Account describes the most relevant results of our group in the utilization of MCRs for ligation/conjugation of biomolecules along with significant contributions from other laboratories that validate the utility of this special class of bioconjugation process. Thus, MCRs have proven to be efficient in the ligation of lipids to peptides and oligosaccharides as well as the ligation of steroids, carbohydrates, and fluorescent and affinity tags to peptides and proteins. In the field of glycolipids, we highlight the power of isocyanide-based MCRs with the one-pot double lipidation of glycan fragments functionalized as either the carboxylic acid or amine. In peptide chemistry, the versatility of the multicomponent ligation strategy is demonstrated in both solution-phase lipidation protocols and solid-phase procedures enabling the simultaneous lipidation and biotinylation of peptides. In addition, we show that MCRs are powerful methods for synchronized lipidation/labeling and macrocyclization of peptides, thus accomplishing in one step what usually requires long sequences. In the realm of protein bioconjugation, MCRs have also proven to be effective in labeling, site-selective modification, immobilization, and glycoconjugation processes. For example, we illustrate a successful application of multicomponent polysaccharide-protein conjugation with the preparation of multivalent

Actinide chemistry in the far field

International Nuclear Information System (INIS)

Livens, F.R.; Morris, K.; Parkman, R.; Moyes, L.

1996-01-01

The environmental chemistry of the actinides is complicated due both to the extensive redox and coordination chemistry of the elements and also to the complexity of the reactive phases encountered in natural environments. In the far field, interactions with reactive surfaces, coatings and colloidal particles will play a crucial role in controlling actinide mobility. By virtue of both their abundance and reactivity; clays and other layer aluminosilicate minerals, hydrous oxides and organic matter (humic substances) are all identified as having the potential to react with actinide ions and some possible modes of interaction are described, together with experimental evidence for their occurrence. (author)

Lanthanide and actinide ion phytoextraction: investigations of biosorption chemistry

International Nuclear Information System (INIS)

Rayson, Gary D.; Serna, Debbie D.; Moore, Jessica L.

2009-01-01

Investigations of the chemical interactions responsible for passive biosorption of a lanthanide (Eu (III)) and an actinide (U (VI)) metal ion is described. Spectroscopic methods for the elucidation of chemical functionalities on cultured anther cell walls from the plant Datura innoxia include metal ion luminescence measurements. These have revealed the presence of distinctly different binding environments involving one, two, and three carboxylate moieties for Eu (III) and UO 2 2+ binding and sulfonates (or sulfates) and phosphates for sequestration of Eu (III) on the uranyl ion, respectively. Additional investigations of the apparent affinities of these metals to this material have revealed the presence of both low and high affinity sites for the binding of Eu (III) with weak electrostatic attractions proposed for binding at high metal concentrations (i.e., low affinities) and surface coordination interactions responsible for higher affinities. Conversely, total uranyl ion binding revealed only a single distribution of interactions based on apparent affinities. (author)

Solution chemistry and separation of metal ions in leached solution

International Nuclear Information System (INIS)

Shibata, J.

1991-01-01

The method to presume a dissolved state of metal ions in an aqueous solution and the technology to separate and concentrate metal ions in a leached solution are described in this paper. It is very important for the separation of metal ions to know the dissolved state of metal ions. If we know the composition of an aqueous solution and the stability constants of metal-ligand complexes, we can calculate and estimate the concentration of each species in the solution. Then, we can decide the policy to separate and concentrate metal ions. There are several methods for separation and purification; hydroxide precipitation method, sulfide precipitation method, solvent extraction method and ion exchange resin method. Solvent extraction has been used in purification processes of copper refinery, uranium refinery, platinum metal refinery and rare earth metal refinery. Fundamental process of solvent extraction, a kind of commercial extractants, a way of determining a suitable extractant and an equipment are discussed. Finally, it will be emphasized how the separation of rare earths is improved in solvent extraction. (author) 21 figs., 8 tabs., 8 refs

Astronomical chemistry.

Science.gov (United States)

Klemperer, William

2011-01-01

The discovery of polar polyatomic molecules in higher-density regions of the interstellar medium by means of their rotational emission detected by radioastronomy has changed our conception of the universe from essentially atomic to highly molecular. We discuss models for molecule formation, emphasizing the general lack of thermodynamic equilibrium. Detailed chemical kinetics is needed to understand molecule formation as well as destruction. Ion molecule reactions appear to be an important class for the generally low temperatures of the interstellar medium. The need for the intrinsically high-quality factor of rotational transitions to definitively pin down molecular emitters has been well established by radioastronomy. The observation of abundant molecular ions both positive and, as recently observed, negative provides benchmarks for chemical kinetic schemes. Of considerable importance in guiding our understanding of astronomical chemistry is the fact that the larger molecules (with more than five atoms) are all organic.

Aqueous vanadium ion dynamics relevant to bioinorganic chemistry: A review.

Science.gov (United States)

Kustin, Kenneth

2015-06-01

Aqueous solutions of the four highest vanadium oxidation states exhibit four diverse colors, which only hint at the diverse reactions that these ions can undergo. Cationic vanadium ions form complexes with ligands; anionic vanadium ions form complexes with ligands and self-react to form isopolyanions. All vanadium species undergo oxidation-reduction reactions. With a few exceptions, elucidation of the dynamics of these reactions awaited the development of fast reaction techniques before the kinetics of elementary ligation, condensation, reduction, and oxidation of the aqueous vanadium ions could be investigated. As the biological roles played by endogenous and therapeutic vanadium expand, it is appropriate to bring the results of the diverse kinetics studies under one umbrella. To achieve this goal this review presents a systematic examination of elementary aqueous vanadium ion dynamics. Copyright © 2014 Elsevier Inc. All rights reserved.

General Synthesis of Transition-Metal Oxide Hollow Nanospheres/Nitrogen-Doped Graphene Hybrids by Metal-Ammine Complex Chemistry for High-Performance Lithium-Ion Batteries.

Science.gov (United States)

Chen, Jiayuan; Wu, Xiaofeng; Gong, Yan; Wang, Pengfei; Li, Wenhui; Mo, Shengpeng; Peng, Shengpan; Tan, Qiangqiang; Chen, Yunfa

2018-02-09

We present a general and facile synthesis strategy, on the basis of metal-ammine complex chemistry, for synthesizing hollow transition-metal oxides (Co 3 O 4 , NiO, CuO-Cu 2 O, and ZnO)/nitrogen-doped graphene hybrids, potentially applied in high-performance lithium-ion batteries. The oxygen-containing functional groups of graphene oxide play a prerequisite role in the formation of hollow transition-metal oxides on graphene nanosheets, and a significant hollowing process occurs only when forming metal (Co 2+ , Ni 2+ , Cu 2+ , or Zn 2+ )-ammine complex ions. Moreover, the hollowing process is well correlated with the complexing capacity between metal ions and NH 3 molecules. The significant hollowing process occurs for strong metal-ammine complex ions including Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ ions, and no hollow structures formed for weak and/or noncomplex Mn 2+ and Fe 3+ ions. Simultaneously, this novel strategy can also achieve the direct doping of nitrogen atoms into the graphene framework. The electrochemical performance of two typical hollow Co 3 O 4 or NiO/nitrogen-doped graphene hybrids was evaluated by their use as anodic materials. It was demonstrated that these unique nanostructured hybrids, in contrast with the bare counterparts, solid transition-metal oxides/nitrogen-doped graphene hybrids, perform with significantly improved specific capacity, superior rate capability, and excellent capacity retention. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics of the glucose/glycine Maillard reaction pathways: influences of pH and reactant initial concentrations

NARCIS (Netherlands)

Martins, S.I.F.S.; Boekel, van M.A.J.S.

2005-01-01

A previously proposed kinetic model for the glucose/glycine Maillard reaction pathways has been validated by changing the initial pH (4.8, 5.5, 6.0, 6.8 and 7.5) of the reaction and reactant initial concentrations (1:2 and 2:1 molar ratios were compared to the 1:1 ratio). The model consists of 10

Measurements of Positively Charged Ions in Premixed Methane-Oxygen Atmospheric Flames

KAUST Repository

Alquaity, Awad

2016-08-22

Cations and anions are formed as a result of chemi-ionization processes in combustion systems. Electric fields can be applied to reduce emissions and improve combustion efficiency by active control of the combustion process. Detailed flame ion chemistry models are needed to understand and predict the effect of external electric fields on combustion plasmas. In this work, a molecular beam mass spectrometer (MBMS) is utilized to measure ion concentration profiles in premixed methane–oxygen argon burner-stabilized atmospheric flames. Lean and stoichiometric flames are considered to assess the dependence of ion chemistry on flame stoichiometry. Relative ion concentration profiles are compared with numerical simulations using various temperature profiles, and good qualitative agreement was observed for the stoichiometric flame. However, for the lean flame, numerical simulations misrepresent the spatial distribution of selected ions greatly. Three modifications are suggested to enhance the ion mechanism and improve the agreement between experiments and simulations. The first two modifications comprise the addition of anion detachment reactions to increase anion recombination at low temperatures. The third modification involves restoring a detachment reaction to its original irreversible form. To our knowledge, this work presents the first detailed measurements of cations and flame temperature in canonical methane–oxygen-argon atmospheric flat flames. The positive ion profiles reported here may be useful to validate and improve ion chemistry models for methane-oxygen flames.

Heteroditopic receptors for ion-pair recognition.

Science.gov (United States)

McConnell, Anna J; Beer, Paul D

2012-05-21

Ion-pair recognition is a new field of research emerging from cation and anion coordination chemistry. Specific types of heteroditopic receptor designs for ion pairs and the complexity of ion-pair binding are discussed to illustrate key concepts such as cooperativity. The importance of this area of research is reflected by the wide variety of potential applications of ion-pair receptors, including applications as membrane transport and salt solubilization agents and sensors. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analytical Chemistry Division annual progress report for period ending December 31, 1990

Energy Technology Data Exchange (ETDEWEB)

1991-04-01

The Analytical Chemistry Division has programs in inorganic mass spectrometry, optical spectroscopy, organic mass spectrometry, and secondary ion mass spectrometry. It maintains a transuranium analytical laboratory and an environmental analytical laboratory. It carries out chemical and physical analysis in the fields of inorganic chemistry, organic spectroscopy, separations and synthesis. (WET)

Abstracts of the 3. Brazilian Meeting on Analytical Chemistry

International Nuclear Information System (INIS)

1985-01-01

Abstracts from experimental research works on analytical chemistry are presented. The following techniques were mainly used: differential pulse polarography, atomic absorption spectrophotometry, ion exchange chromatography and gamma spectroscopy. (C.L.B.) [pt

Characterization of iminothiosulfine-type ions [HNCS 2] rad +/ rad - and their neutral counterparts by mass spectrometry and computational chemistry

Science.gov (United States)

Vivekananda, S.; Raghunath, P.; Bhanuprakash, K.; Srinivas, R.; Trikoupis, Moschoula A.; Terlouw, Johan K.

2000-12-01

Electron ionization of rhodanine yields iminothiosulfine ions H- N C- S- Srad + , 1brad + , which readily communicate with the higher energy cyclic isomer H- N CS2rad + , 1arad + . CBS-QB3 and G AUSSIAN-2 model chemistries predict that one electron reduction reverses the stability order but that the (singlet) neutrals remain connected via a negligible energy barrier. Neutralization-reionization (NR) experiments demonstrate that singlet 1a and its heterocumulene isomer 1b are stable species in the gas-phase. However, the co-generated triplet species readily dissociate into 3S2rad + + HNC. Confirmatory experimental evidence comes from charge reversal (CR) and NR experiments on the cyclic anion H- N CS2rad - , 1arad - .

The influence of projectile ion induced chemistry on surface pattern formation

Energy Technology Data Exchange (ETDEWEB)

Karmakar, Prasanta, E-mail: prasantak@vecc.gov.in [Variable Energy Cyclotron Centre, 1/AF, Bidhannagar, Kolkata 700064 (India); Satpati, Biswarup [Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India)

2016-07-14

We report the critical role of projectile induced chemical inhomogeneity on surface nanostructure formation. Experimental inconsistency is common for low energy ion beam induced nanostructure formation in the presence of uncontrolled and complex contamination. To explore the precise role of contamination on such structure formation during low energy ion bombardment, a simple and clean experimental study is performed by selecting mono-element semiconductors as the target and chemically inert or reactive ion beams as the projectile as well as the source of controlled contamination. It is shown by Atomic Force Microscopy, Cross-sectional Transmission Electron Microscopy, and Electron Energy Loss Spectroscopy measurements that bombardment of nitrogen-like reactive ions on Silicon and Germanium surfaces forms a chemical compound at impact zones. Continuous bombardment of the same ions generates surface instability due to unequal sputtering and non-uniform re-arrangement of the elemental atom and compound. This instability leads to ripple formation during ion bombardment. For Argon-like chemically inert ion bombardment, the chemical inhomogeneity induced boost is absent; as a result, no ripples are observed in the same ion energy and fluence.

Chemistry in protoplanetary disks

Science.gov (United States)

Semenov, D. A.

2012-01-01

In this lecture I discuss recent progress in the understanding of the chemical evolution of protoplanetary disks that resemble our Solar system during the first ten million years. At the verge of planet formation, strong variations of temperature, density, and radiation intensities in these disks lead to a layered chemical structure. In hot, dilute and heavily irradiated atmosphere only simple radicals, atoms, and atomic ions can survive, formed and destroyed by gas-phase processes. Beneath the atmosphere a partly UV-shielded, warm molecular layer is located, where high-energy radiation drives rich chemistry, both in the gas phase and on dust surfaces. In a cold, dense, dark disk midplane many molecules are frozen out, forming thick icy mantles where surface chemistry is active and where complex (organic) species are synthesized.

Effects of annealing on the properties of atomic layer deposited Ru thin films deposited by NH{sub 3} and H{sub 2} as reactants

Energy Technology Data Exchange (ETDEWEB)

Lee, Seung-Joon; Kim, Soo-Hyun, E-mail: soohyun@ynu.ac.kr

2016-08-01

Atomic layer deposition (ALD) of Ru using a non-oxidizing reactant is indispensable considering its application as a seed layer for Cu electroplating and a bottom electrode for dynamic random access memory capacitors. In this study, ALD-Ru films were deposited using a sequential supply of dicarbonyl-bis(5-methyl-2,4-hexanediketonato) Ru(II) (C{sub 16}H{sub 22}O{sub 6}Ru) and potential non-oxidizing reducing agents, NH{sub 3} or H{sub 2}, as the reactants at a substrate temperature of 250 °C, and the effects of post-annealing in a H{sub 2} ambient on the film properties were investigated. The highly conformal deposition of Ru films was possible using the present reaction scheme but its resistivity was as high as ~ 750 μΩ-cm due to carbon incorporation into the film and the formation of an amorphous structure. Low temperature annealing at 300 °C at H{sub 2} ambient after deposition was found to improve the properties significantly in terms of the resistivity, impurities contents and crystallinity. For example, the film resistivity was decreased drastically to ~ 40 μΩ-cm with both the release of C in the film and crystallization after annealing based on secondary ion mass spectrometry and transmission electron microscopy, whereas perfect step coverage at a very small-sized dual trench (aspect ratio: ~ 3, the top opening size of 45 nm and bottom size of 20 nm) was maintained after annealing. - Highlights: • Ru thin films were deposited by atomic layer deposition (ALD) using NH{sub 3} and H{sub 2} molecules. • Effects of low temperature (300 °C) post-annealing on the film properties were investigated. • Post annealing improved the properties of ALD-Ru films. • Perfect step coverage of ALD-Ru was confirmed at trench structure (top opening width: 45 nm).

Ion Internal Excitation and Co++ 2 Reactivity: Effect On The Titan, Mars and Venus Ionospheric Chemistry

Science.gov (United States)

Nicolas, C.; Zabka, J.; Thissen, R.; Dutuit, O.; Alcaraz, C.

In planetary ionospheres, primary molecular and atomic photoions can be produced with substantial electronic and vibrational internal energy. In some cases, this is known to strongly affect both the rate constants and the branching ratio between the reac- tion products. A previous experimental study (Nicolas et al.) made at the Orsay syn- chrotron radiation facility has shown that many endothermic charge transfer reactions which were not considered in the ionospheric chemistry models of Mars, Venus and Earth have to be included because they are driven by electronic excitation of the parent ions. New measurements on two important reactions for Titan and Mars ionospheres, N+ + CH4 and O+ + CO2, will be presented. Branching ratios between products are very different when the parent atomic ions are prepared in their ground states, N+(3P) and O+(4S), or in their first electronic metastable states N+(1D) and O+(2D or P). 2 As the lifetime of these states are long enough, they survive during the mean time be- tween two collisions in the ionospheric conditions. So, the reactions of these excited states must be included in the ionospheric models. Absolute cross section measurements of the reactivity of stable doubly charged molec- ular ions CO++ and their implications for the Martian ionosphere will also be pre- 2 sented. The molecular dication CO++ production by VUV photoionisation and elec- 2 tron impact in the upper ionosphere of Mars is far from being negligible. However, to determine its concentration, it was necessary to evaluate the major loss channels of these ions. For this purpose, we measured the absolute reaction cross section of the sta- ble dications with CO2, the major neutral species of the Mars ionosphere. CO++ ions 2 were produced either by photoionisation or by electron impact, and a reaction cross section of 45 Å2 with 13CO2 was measured. The reaction leads to charge transfer or to collision induced dissociation. These results were integrated in a model

Improving chemistry performance in CANDU plants

International Nuclear Information System (INIS)

Turner, C.; Guzonas, D.

2010-01-01

There is a strong interplay between coolant chemistry and materials selection in any nuclear power plant system. To achieve the design life of reactor components it is necessary to monitor and control relevant chemistry parameters, such as ionic conductivity, pH, concentrations of dissolved ions and redox species (e.g., hydrogen, hydrazine, oxygen) and the concentrations of suspended corrosion products. Chemistry specifications are set to achieve a balance between the sometimes conflicting requirements to minimize corrosion and radiological dose and to minimize operating and maintenance costs over the lifetime of the plant. For the past decade, Atomic Energy of Canada Limited (AECL) has taken a rigorous and disciplined approach to reviewing and updating all aspects of chemistry control in the CANDU® nuclear power plant (NPP). This approach has included proactively reviewing chemistry operating experience from existing CANDU® and other water-cooled NPPs worldwide to identify and address emerging issues, updating all of our chemistry control documentation to ensure that each chemistry parameter is linked to a specific requirement (e.g., reduce activity transport, monitor for condenser leak) and incorporating the latest results from our Research and Development (R and D) programs to ensure that all chemistry specifications are supported by a sound rationale. The results of this review and update have been incorporated into updated chemistry specifications and, in some cases, modified operating procedures for new and existing plants. In addition, recommendations have been made for design modifications to improve chemistry control in new build plants, especially during periods of shutdown and startup when chemistry control has traditionally been more challenging. Chemistry control in new-build CANDU® plants will rely increasingly on the use of on-line instrumentation interfaced directly to AECL's state-of-the-art chemistry monitoring, diagnostics and analysis

Cellular radiobiology of heavy-ion beams

International Nuclear Information System (INIS)

Tobias, C.A.; Blakely, E.A.; Ngo, F.Q.H.; Roots, R.J.; Yang, T.C.

1981-01-01

Progress is reported in the following areas of this research program: relative biological effectiveness and oxygen enhancement ratio of silicon ion beams; heavy ion effects on the cell cycle; the potentiation effect (2 doses of high LET heavy-ion radiations separated by 2 to 3 hours); potentially lethal damage in actively growing cells and plateau growth cells; radiation induced macromolecular lesions and cellular radiation chemistry; lethal effects of dual radiation; and the development of a biophysical repair/misrepair model

Are clusters important in understanding the mechanisms in atmospheric pressure ionization? Part 1: Reagent ion generation and chemical control of ion populations.

Science.gov (United States)

Klee, Sonja; Derpmann, Valerie; Wißdorf, Walter; Klopotowski, Sebastian; Kersten, Hendrik; Brockmann, Klaus J; Benter, Thorsten; Albrecht, Sascha; Bruins, Andries P; Dousty, Faezeh; Kauppila, Tiina J; Kostiainen, Risto; O'Brien, Rob; Robb, Damon B; Syage, Jack A

2014-08-01

It is well documented since the early days of the development of atmospheric pressure ionization methods, which operate in the gas phase, that cluster ions are ubiquitous. This holds true for atmospheric pressure chemical ionization, as well as for more recent techniques, such as atmospheric pressure photoionization, direct analysis in real time, and many more. In fact, it is well established that cluster ions are the primary carriers of the net charge generated. Nevertheless, cluster ion chemistry has only been sporadically included in the numerous proposed ionization mechanisms leading to charged target analytes, which are often protonated molecules. This paper series, consisting of two parts, attempts to highlight the role of cluster ion chemistry with regard to the generation of analyte ions. In addition, the impact of the changing reaction matrix and the non-thermal collisions of ions en route from the atmospheric pressure ion source to the high vacuum analyzer region are discussed. This work addresses such issues as extent of protonation versus deuteration, the extent of analyte fragmentation, as well as highly variable ionization efficiencies, among others. In Part 1, the nature of the reagent ion generation is examined, as well as the extent of thermodynamic versus kinetic control of the resulting ion population entering the analyzer region.

Cellular uptake: lessons from supramolecular organic chemistry.

Science.gov (United States)

Gasparini, Giulio; Bang, Eun-Kyoung; Montenegro, Javier; Matile, Stefan

2015-07-04

The objective of this Feature Article is to reflect on the importance of established and emerging principles of supramolecular organic chemistry to address one of the most persistent problems in life sciences. The main topic is dynamic covalent chemistry on cell surfaces, particularly disulfide exchange for thiol-mediated uptake. Examples of boronate and hydrazone exchange are added for contrast, comparison and completion. Of equal importance are the discussions of proximity effects in polyions and counterion hopping, and more recent highlights on ring tension and ion pair-π interactions. These lessons from supramolecular organic chemistry apply to cell-penetrating peptides, particularly the origin of "arginine magic" and the "pyrenebutyrate trick," and the currently emerging complementary "disulfide magic" with cell-penetrating poly(disulfide)s. They further extend to the voltage gating of neuronal potassium channels, gene transfection, and the delivery of siRNA. The collected examples illustrate that the input from conceptually innovative chemistry is essential to address the true challenges in biology beyond incremental progress and random screening.

Nuclear analytical chemistry 5. Tables, nomograms and schemes

Energy Technology Data Exchange (ETDEWEB)

Tolgyessy, J; Varga, S; Dillinger, P; Kyrs, M

1976-01-01

Tables, graphs and nomograms are given on aspects of nuclear analytical chemistry. The tables contain data on physical and chemical units and their conversion, exponential functions, the characteristics of radioactive nuclides, data on the interaction of nuclear radiation with matter, data useful in measuring nuclear radiation, in scintillation and semiconductor spectrometry, activation analysis, data on masking reactions of ions in chemical separation, on extraction, ion exchange, accuracy in applying the method of isotope dilution, on radiochemical analysis.

Development of High Temperature Chemistry Measurement System for Establishment of On-Line Water Chemistry Surveillance Network in Nuclear Power Plant

International Nuclear Information System (INIS)

Yeon, Jei Won; Kim, Won Ho; Song, Kyu Seok; Joo, Ki Soo; Choi, Ke Chon; Ha, Yeong Keong; Ahn, Hong Joo; Im, Hee Jung; Maeng, Wan Young

2010-07-01

An integrated high-temperature water chemistry sensor (pH, E redox ) was developed for the establishment of the on-line water chemistry surveillance system in nuclear power plants. The basic performance of the integrated sensor was confirmed in high-temperature (280 .deg. C, 150kg/m 2 ) lithium borate solutions by using the relationship between the concentration of lithium ion and pH-E redox values. Especially, the effects of various environmental factors such as temperature, pressure, and flow rate on YSZ-based pH electrode were evaluated for ensuring the accuracy of high-temperature pH measurement. And the relationships between each water chemistry factor (pH, redox potential, electrical conductivity) were induced for enhancing the credibility of water chemistry measurement. In addition, on the basis of the evaluation of a nuclear plant design company, we suggested potential installation positions of the measurement system in a nuclear power plant

Nuclear chemistry of transactinide elements

Energy Technology Data Exchange (ETDEWEB)

Nagame, Yuichiro [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

1997-07-01

The current status on the nuclear chemistry studies of transactinide elements is reviewed. The production of transactinides in heavy ion reactions is briefly discussed, and nuclear properties on the stability of transactinides are presented. Chemical properties of the trans-actinide elements 104, 105 and 106, and a typical experimental technique used to study these properties on an atom-at-a-time base are introduced. (author)

Advances in BWR water chemistry

International Nuclear Information System (INIS)

Garcia, Susan E.; Giannelli, Joseph F.; Jarvis, Mary L.

2012-09-01

This paper reviews recent advances in Boiling Water Reactor (BWR) water chemistry control with examples of plant experiences at U.S. designed BWRs. Water chemistry advances provide some of the most effective methods for mitigating materials degradation, reducing fuel performance concerns and lowering radiation fields. Mitigation of stress corrosion cracking (SCC) of materials remains a high priority and improved techniques that have been demonstrated in BWRs will be reviewed, specifically hydrogen injection combined with noble metal chemical addition (NMCA) and the newer on-line noble metal application process (OLNC). Hydrogen injection performance, an important part of SCC mitigation, will also be reviewed for the BWR fleet, highlighting system improvements that have enabled earlier injection of hydrogen including the potential for hydrogen injection during plant startup. Water chemistry has been significantly improved by the application of pre-filtration and optimized use of ion exchange resins in the CP (condensate polishing) and reactor water cleanup (RWCU) systems. EPRI has monitored and supported water treatment improvements to meet water chemistry goals as outlined in the EPRI BWR Water Chemistry Guidelines, particularly those for SCC mitigation of reactor internals and piping, minimization of fuel risk due to corrosion and crud deposits and chemistry control for radiation field reduction. In recent years, a significant reduction has occurred in feedwater corrosion product input, particularly iron. A large percentage of plants are now reporting <0.1 ppb feedwater iron. The impacts to plant operation and chemistry of lower feedwater iron will be explored. Depleted zinc addition is widely practiced across the fleet and the enhanced focus on radiation reduction continues to emphasize the importance of controlling radiation source term. In addition, shutdown chemistry control is necessary to avoid excessive release of activated corrosion products from fuel

Photochemical Study of Silver Nanoparticles Formed from the Reduction of Silver Ions by Humic Acid

Science.gov (United States)

Leslie, Renee M.

This study focuses on the ability of silver ions and humic acid to form silver nanoparticles in the presence of UV and visible light. Silver nanoparticles have a number of industrial applications due primarily to their antimicrobial properties, but these properties pose an environmental threat. Silver nanoparticles can directly disrupt sensitive ecosystems by harming bacteria. Consumption of silver nanoparticles results in silver ions and silver nanoparticles entering waterways; the presence of silver ions raises the question of whether nanoparticles can reform in environmental waters. As our data show, silver nanoparticles can form from the reduction of silver ions by humic acid after irradiation with UV and visible light. In order to better understand the mechanism of these naturally synthesized silver nanoparticles, we investigated the effects of reactant concentration, experimental conditions and presence of ions/reactive species. We monitored silver nanoparticle growth with UV-visible spectroscopy. The evolution in time of nanoparticle size was monitored by dynamic light scattering (DLS).

Ion-selective electrodes

CERN Document Server

Mikhelson, Konstantin N

2013-01-01

Ion-selective electrodes (ISEs) have a wide range of applications in clinical, environmental, food and pharmaceutical analysis as well as further uses in chemistry and life sciences. Based on his profound experience as a researcher in ISEs and a course instructor, the author summarizes current knowledge for advanced teaching and training purposes with a particular focus on ionophore-based ISEs. Coverage includes the basics of measuring with ISEs, essential membrane potential theory and a comprehensive overview of the various classes of ion-selective electrodes. The principles of constructing I

Development of Large Li-Ion Batteries for Aircraft and Spacecraft Applications

National Research Council Canada - National Science Library

Bruce, Gregg

1998-01-01

.... Concurrent was a chemical direction which changed the emphasis of the program from the rechargeable Li/SO2 chemistry to that of the family of cell chemistries which are collectively referred to as lithium ion...

Relationships between nitric oxide, nitroxyl ion, nitrosonium cation and peroxynitrite.

Science.gov (United States)

Hughes, M N

1999-05-05

This review is concerned mainly with the three redox-related, but chemically distinct, species NO-, NO. and NO+, with greatest emphasis being placed on the chemistry and biology of the nitroxyl ion. Biochemical routes for the formation of nitroxyl ion and methods for showing the intermediacy of this species are discussed, together with chemical methods for generating nitroxyl ion in solution. Reactions of nitroxyl ion with NO., thiols, iron centres in haem and with dioxygen are reviewed The significance of the reaction between NO- and dioxygen as a source of peroxynitrite is assessed, and attention drawn to the possible significance of the spin state of the nitroxyl ion in this context. The biological significance of nitrosation and the importance of S-nitrosothiols and certain metal nitrosyl complexes as carriers of NO+ at physiological pH is stressed. Some features in the chemistry of peroxynitrite are noted.

Proceedings of the 8th Japan-China bilateral symposium on radiation chemistry

Energy Technology Data Exchange (ETDEWEB)

Yamaoka, Hitoshi; Hase, Hirotomo; Makuuchi, Keizou [eds.

2000-03-01

This issue is the collection of papers presented at The 8th Japan-China Bilateral Symposium on Radiation Chemistry held on October 25-29, 1999 at Kyodai Kaikan in Kyoto. The total number of the contributed papers is 69 which consists of 41 and 28 papers for oral and poster presentations, respectively. The papers presented are classified into five categories: A: Radiation Chemistry - Fundament (21 papers), B: Radiation Chemistry - Polymer (10 papers), C: Radiation Chemistry - Biological System (8 papers), D: Radiation Processing (19 papers), and E: Advanced Radiation Chemistry - Ion Beams and Positron (11 papers). The output of the Symposium and the history of the Bilateral Symposium were compiled in the Closing. (J.P.N.)

Facile synthesis of hierarchical nanostructured rutile titania for lithium-ion battery

International Nuclear Information System (INIS)

Fei Hailong; Wei Mingdeng

2011-01-01

Highlights: → Rutile TiO 2 sub-microflowers and sub-microspheres with different building blocks as anode materials of lithium-ion battery. → Controllable morphologies with oxalic acid by the hydrothermal technique. → Sub-microflower and sub-microspheres constructed by well organized nanorods exhibited high capacity and good cycle stability. → Small size building blocks nanorods enhance the transfer rate of Li-ion. - Abstract: A facile hydrothermal method is developed to prepare rutile titania sub-microflowers consisting of nanorods with oxalic acid and TiOSO 4 as reagents. The diameter of sub-microflowers and nanorods is found to be ca. 800 and 40 nm, respectively. Also, the shape and size of building blocks in rutile titania sub-microflowers can be considerably controlled via adjusting the reaction time and reactant amounts. Rutile titania sub-microflowers composed of nanorods display higher discharge capacity and better rate cycle stability than other rutile titania nanostructures as lithium-ion battery anode material due to enhancing the Li-ion transfer rate for small size building blocks.

Lifetime Models for Lithium-ion Batteries used in Virtual Power Plant Applications

DEFF Research Database (Denmark)

Stroe, Daniel Ioan

; however, because of their advantages, which include fast response, high efficiency, long lifetime and environmental friendliness, Lithium-ion (Li-ion) batteries represent suitable candidates for integration within VPPs, especially when they are required to provide short- and medium-time services....... The family of Li-ion batteries is broad with many different chemistries available at present on the market. Nonetheless, the Li-ion battery based on the lithium iron phosphate/graphite (further referred LFP/C) chemistry is investigated in this thesis. The lifetime of the Li-ion battery ESS represents a key...... parameter in the analysis of the economic feasibility of integrating such systems in WPPs. Even though their price is decreasing due to the research carried out mainly in the automotive sector, Li-ion batteries are still expensive energy storage devices. Therefore, accurate information about Li...

The application of synthetic inorganic ion exchangers to analytical chemistry, 2

International Nuclear Information System (INIS)

Abe, Mitsuo

1974-01-01

Regarding acidic salts, description is made on the general behaviour of the acidic salts of tetravalent metals and each of zirconium salts, titanium salts, stannic salts, cerium salts, thorium salts, chromium salts, and others. On heteropolyacid salts, ammonium 12-molybdophosphated and phosphorus wolframate are described. On insoluble ferrocyanides, the behaviour of various complex salts is explained. In the discussion on the general behaviour of the acidic salts of tetravalent metals, the ideality of ion exchange, the stability and solubility of the acidic salts, thermal stability and radiation resistance, the ion sieving effect of various acidic salts, and the selectivity of the acidic salts are stated. Zirconium gives a number of acidic salts, such as zirconium phosphate, crystalline zirconium phosphate, zirconium phrophosphate, various polyphosphates of zirconium, zirconium phosphate-silicate, zirconium arsenate, zirconium antimonate, zirconium molybdate, zirconium tungstate, etc. Useful titanium salts for ion exchange are titanium phosphate, titanium aresenate, titanium antimonate, titanium tungstate, titanium molybdate, titanium vanadate, and titanium selenate. The distribution coefficients of metal ions, inorganic-separation of various inorganic ion exchangers, the exchange characteristics of various elements on various ion exchangers, and the selectivity of various inorganic ion-exchangers are tabulated. (Fukutomi, T.)

Computational Modelling of Thermal Stability in a Reactive Slab with Reactant Consumption

Directory of Open Access Journals (Sweden)

O. D. Makinde

2012-01-01

Full Text Available This paper investigates both the transient and the steady state of a one-step nth-order oxidation exothermic reaction in a slab of combustible material with an insulated lower surface and an isothermal upper surface, taking into consideration reactant consumption. The nonlinear partial differential equation governing the transient reaction-diffusion problem is solved numerically using a semidiscretization finite difference technique. The steady-state problem is solved using a perturbation technique together with a special type of the Hermite-Padé approximants. Graphical results are presented and discussed quantitatively with respect to various embedded parameters controlling the systems. The crucial roles played by the boundary conditions in determining the thermal ignition criticality are demonstrated.

Report of the joint seminar on heavy-ion nuclear physics and nuclear chemistry in the energy region of tandem accelerators (II)

International Nuclear Information System (INIS)

1986-04-01

A meeting of the second joint seminar on Heavy-Ion Nuclear Physics and Nuclear Chemistry in the Energy Region of Tandem Accelerators was held after an interval of two years at the Tokai Research Establishment of the JAERI, for three days from January 9 to 11, 1986. In the seminar, about 70 nuclear physicists and nuclear chemists of JAERI and other Institutes participated, and 38 papers were presented. These include general reviews and topical subjects which have been developed intensively in recent years, as well as the new results obtained by using the JAERI tandem accelerator. This report is a collection of the papers presented to the seminar. (author)

Ion beam modification of surfaces for biomedical applications

International Nuclear Information System (INIS)

Sommerfeld, Jana

2014-01-01

Human life expectancy increased significantly within the last century. Hence, medical care must ever be improved. Optimizing artificial replacements such as hip joints or stents etc. is of special interest. For this purpose, new materials are constantly developed or known ones modified. This work focused on the possibility to change the chemistry and topography of biomedically relevant materials such as diamond-like carbon (DLC) and titanium dioxide (TiO 2 ) by means of ion beam irradiation. Mass-separated ion beam deposition was used in order to synthesize DLC layers with a high sp 3 content (> 70%), a sufficiently smooth surface (RMS<1 nm) and a manageable film thickness (50 nm). The chemistry of the DLC layers was changed by ion beam doping with different ion species (Ag,Ti) and concentrations. Additionally, the surface topography of silicon and titanium dioxide was altered by ion beam irradiation under non-perpendicular angle of incidence. The created periodic wave structures (so-called ripples) were characterized and their dependency on the ion energy was investigated. Moreover, ripples on silicon were covered with a thin DLC layer in order to create DLC ripples. The biocompatibility of all samples was investigated by adsorption experiments. For this purpose, human plasma fibrinogen (HPF) was used due to its ambiphilic character, which allows the protein to assume different conformations on materials with different hydrophilicities. Moreover, HPF is a crucial factor in the blood coagulation process. This work comes to the conclusion that the interaction of both, the surface chemistry and topography, has a strong influence on the adsorption behavior of HPF and thus the biocompatibility of a material. Both factors can be specifically tuned by means of ion beam irradiation.

Influence of weakly bound adduct ions on breath trace gas analysis by selected ion flow tube mass spectrometry (SIFT-MS)

Czech Academy of Sciences Publication Activity Database

Španěl, Patrik; Smith, D.

2009-01-01

Roč. 280, 1-3 (2009), s. 128-135 ISSN 1387-3806 R&D Projects: GA AV ČR IAA400400702 Institutional research plan: CEZ:AV0Z40400503 Keywords : ion-molecule association * adduct ion * SIFT-MS * breath analysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.117, year: 2009

Long range implantation by MEVVA metal ion source

International Nuclear Information System (INIS)

Zhang Tonghe; Wu Yuguang; Ma Furong; Liang Hong

2001-01-01

Metal vapor vacuum arc (MEVVA) source ion implantation is a new technology used for achieving long range ion implantation. It is very important for research and application of the ion beam modification of materials. The results show that the implanted atom diffusion coefficient increases in Mo implanted Al with high ion flux and high dose. The implanted depth is 311.6 times greater than that of the corresponding ion range. The ion species, doses and ion fluxes play an important part in the long-range implantation. Especially, thermal atom chemistry have specific effect on the long-range implantation during high ion flux implantation at transient high target temperature

Electron capture in very low energy collisions of multicharged ions with H and D in merged beams

International Nuclear Information System (INIS)

Havener, C.C.; Meyer, F.W.; Phaneuf, R.A.

1991-01-01

An ion-atom merged-beams technique is being used to measure total absolute electron-capture cross sections for multicharged ions in collisions with H (or D) in the energy range between 0.1 and 1000 eV/amu. Comparison between experiment and theory over such a large energy range constitutes a critical test for both experiment and theory. Total capture cross-section measurements for O 3+ H(D) and O 5+ + H(D) are presented and compared to state selective and differential cross section calculations. Landau-Zener calculations show that for O 5+ the sharp increase in the measured cross section below 1 eV/amu is partly due to trajectory effects arising from the ion-induced dipole interaction between the reactants. 20 refs., 8 figs

Review of ISOL target-ion-source systems

CERN Document Server

Kirchner, R

2003-01-01

Any review of target-ion-source systems (TISS) is necessarily a variation of the ISOL-theme 'efficient, fast, selective'. In the first part, more than 30 years of TISS development are examined in view of these key characteristics. By looking at the lines of development that were successful, at the lines that were abandoned (partly for good, partly for less good reasons), the lines with the most promising perspectives emerge. The second part deals with on-line chemistry in the TISS and its possibly double benefits: enhanced selectivity or increased separation speed, or both in favourable cases, as the relatively new sulfide chemistry. For the group-IVa-elements germanium and tin, the separation as sulfide-ions does not only suppress strongly the contamination by the neighbouring elements. It also reduces the effusion part of the release by orders of magnitude to the level of the intrinsic delay caused by molecular flow. The homologue chemistry is likely to work for silicon, but not for lead. While selectivity ...

Detection of nitro-based and peroxide-based explosives by fast polarity-switchable ion mobility spectrometer with ion focusing in vicinity of Faraday detector.

Science.gov (United States)

Zhou, Qinghua; Peng, Liying; Jiang, Dandan; Wang, Xin; Wang, Haiyan; Li, Haiyang

2015-05-29

Ion mobility spectrometer (IMS) has been widely deployed for on-site detection of explosives. The common nitro-based explosives are usually detected by negative IMS while the emerging peroxide-based explosives are better detected by positive IMS. In this study, a fast polarity-switchable IMS was constructed to detect these two explosive species in a single measurement. As the large traditional Faraday detector would cause a trailing reactant ion peak (RIP), a Faraday detector with ion focusing in vicinity was developed by reducing the detector radius to 3.3 mm and increasing the voltage difference between aperture grid and its front guard ring to 591 V, which could remove trailing peaks from RIP without loss of signal intensity. This fast polarity-switchable IMS with ion focusing in vicinity of Faraday detector was employed to detect a mixture of 10 ng 2,4,6-trinitrotoluene (TNT) and 50 ng hexamethylene triperoxide diamine (HMTD) by polarity-switching, and the result suggested that [TNT-H](-) and [HMTD+H](+) could be detected in a single measurement. Furthermore, the removal of trailing peaks from RIP by the Faraday detector with ion focusing in vicinity also promised the accurate identification of KClO4, KNO3 and S in common inorganic explosives, whose product ion peaks were fairly adjacent to RIP.

Irradiation influence on Mylar and Makrofol induced by argon ions in a plasma immersion ion implantation system

Energy Technology Data Exchange (ETDEWEB)

Hassan, A. [Accelerators & Ion Sources Department, Nuclear Research Center, Atomic Energy Authority, P.O. 13759, Cairo (Egypt); El-Saftawy, A.A., E-mail: aama1978@yahoo.com [Accelerators & Ion Sources Department, Nuclear Research Center, Atomic Energy Authority, P.O. 13759, Cairo (Egypt); Aal, S.A. Abd El [Central Lab. for Elemental & Isotopic Analysis, Nuclear Research Center, Atomic Energy Authority, P.O. 13759, Cairo (Egypt); Ghazaly, M. El [Physiology Department, College of Medicine, Taif University, P.O. 888, Taif (Saudi Arabia); Physics Department, Faculty of Science, Zagazig University, P.O. 44519, Zagazig (Egypt)

2015-08-30

Highlights: • A home-built plasma immersion ion implantation system was tested in modifying surfaces. • Wettability modifications within the energy range 10 keV implantation are not investigated elsewhere, up to our knowledge. • The wettability of Mylar and Makrofol surface was enhanced by the dual effect of ion implantation and plasma treatment. • The improved wettability was found to depend on both surface roughness and chemistry. • The adhesive bonding and surface energy of the polymers are improved. - Abstract: Mylar and Makrofol polycarbonate polymers were irradiated by Ar ions in a plasma immersion ion implantation (PIII) system. The surface wettability of both polymers was investigated by employing the contact angle method. The measured contact angles were found to depend on the surface layer properties. Good wetting surfaces were found to depend not only on surface roughness but also on its chemistry that analyzed by Fourier transform infrared (FTIR) spectroscopy. Surfaces topography and roughness was investigated and correlated to their surface energy which studied with the aid of acid-base model for evaluating the improvement of surface wettability after irradiation. PIII improves polymers surface properties efficiently in a controllable way.

Status report on electron cyclotron resonance ion sources at the Heavy Ion Medical Accelerator in Chiba

CERN Document Server

Kitagawa, A; Sekiguchi, M; Yamada, S; Jincho, K; Okada, T; Yamamoto, M; Hattori, T G; Biri, S; Baskaran, R; Sakata, T; Sawada, K; Uno, K

2000-01-01

The Heavy Ion Medical Accelerator in Chiba at the National Institute of Radiological Sciences (NIRS) is not only dedicated to cancer therapy, it is also utilized with various ion species for basic experiments of biomedical science, physics, chemistry, etc. Two electron cyclotron resonance (ECR) ion sources are installed for production of gaseous ions. One of them, the NIRS-ECR, is a 10 GHz ECR ion source, and is mainly operated to produce C/sup 4+/ ions for daily clinical treatment. This source realizes good reproducibility and reliability and it is easily operated. The other source, the NIRS-HEC, is an 18 GHz ECR ion source that is expected to produce heavier ion species. The output ion currents of the NIRS-ECR and the NIRS-HEC are 430e mu A for C/sup 4+/ and 1.1e mA for Ar/sup 8+/, respectively. (14 refs).

Predicting Upscaled Behavior of Aqueous Reactants in Heterogeneous Porous Media

Science.gov (United States)

Wright, E. E.; Hansen, S. K.; Bolster, D.; Richter, D. H.; Vesselinov, V. V.

2017-12-01

When modeling reactive transport, reaction rates are often overestimated due to the improper assumption of perfect mixing at the support scale of the transport model. In reality, fronts tend to form between participants in thermodynamically favorable reactions, leading to segregation of reactants into islands or fingers. When such a configuration arises, reactions are limited to the interface between the reactive solutes. Closure methods for estimating control-volume-effective reaction rates in terms of quantities defined at the control volume scale do not presently exist, but their development is crucial for effective field-scale modeling. We attack this problem through a combination of analytical and numerical means. Specifically, we numerically study reactive transport through an ensemble of realizations of two-dimensional heterogeneous porous media. We then employ regression analysis to calibrate an analytically-derived relationship between reaction rate and various dimensionless quantities representing conductivity-field heterogeneity and the respective strengths of diffusion, reaction and advection.

Major ion chemistry of the Son River, India: Weathering processes ...

Indian Academy of Sciences (India)

solute flux and CDR values. The water chemistry indicates that the Son River water is good to excellent .... to separate suspended sediments and preserved at. 4◦C for further ...... and waste water, 20th edn; American Public Health. Association ...

Cytosine Radical Cations: A Gas-Phase Study Combining IRMPD Spectroscopy, UVPD Spectroscopy, Ion-Molecule Reactions, and Theoretical Calculations

Czech Academy of Sciences Publication Activity Database

Lesslie, M.; Lawler, J. T.; Dang, A.; Korn, J. A.; Bím, Daniel; Steinmetz, V.; Maitre, P.; Tureček, F.; Ryzhov, V.

2017-01-01

Roč. 18, č. 10 (2017), s. 1293-1301 ISSN 1439-4235 Institutional support: RVO:61388963 Keywords : ion-molecule reactions * IRMPD spectroscopy * nucleobases * radical ions * UVPD spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 3.075, year: 2016

Kinetics in radiation chemistry

International Nuclear Information System (INIS)

Hummel, A.

1987-01-01

In this chapter the authors first briefly review the kinetics of first- and second-order processes for continuous and pulsed irradiation, without taking the effects of nonhomogeneous formation of the species into consideration. They also discuss diffusion controlled reactions under conditions where interactions of more than two particles can be neglected, first the kinetics of the diffusion-controlled reaction of randomly generated species (homogeneous reaction) and then that of isolated pairs of reactants. The latter is often called geminate kinetics when dealing with pairs of oppositely charged species; they shall use this term for the kinetics of isolated pairs in general. In the last section they discuss briefly the kinetics of groups of more than two reactants

New electronics stuff chemistry

International Nuclear Information System (INIS)

Byeon, Su Il

2003-04-01

The first part of this book is about equilibrium electrochemistry on electric thermo dynamic equilibrium state of electrochemistry, crystal defect of solid, thermodynamics on defect electron and election in semiconductor, Gawani potential, volta potential and equilibrium potential and thermodynamics application in Gawani battery. The second part deals with dynamic electrochemistry electrode reaction kinetics and corrosion potential in normal state, diffusion and transport of ion and electron and current impedance spectroscopy. It also mentions industrial electrochemistry and laboratory works in electronics chemistry course.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Excited state intramolecular charge transfer reaction of 4-(morpholenyl) benzonitrile in solution: Effects ... in (mixed solvent + electrolyte) systems: Role of reactant-solvent and reactant-ion interactions .... A molecular dynamics simulation study.

Time resolved FTIR study of the catalytic CO oxidation under periodic variation of the reactant concentration

Energy Technology Data Exchange (ETDEWEB)

Kritzenberger, J; Wokaun, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1997-06-01

Oxidation of CO over palladium/zirconia catalyst obtained from an amorphous Pd{sub 25}Zr{sub 75} precursor was investigated by time resolved FTIR spectroscopy. Sine wave shaped modulation of the reactant concentration, i.e. variation of CO or O{sub 2} partial pressure, was used to induce variations of the IR signals of product (CO{sub 2}) and unconverted reactant (CO), which were detected in a multi-pass absorption cell. The phase shift {phi} between external perturbation and variation of the CO{sub 2} signal was examined in dependence on temperature (100{sup o}C{<=}T{<=}350{sup o}C) and modulation frequency (1.39x10{sup -4}Hz{<=}{omega}{<=}6.67x10{sup -2}Hz). From the phase shift values, a simple Eley-Rideal mechanism is excluded, and the rate limiting step of the Langmuir-Hinshelwood mechanism for the CO oxidation may be identified. Adsorption and possible surface movement of CO to the actual reaction site determine the rate of the CO oxidation on the palladium/zirconia catalyst used in our study. The introduction of an external perturbation is a first step towards the application of two-dimensional infrared spectroscopy to heterogeneous catalyzed reactions. (author) 3 figs., 4 refs.

Theory of heavy ion collision physics in hadron therapy

CERN Document Server

2013-01-01

Advances in Quantum Chemistry presents surveys of current topics in this rapidly developing field that has emerged at the cross section of the historically established areas of mathematics, physics, chemistry, and biology. It features detailed reviews written by leading international researchers. This volume focuses on the theory of heavy ion physics in medicine.

Simple area determination of strongly overlapping ion mobility peaks

Czech Academy of Sciences Publication Activity Database

Borovcová, L.; Hermannová, M.; Pauk, V.; Šimek, M.; Havlíček, Vladimír; Lemr, Karel

2017-01-01

Roč. 981, AUG 15 (2017), s. 71-79 ISSN 0003-2670 Grant - others:GA MŠk(CZ) LO1305 Institutional support: RVO:61388971 Keywords : Ion mobility-mass spectrometry * Fitting of mobility peaks * Analysis of isomers Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 4.950, year: 2016

Transactinide nuclear chemistry at JAERI

International Nuclear Information System (INIS)

Nagame, Y.; Haba, H.; Tsukada, K.

2002-01-01

Nuclear chemistry study of trans actinide elements in Japan is currently being in progress at JAERI (Japan Atomic Energy Research Institute). We have developed new experimental apparatuses: a beam-line safety system for the usage of the gas-jet coupled radioactive 248 Cm target chamber, a rotating wheel catcher apparatus for the measurement of α and spontaneous fission decay of the transactinides, MANON (Measurement system for Alpha particles and spontaneous fission events ON line), and an automated rapid chemical separation apparatus based on the high performance liquid chromatography, AIDA (Automated Ion exchange separation system coupled with the Detection apparatus for Alpha spectroscopy). The transactinide nuclei, 261 Rf and 262 Db, have been successfully produced via the reactions of 248 Cm( 18 O,5n) and 248 Cm( 19 F,5n), respectively, and the excitation functions for each reaction have been measured to evaluate the optimum irradiation condition for the production of these nuclei. The maximum cross sections in each reaction were 13 nb at the 18 O beam energy of 94-MeV and 1.5 Nb at the 103-MeV 19 F beam energy. On-line ion exchange experiments of Rf together with the lighter homologues Zr and Hf in the HCl, HNO 3 and HF solutions with AIDA have been carried out, and the results clearly show that the behavior of Rf is typical of the group-4 element. Relativistic molecular orbital calculations of the chloride and nitrate complexes of tetravalent Rf are also being performed to gain an understanding of the complex chemistry. Prospects and some recent experimental results for the nuclear chemistry study of the transactinide elements at JAERI are discussed. (author)

Phage based green chemistry for gold ion reduction and gold retrieval.

Science.gov (United States)

Setyawati, Magdiel I; Xie, Jianping; Leong, David T

2014-01-22

The gold mining industry has taken its toll on the environment, triggering the development of more environmentally benign processes to alleviate the waste load release. Here, we demonstrate the use of bacteriophages (phages) for biosorption and bioreduction of gold ions from aqueous solution, which potentially can be applied to remediate gold ions from gold mining waste effluent. Phage has shown a remarkably efficient sorption of gold ions with a maximum gold adsorption capacity of 571 mg gold/g dry weight phage. The product of this phage mediated process is gold nanocrystals with the size of 30-630 nm. Biosorption and bioreduction processes are mediated by the ionic and covalent interaction between gold ions and the reducing groups on the phage protein coat. The strategy offers a simple, ecofriendly and feasible option to recover of gold ions to form readily recoverable products of gold nanoparticles within 24 h.

Progress report, Chemistry and Materials Division

International Nuclear Information System (INIS)

1982-02-01

A marked asymmetry has been observed in the intensity of ions scattered from manganese atoms in a Mn-Al alloy as a function of incidence angle, under near-axial channeling conditions. Proton dechanneling has been used to discriminate between simple and cluster defects created by He-ion irradiation of an Al-Ag alloy crystal. An automated Langmuir surface has been constructed for study of the radiation chemistry of polyunsaturated compounds organized in molecular films. New information about reactions of nitric oxide (NO) has been obtained which suggests that the reaction of NO with O 2 in the gas phase is also an important reaction in the radiation chemistry of oxygenated nitrate and nitrite solutions. Development work on an ion-selective electrode for the determination of boron has been completed. Recent studies have resulted in improvements to the mass spectrometric determination of thorium, uranium and plutonium. Good agreement between the results of the determinations of atom percent fission by a stable isotope dilution Nd-148 and a uranium isotope ratio method was observed. Examination of a large number of iodine-induced crack initiation sites formed under conditions where the hydrides are in solution has shown no evidence for the involvement of any second phase particles, or any local segregation of impurities or alloying elements. Reproducible improvement in the purity of zirconium has been achieved by the electrotransport method. Doppler broadening studies of positron annihilation in electron irradiated Zr and Ti have been completed

Ion-selective electrodes

Energy Technology Data Exchange (ETDEWEB)

Mikhelson, Konstantin N. [St. Petersburg State Univ. (Russian Federation). Ion-Selective Electrode Laboratory

2013-06-01

Ion-selective electrodes (ISEs) have a wide range of applications in clinical, environmental, food and pharmaceutical analysis as well as further uses in chemistry and life sciences. Based on his profound experience as a researcher in ISEs and a course instructor, the author summarizes current knowledge for advanced teaching and training purposes with a particular focus on ionophore-based ISEs. Coverage includes the basics of measuring with ISEs, essential membrane potential theory and a comprehensive overview of the various classes of ion-selective electrodes. The principles of constructing ISEs are outlined, and the transfer of methods into routine analysis is considered.

Microwave chemistry: Effect of ions on dielectric heating in microwave ovens

Directory of Open Access Journals (Sweden)

Jamil Anwar

2015-01-01

Full Text Available To understand the interactions of microwaves with dielectric materials and their conversion to thermal energy in aqueous systems, the effect of ionic concentration has been studied. Aqueous solutions of inorganic ions were exposed to microwaves (2.45 GHz in a modified oven under identical conditions. Difference in solution temperatures with reference to pure (deionized water was monitored in each case. A significant decrease in the temperature was observed with an increase in the quantity of ions. Experiments were repeated with several inorganic ions varying in size and charge. The information can be helpful in understanding the role of ions during dielectric heating.

Progress report: Chemistry and Materials Division, 1982 April 1 - June 30

International Nuclear Information System (INIS)

1982-08-01

The work of the division in the areas of solid state studies, radiation chemistry, isotope separation, analytical chemistry and materials science is described. The solid state science group studied solute atom vacancy trapping in irradiated f.c.c. alloys as well as the rearrangement of atoms in solids bombarded by energetic heavy ions. In radiation chemistry, work was done on the pulse radiolysis of NO in argon. Isotope separation studies were done on fluoroform and uranium. Fuel burnup determination using 148 Nd and 139 La was investigated. Zirconium alloy studies included work on stress corrosion cracking and the Baushinger effect

Scalable Computational Chemistry: New Developments and Applications

Energy Technology Data Exchange (ETDEWEB)

Alexeev, Yuri [Iowa State Univ., Ames, IA (United States)

2002-01-01

The computational part of the thesis is the investigation of titanium chloride (II) as a potential catalyst for the bis-silylation reaction of ethylene with hexaclorodisilane at different levels of theory. Bis-silylation is an important reaction for producing bis(silyl) compounds and new C-Si bonds, which can serve as monomers for silicon containing polymers and silicon carbides. Ab initio calculations on the steps involved in a proposed mechanism are presented. This choice of reactants allows them to study this reaction at reliable levels of theory without compromising accuracy. The calculations indicate that this is a highly exothermic barrierless reaction. The TiCl₂ catalyst removes a 50 kcal/mol activation energy barrier required for the reaction without the catalyst. The first step is interaction of TiCl₂ with ethylene to form an intermediate that is 60 kcal/mol below the energy of the reactants. This is the driving force for the entire reaction. Dynamic correlation plays a significant role because RHF calculations indicate that the net barrier for the catalyzed reaction is 50 kcal/mol. They conclude that divalent Ti has the potential to become an important industrial catalyst for silylation reactions. In the programming part of the thesis, parallelization of different quantum chemistry methods is presented. The parallelization of code is becoming important aspects of quantum chemistry code development. Two trends contribute to it: the overall desire to study large chemical systems and the desire to employ highly correlated methods which are usually computationally and memory expensive. In the presented distributed data algorithms computation is parallelized and the largest arrays are evenly distributed among CPUs. First, the parallelization of the Hartree-Fock self-consistent field (SCF) method is considered. SCF method is the most common starting point for more accurate calculations. The Fock build (sub step of SCF) from AO integrals is

General theory of the multistage geminate reactions of the isolated pairs of reactants. II. Detailed balance and universal asymptotes of kinetics.

Science.gov (United States)

Kipriyanov, Alexey A; Doktorov, Alexander B

2014-10-14

The analysis of general (matrix) kinetic equations for the mean survival probabilities of any of the species in a sample (or mean concentrations) has been made for a wide class of the multistage geminate reactions of the isolated pairs. These kinetic equations (obtained in the frame of the kinetic approach based on the concept of "effective" particles in Paper I) take into account various possible elementary reactions (stages of a multistage reaction) excluding monomolecular, but including physical and chemical processes of the change in internal quantum states carried out with the isolated pairs of reactants (or isolated reactants). The general basic principles of total and detailed balance have been established. The behavior of the reacting system has been considered on macroscopic time scales, and the universal long-term kinetics has been determined.

Excitation in the radiation chemistry of inorganic gases

International Nuclear Information System (INIS)

Willis, C.; Boyd, A.W.

1976-01-01

Gas phase radiation chemistry yield data and electron impact cross-section data are used to derive excitation mechanisms and to discuss the role of excited states in the radiation chemistry of O 2 , N 2 , N 2 O, CO, CO 2 , H 2 S, H 2 O and NH 3 . For each of these systems available cross-sections for ionization and neutral excitation are listed, together with relevant reaction rate data and a summary of the radiation chemistry studies at both high and low dose rates. In general, fairly complete mechanisms are derived and further tested by energy balance calculations. In order to present as complete a picture as possible, a summary of rates and products of ion-neutralization reactions is given at the end of the paper. (author)

Non-traditional Oxidants in Preparative Coordination Chemistry

Science.gov (United States)

Kukushkin, Vadim Yu; Kukushkin, Yurii N.

1986-10-01

The application of nitrosonium and arenediazonium salts, carbenium, silver(I), and mercury(II) ions, protic acids, and amine oxides as oxidants in preparative coordination chemistry is examined. Specific examples illustrate which problems in the field of the synthesis and reactions of coordination compounds can be solved with the aid of these oxidants. The bibliography includes 158 references.

Supplementary Material for: Measurements of Positively Charged Ions in Premixed Methane-Oxygen Atmospheric Flames

KAUST Repository

Alquaity, Awad B. S.

2017-01-01

Cations and anions are formed as a result of chemi-ionization processes in combustion systems. Electric fields can be applied to reduce emissions and improve combustion efficiency by active control of the combustion process. Detailed flame ion chemistry models are needed to understand and predict the effect of external electric fields on combustion plasmas. In this work, a molecular beam mass spectrometer (MBMS) is utilized to measure ion concentration profiles in premixed methane–oxygen argon burner-stabilized atmospheric flames. Lean and stoichiometric flames are considered to assess the dependence of ion chemistry on flame stoichiometry. Relative ion concentration profiles are compared with numerical simulations using various temperature profiles, and good qualitative agreement was observed for the stoichiometric flame. However, for the lean flame, numerical simulations misrepresent the spatial distribution of selected ions greatly. Three modifications are suggested to enhance the ion mechanism and improve the agreement between experiments and simulations. The first two modifications comprise the addition of anion detachment reactions to increase anion recombination at low temperatures. The third modification involves restoring a detachment reaction to its original irreversible form. To our knowledge, this work presents the first detailed measurements of cations and flame temperature in canonical methane–oxygen-argon atmospheric flat flames. The positive ion profiles reported here may be useful to validate and improve ion chemistry models for methane-oxygen flames.

Solid-state photoelectrochemical H2 generation with gaseous reactants

International Nuclear Information System (INIS)

Iwu, Kingsley O.; Galeckas, Augustinas; Kuznetsov, Andrej Yu.; Norby, Truls

2013-01-01

Photocurrent and H 2 production were demonstrated in an all solid-state photoelectrochemical cell employing gaseous methanol and water vapour at the photoanode. Open circuit photovoltage of around −0.4 V and short circuit photocurrent of up to 250 μA/cm 2 were obtained. At positive bias, photocurrent generation was limited by the irradiance, i.e., the amount of photogenerated charge carriers at the anode. Time constants and impedance spectra showed an electrochemical capacitance of the cell of about 15 μF/cm 2 in the dark, which increased with increasing irradiance. With only water vapour at the anode, the short circuit photocurrent was about 6% of the value with gaseous methanol and water vapour. The photoanode and electrocatalyst on carbon paper support were affixed to the proton conducting membrane using Nafion ® as adhesive, an approach that yielded photocurrents up to 15 times better than that of a cell assembled by hot-pressing, in spite of the overall cell resistance of the latter being up to five times less than that of the former. This is attributed, at least partially, to reactants being more readily available at the photoanode of the better performing cell

Green chemistry perspectives of methane conversion via oxidative methylation of aromatics over zeolite catalysts

Energy Technology Data Exchange (ETDEWEB)

Adebajo, M.O. [University of Queensland, St Lucia, Qld. (Australia)

2007-06-15

This paper provides a general overview of the recent work that we and other researchers have done on the utilisation of methane for catalytic methylation of aromatic compounds and for direct coal liquefaction for the production of liquid hydrocarbons. In particular, the paper presents a detailed description of more recent substantial experimental evidence that we have provided for the requirement of oxygen as a stoichiometry reactant for benzene methylation with methane over moderately acidic zeolite catalysts. The reaction, which has been termed 'oxidative methylation', was thus postulated to involve a two-step mechanism involving intermediate methanol formation by methane partial oxidation, followed by benzene methylation with methanol in the second step. However, strongly acidic zeolites can cause cracking of benzene to yield methylated products in the absence of oxygen. The participation of methane and oxygen, and the effective use of zeolite catalysts in this methylation reaction definitely have some positive green chemistry implications. Thus, the results of these previous studies are also discussed in this review in light of the principles and tools of green chemistry. Various metrics were used to evaluate the greenness, cost-effectiveness, and material and energy efficiency of the oxidative methylation reaction.

Synthesis and Characterization of Calixarene Tetraethers: An Exercise in Supramolecular Chemistry for the Undergraduate Organic Laboratory

Science.gov (United States)

Debbert, Stefan L.; Hoh, Bradley D.; Dulak, David J.

2016-01-01

In this experiment for an introductory undergraduate organic chemistry lab, students tetraalkylate tertbutylcalix[4]arene, a bowl-shaped macrocyclic oligophenol, and examine the supramolecular chemistry of the tetraether product by proton nuclear magnetic resonance (NMR) spectroscopy. Complexation with a sodium ion reduces the conformational…

Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes

KAUST Repository

Chan, Candace K.

2009-04-01

Silicon nanowires (SiNWs) have the potential to perform as anodes for lithium-ion batteries with a much higher energy density than graphite. However, there has been little work in understanding the surface chemistry of the solid electrolyte interphase (SEI) formed on silicon due to the reduction of the electrolyte. Given that a good, passivating SEI layer plays such a crucial role in graphite anodes, we have characterized the surface composition and morphology of the SEI formed on the SiNWs using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). We have found that the SEI is composed of reduction products similar to that found on graphite electrodes, with Li2CO3 as an important component. Combined with electrochemical impedance spectroscopy, the results were used to determine the optimal cycling parameters for good cycling. The role of the native SiO2 as well as the effect of the surface area of the SiNWs on reactivity with the electrolyte were also addressed. © 2009 Elsevier B.V. All rights reserved.

f-Element Ion Chelation in Highly Basic Media

International Nuclear Information System (INIS)

Paine, Robert T.

1999-01-01

High-level radioactive waste (HLW) generated in the DOE complex is stored in tanks at several sites, but predominantly it is found at the Hanford reservation. Much of the material has been exposed to high pHs, consequently the waste exists in a complex, poorly understood mixture of solids, gels and solutions. The final waste remediation plan may involve chemical separation of fractions and a suitable, well developed molecular chemistry basis for performing these separations is not available. Indeed, the fundamental chemical behavior of most radioactive nuclides in basic media is not known. The goal of this project is to undertake fundamental studies of the coordination chemistry of f-element species in basic aqueous solutions containing common waste treatment ions (e.g., NO3 -, CO3 2-, organic carboxylates, and EDTA), as well as new waste scrubbing chelators produced in this study. The experimental agenda includes: 1. Studies of the speciation of Sr and Ln ions in basic solutions wit h and without common counterions; 2. Preparations of new multifunctional ligands that may act as strong, ion-specific chelators for Sr and/or Ln ions in basic media; and 3. Studies of the coordination and dissolution behavior of oxide-hydroxide species, as well as in insoluble sols, gels, and precipitates in combination with new chelating ligands. It is anticipated that this coordination chemistry will facilitate the design of advanced separation schemes required for handling the complex waste matrices found at the Hanford HLW facility

Study on actinoids in boundary ion transfer from an aspect of solution chemistry

Energy Technology Data Exchange (ETDEWEB)

Kihara, Sorin; Shirai, Makoto; Matsui, Masakazu [Kyoto Univ., Uji (Japan). Inst. for Chemical Research; Yoshida, Zenko; Aoyagi, Hisao; Kitatsuji, Yoshihiro

1996-01-01

This study aimed to elucidate the fundamental properties of boundary ion transfer between water (W) and organic solvent (O) and to apply the results to the study on actinoid ions. First, dissolved states of ion in W and O in relation to boundary transfer were investigated and the transfer stimulation effects by an addition of some agents which can induce their complex formation were examined. Then, a theoretical equation which expresses a relationship between ion-pair extraction reaction and {Delta}Gtr was proposed and proved with {Delta}Gtr of single ion obtained by the use of VITIES, which is an apparatus for voltammetric determination of boundary ion transfer developed by the authors. Single ion transfer in W/O was estimated from the voltammogram based on I-{Delta}V curve (I; electric current which corresponds to the amount of ion transfer and {Delta}V; phase boundary voltage). In addition, determination of actinoid ion transfer in W/O boundary was made by VITIES to clarify the ion transfer energy, velocity and transferred molecular species. Thus, developments of a new isolation method and a trial sensor for actinoid ions were undertaken based on these results. (M.N.)

Modelling the chemistry of iodine

International Nuclear Information System (INIS)

Paquette, J.

1989-01-01

We have assembled a kinetic model, based on elementary chemical reactions, that describes the chemical behaviour of iodine in aqueous solution as a function of time and various parameters such as pH, concentration and radiation field. The model is conceptually divided into six section: aqueous iodine chemistry, aqueous organic iodide chemistry, water radiolysis, radiolysis of iodine solutions, radiolysis of organic iodide solutions and mass transfer. The model indicates that, in the absence of a radiation field, the rate of production of volatile iodine species is controlled by the rate of oxidation of the iodide ion. The volatile iodine species are dominated by organic iodides if organic impurities are present. The single most important parameter controlling iodine volatility is the pH of the solution; high pH values tend to minimize iodine volatility. In the presence of a radiation field, the volatility of iodine is controlled by the radiation-induced oxidation of the iodide ion. Again, iodine volatility is dominated by organic iodides if organic impurities are present. High pH values minimize iodine volatility. A sensitivity analysis has been performed on some sections of the model to identify reactions to which the volatility of iodine is most sensitive. In the absence of a radiation field, the volatility is most sensitive, first, to the rate of oxidation of the iodide ion, and, second, to the rate of mass transfer of volatile species between the aqueous and the gaseous phases. This approach should be useful in identifying reactions for which accurate rate constants are required and in decreasing the complexity of the model. 37 refs

Effect of reactant concentration on the structural properties of hydrothermally-grown ZnO rods on seed-layer ZnO / polyethylene terephthalate substrates

Energy Technology Data Exchange (ETDEWEB)

Jeong, Y. I.; Shin, C. M.; Heo, J. H.; Ryu, H. [Inje University, Gimhae (Korea, Republic of); Lee, W. J. [Dong-Eui University, Busan (Korea, Republic of); Son, C. S. [Silla University, Busan (Korea, Republic of); Choi, H. [Pukyong National University, Busan (Korea, Republic of)

2011-09-15

The morphology and the structural properties were studied for zinc-oxide (ZnO) rods hydrothermally grown on seed-layer ZnO/polyethylene terephthalate (PET) substrates at various reactant concentrations. Dissolved solutions with de-ionized water, zinc nitrate hexahydrate (Zn(NO{sub 3}){sub 2}{center_dot}6H{sub 2}O, ZNH) and hexamethylenetetramine (C{sub 6}H{sub 12}N{sub 4}, HMT) were employed as reactants for hydrothermal growth of ZnO. The transparency of the mixtures (ZNH+HMT) with increasing reactant concentration from 0.025 to 0.25 M changed from transparent to translucent to opaque (white colors) due to Zn(OH){sub 2} precipitates. When the concentration was increased, the density of the ZnO rods increased, and the morphology of the ZnO rods changed from a hexagonal flat-end shape to a sharp-end or flake-like structure. The sharp-end rods with increasing concentration from 0.1 to 0.15 M resulted from the etching process at a lower pH condition (less than pH 6) after the ZnO rod growth, and the flake-like structure was due to a high growth rate. The ZnO seed layer might have improved the alignment of ZnO rods and made a high density of ZnO rods. In addition, the structural properties were improved at lower concentrations by inserting a seed layer.

Liquid-liquid extraction of ion-association complexes of cobalt(II-4-(2-pyridylazoresorcinol with ditetrazolium salts

Directory of Open Access Journals (Sweden)

Divarova Vidka V.

2015-01-01

Full Text Available The formation and liquid-liquid extraction of ion-association complexes between Co(II-4-(2-Pyridylazoresorcinol (PAR anionic chelates and cations of three ditetrazolium chlorides were studied: Blue Tetrazolium chloride (BTC, Neotetrazolium chloride (NTC and Nitro Blue Tetrazolium chloride (NBT. The optimum conditions for the formation and solvent extraction of the ion-association comlpex chelates were determined. It has been found that in the systems of Co(II-PAR-DTS, the reactants are reacted in molar ratios 1:2:1 and the general formula of complexes was suggested. The extraction equilibria were investigated and quantitatively characterized by the equilibrium constants and the recovery factors. The analytical characteristics of the complexes were calculated.

Microwave plasma ion sources for selected ion flow tube mass spectrometry: Optimizing their performance and detection limits for trace gas analysis

Czech Academy of Sciences Publication Activity Database

Španěl, Patrik; Dryahina, Kseniya; Smith, D.

2007-01-01

Roč. 267, 1-3 (2007), s. 117-124 ISSN 1387-3806 R&D Projects: GA ČR GA202/06/0776 Institutional research plan: CEZ:AV0Z40400503 Keywords : microwave plasma ion source * selected ion flow tube mass spectrometry * SIFT-MS * breath analysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.411, year: 2007

Secondary ion mass spectroscopy (SIMS)

International Nuclear Information System (INIS)

Naik, P.K.

1975-01-01

Secondary Ion Mass Spectrometry (SIMS) which is primarily a method for investigating the chemical composition of the uppermost atomic layer of solid surfaces is explained. In this method, the specimen is bombarded with a primary positive ion beam of small current density monolayer. Positive and negative ions sputtered from the specimen are mass analysed to give the surface chemical composition. The analytical system which consists of a primary ion source, a target manipulator and a mass spectrometer housed in an ultrahigh vacuum system is described. This method can also be used for profile measurements in thin films by using higher current densities of the primary ions. Fields of application such as surface reactions, semiconductors, thin films emission processes, chemistry, metallurgy are touched upon. Various aspects of this method such as the sputtering process, instrumentation, and applications are discussed. (K.B.)

$^{31}$Mg $\\beta$-NMR applied in chemistry and biochemistry

CERN Multimedia

Magnesium ions, Mg$^{2+}$, are essential in biological systems, taking part in practically all phosphate chemistry, in photosynthesis as an integral component of chlorophyll, and they are regulated via transport through selective membrane proteins. Nonetheless, the function of magnesium ions in biochemistry is difficult to characterize, as it is practically invisible to current experimental techniques. With this proposal we aim to advance the use of $^{31}$Mg $\\beta$-NMR to liquid samples, building on the experience from the successful Letter of Intent INTC-I-088 “$\\beta$-NMR as a novel technique for biological applications”. Initially a series of experiments will be conducted aiming to characterize the coordination chemistry of Mg$^{2+}$ in ionic liquids (ILs), demonstrating that it is possible within the lifetime of the radioisotope to achieve binding of Mg$^{2+}$ to a molecule dissolved in the IL. ILs are chosen as they display a very low vapor pressure, and are thus straightforwardly compatible with t...

Negative ion formation in collisions involving excited alkali atoms

International Nuclear Information System (INIS)

Cheret, M.

1988-01-01

Ion-pair production is considered as the prototype of the crossing problem between potential energy curves. In general an alkali atom is one of the reactants the other being an halogen, hydrogen atom or molecule. Experimental results are generally analyzed in the framework of the Landau-Zener-Stuekelberg theory, ionization potential and electron affinity, being the most important parameters. In order to vary these parameters over a wide range two experimental works have been devoted to systems of excited alkali atoms colliding with ground state alkali atoms. In the first study Rb atoms are excited to various ns or nd states from Rb(5d) to Rb(9s) in a cell. The second study is devoted to the Na(3p)-Na(3s) system, in this study also the possibility of creating excited negative ions (Na - (3s3p)) has been investigated. These results are presented and analyzed. Finally further developments of the subject are suggested. 17 refs.; 8 figs.; 1 table

Evaluation of the effect of reactant gases mass flow rates on power density in a polymer electrolyte membrane fuel cell

Science.gov (United States)

Kahveci, E. E.; Taymaz, I.

2018-03-01

In this study it was experimentally investigated the effect of mass flow rates of reactant gases which is one of the most important operational parameters of polymer electrolyte membrane (PEM) fuel cell on power density. The channel type is serpentine and single PEM fuel cell has an active area of 25 cm2. Design-Expert 8.0 (trial version) was used with four variables to investigate the effect of variables on the response using. Cell temperature, hydrogen mass flow rate, oxygen mass flow rate and humidification temperature were selected as independent variables. In addition, the power density was used as response to determine the combined effects of these variables. It was kept constant cell and humidification temperatures while changing mass flow rates of reactant gases. From the results an increase occurred in power density with increasing the hydrogen flow rates. But oxygen flow rate does not have a significant effect on power density within determined mass flow rates.

The effects of reactants ratios, reaction temperatures and times on Maillard reaction products of the L-ascorbic acid/L-glutamic acid system

Directory of Open Access Journals (Sweden)

Yong-Yan ZHOU

2016-01-01

Full Text Available Abstract The transformation law of the Maillard reaction products with three different reactants ratios - equimolar reactants, excess L-glutamic acid and excess L-ascorbic acid reaction respectively, five different temperatures, and different time conditions for the L-ascorbic acid / L-glutamic acid system were investigated. Results showed that, the increase of the reaction time and temperature led to the increase of the browning products, uncoloured intermediate products, as well as aroma compounds. Compared with the equimolar reaction system, the excess L-ascorbic acid reaction system produced more browning products and uncoloured intermediate products, while the aroma compounds production remained the same. In the excess L-glutamic acid system, the uncoloured intermediate products increased slightly, the browning products remained the same, while the aroma compounds increased.

Investigation of coupling between chemistry and discharge dynamics in radio frequency hydrogen plasmas in the Torr regime

International Nuclear Information System (INIS)

Kalache, B; Novikova, T; Morral, A Fontcuberta i; Cabarrocas, P Roca i; Morscheidt, W; Hassouni, K

2004-01-01

We present the results of a study of a capacitively coupled hydrogen discharge by means of a one-dimensional numerical fluid model and experiments. The model includes a detailed description of the gas-phase chemistry taking into account the production of H - ions by dissociative attachment of H 2 vibrational levels. The population of these levels is described by a Boltzmann vibrational distribution function characterized by a vibrational temperature T V . The effect of the dissociative-attachment reaction on the discharge dynamics was investigated by varying the vibrational temperature, which was used as a model input parameter. Increasing the vibrational temperature from 1000 to 6000 K affects both the chemistry and the dynamics of the electrical discharge. Because of dissociative attachment, the H - ion density increases by seven orders of magnitude and the H - ion density to electron density ratio varies from 10 -7 to 6, while the positive ion density increases slightly. As a consequence, the atomic hydrogen density increases by a factor of three, and the sheath voltage drops from 95 to 75 V. Therefore, clear evidence of a strong coupling between chemistry and electrical dynamics through the production of H - ions is demonstrated. Moreover, satisfactory agreement between computed and measured values of atomic hydrogen and H - ion densities gives further support to the requirement of a detailed description of the hydrogen vibrational kinetics for capacitively coupled radio frequency discharge models in the Torr regime

Progress in liquid ion exchangers

International Nuclear Information System (INIS)

Nakagawa, Genkichi

1974-01-01

Review is made on the extraction with anion exchangers and the extraction with liquid cation exchangers. On the former, explanation is made on the extraction of acids, the relation between anion exchange and the extraction of metals, the composition of the metallic complexes that are extracted, and the application of the extraction with anion exchangers to analytical chemistry. On the latter, explanation is made on the extraction of metals and its application to analytical chemistry. The extraction with liquid ion exchangers is suitable for the operation in chromatography, because the distribution of extracting agents into aqueous phase is small, and extraction equilibrium is quickly reached, usually within 1 to several minutes. The separation by means of anion exchangers is usually made from hydrochloric acid solution. For example, Brinkman et al. determined Rf values for more than 50 elements by thin layer chromatography. Tables are given for showing the structure of the liquid ion exchangers and the polymerized state of various amines. (Mori, K.)

A compact high resolution ion mobility spectrometer for fast trace gas analysis.

Science.gov (United States)

Kirk, Ansgar T; Allers, Maria; Cochems, Philipp; Langejuergen, Jens; Zimmermann, Stefan

2013-09-21

Drift tube ion mobility spectrometers (IMS) are widely used for fast trace gas detection in air, but portable compact systems are typically very limited in their resolving power. Decreasing the initial ion packet width improves the resolution, but is generally associated with a reduced signal-to-noise-ratio (SNR) due to the lower number of ions injected into the drift region. In this paper, we present a refined theory of IMS operation which employs a combined approach for the analysis of the ion drift and the subsequent amplification to predict both the resolution and the SNR of the measured ion current peak. This theoretical analysis shows that the SNR is not a function of the initial ion packet width, meaning that compact drift tube IMS with both very high resolution and extremely low limits of detection can be designed. Based on these implications, an optimized combination of a compact drift tube with a length of just 10 cm and a transimpedance amplifier has been constructed with a resolution of 183 measured for the positive reactant ion peak (RIP(+)), which is sufficient to e.g. separate the RIP(+) from the protonated acetone monomer, even though their drift times only differ by a factor of 1.007. Furthermore, the limits of detection (LODs) for acetone are 180 pptv within 1 s of averaging time and 580 pptv within only 100 ms.

Voltage-Sensitive Ion Channels Biophysics of Molecular Excitability

CERN Document Server

Leuchtag, H. Richard

2008-01-01

Voltage-sensitive ion channels are macromolecules embedded in the membranes of nerve and muscle fibers of animals. Because of their physiological functions, biochemical structures and electrical switching properties, they are at an intersection of biology, chemistry and physics. Despite decades of intensive research under the traditional approach of gated structural pores, the relation between the structure of these molecules and their function remains enigmatic. This book critically examines physically oriented approaches not covered in other ion-channel books. It looks at optical and thermal as well as electrical data, and at studies in the frequency domain as well as in the time domain. Rather than presenting the reader with only an option of mechanistic models at an inappropriate pseudo-macroscopic scale, it emphasizes concepts established in organic chemistry and condensed state physics. The book’s approach to the understanding of these unique structures breaks with the unproven view of ion channels as...

Mainz University, Institute of Nuclear Chemistry. Annual report 1993

International Nuclear Information System (INIS)

Denschlag, H.O.

1994-03-01

The report presents the results achieved by the Institute's five working groups in the following fields: Development of chemical separation processes, chemistry of ultraheavy elements; Developments in instrumentation; Nuclear fission and heavy ion reactions; Nuclear astrophysics, decay characteristics, structure of atoms and nuclei; Environmental pollution analysis. (orig./EF) [de

Analytical Chemistry Division : annual report for the year 1980

International Nuclear Information System (INIS)

Sathe, R.M.

1981-01-01

The research and development activities of the Analytical Chemistry Division of the Bhabha Atomic Research Centre, during 1980 are reported in the form of abstracts. Various methods nuclear, spectral, thermal, electrochemical ion exchange developed for chemical analysis are described. Solvent extraction studies are also reviewed. (M.G.B.)

Streamwater chemistry and nutrient budgets for forested watersheds in New England: variability and management implications

Science.gov (United States)

J.W. Hornbeck; S.W. Bailey; D.C. Buso; J.B. Shanley

1997-01-01

Chemistry of precipitation and streamwater and resulting input-output budgets for nutrient ions were determined concurrently for three years on three upland, forested watersheds located within an 80 km radius in central New England. Chemistry of precipitation and inputs of nutrients via wet deposition were similar among the three watersheds and were generally typical...

Developments and prospects of radiation chemistry

International Nuclear Information System (INIS)

Imamura, Masashi

1984-01-01

The fruitful achievement which has been obtained in the radiation chemistry laboratory of the Institute of Physical and Chemical Research during the research for twenty years from 1963 to 1983 is summarized in this review. In the section of investigation of radiation-induced chemical reaction, the new problems and their interpretation of LET effect in the case of aqueous solution of ferrous chloride and liquid organic compound, and the radiation chemistry of liquid methanol are described, and in the section of investigation of ion-radicals, low temperature rigid solution-γ-ray irradiation method including the outline of the method and the electron absorption spectra of ion-radicals and the structure are described. In the section of pulse-radiolysis method (pulsed electron beam irradiation method), the application to the investigation of dimer cations, the initial process of dimer anions and ionic polymerization, the solvation process of anion radicals, and the long distance transfer of electrons in amorphous solid are explained. In the section of research on metal porphyrin complex related to the chemical conversion of solar energy, chlorophyll-a and its dimer, and synthetic metal porphyrin complex, and in the section of research on photochemical reaction, photochemical reaction and the chemical effect on radioactive disintegration are explained. (Yoshitake, I.)

Hydration energies and specific influence of oxo complexes and high coordination numbers on the predicted chemistry of superheavy elements

International Nuclear Information System (INIS)

Jorgensen, C.K.; Penneman, R.A.

1975-01-01

On the basis of an analysis of the known ionization energies of gaseous ions and aqua ions of the 3d, 4f, and 6d transition groups and the radius effects, the chemistry of the superheavy elements is predicted. The formation of aqua ion and oxo complexes in the elements with Z below 121 is considered. It is probable that the series from 123 to 140 constitute a close analogy to the lanthanides with Th-like chemistry. Above Z = 140 the elements will probably displace a transition group behavior. A brief comment is made on the analytical aspects to be expected. (U.S.)

Interfaces and Materials in Lithium Ion Batteries: Challenges for Theoretical Electrochemistry.

Science.gov (United States)

Kasnatscheew, Johannes; Wagner, Ralf; Winter, Martin; Cekic-Laskovic, Isidora

2018-04-18

Energy storage is considered a key technology for successful realization of renewable energies and electrification of the powertrain. This review discusses the lithium ion battery as the leading electrochemical storage technology, focusing on its main components, namely electrode(s) as active and electrolyte as inactive materials. State-of-the-art (SOTA) cathode and anode materials are reviewed, emphasizing viable approaches towards advancement of the overall performance and reliability of lithium ion batteries; however, existing challenges are not neglected. Liquid aprotic electrolytes for lithium ion batteries comprise a lithium ion conducting salt, a mixture of solvents and various additives. Due to its complexity and its role in a given cell chemistry, electrolyte, besides the cathode materials, is identified as most susceptible, as well as the most promising, component for further improvement of lithium ion batteries. The working principle of the most important commercial electrolyte additives is also discussed. With regard to new applications and new cell chemistries, e.g., operation at high temperature and high voltage, further improvements of both active and inactive materials are inevitable. In this regard, theoretical support by means of modeling, calculation and simulation approaches can be very helpful to ex ante pre-select and identify the aforementioned components suitable for a given cell chemistry as well as to understand degradation phenomena at the electrolyte/electrode interface. This overview highlights the advantages and limitations of SOTA lithium battery systems, aiming to encourage researchers to carry forward and strengthen the research towards advanced lithium ion batteries, tailored for specific applications.

Ion exchange filter transition plan for BWRs and PWRs

International Nuclear Information System (INIS)

Garcia, Susan; McElrath, Joel; Varnam, Jeremie; Giannelli, Joseph F.

2014-01-01

Analysis and quantification of reactor water, feedwater, and chemical and volume control system (CVCS) soluble metals and radioisotopes are essential for monitoring species that impact fuel performance, steam generator and heat exchanger performance, mitigation of stress corrosion cracking of reactor piping and internals, radiation fields and ensuring that dose mitigation techniques are effective. Soluble species in the CVCS, feedwater, reactor water and other process sample streams are usually collected on ion exchange membranes after the sample has passed through a 0.45 or 0.1 μm membrane filter. Cationic species are predominantly of interest. Most nuclear plants currently use cation exchange membranes from Toray Industries, Inc. In September 2012, it was reported that Toray Industries, Inc. would discontinue the manufacturing of cation exchange membranes at the end of 2012. Similar reports were received concerning ion exchange membranes manufactured by Pall Corporation. These reports prompted several plants and utilities to begin evaluating other products from various vendors to replace their current ion exchange membranes in preparation for a transition. With this possible change having a potential impact on the water chemistry analyses that are important for monitoring fuel reliability and corrosion and dose control, an initial scoping evaluation of ion exchange membrane availability from various vendor and plant experiences was conducted. Recommended approaches were provided to close identified gaps and reduce burden on nuclear plant chemistry laboratories. Additional work required in 2014, includes an independent laboratory review of membrane performance and in-plant demonstrations. These demonstrations and evaluations will assist the industry by providing the technical input needed to manage a change in membrane use so that preferred processes and media can be identified to minimize any adverse impacts on chemistry analyses that support chemistry control

Negative ions in the auroral mesosphere during a PCA event around sunset

Directory of Open Access Journals (Sweden)

C. F. del Pozo

Full Text Available This is a study of the negative ion chemistry in the mesosphere above Tromsø using a number of EISCAT observations of high energy proton precipitation events during the last solar maximum, and in particular around sunset on 23 October, 1989. In these conditions it is possible to look at the relative importance of the various photodetachment and photodissociation processes controlling the concentration of negative ions. The data analysed are from several UHF GEN11 determinations of the ion-plasma ACF together with the pseudo zero-lag estimate of the `raw' electron density, at heights between 55 km and 85 km, at less than 1 km resolution. The power profiles from the UHF are combined with the 55-ion Sodankylä model to obtain consistent estimates of the electron density, the negative ion concentrations, and the average ion mass with height. The neutral concentrations and ion temperature are given by the MSIS90 model. These parameters are then used to compare the calculated widths of the ion-line with the GEN11 determinations. The ion-line spectrum gives information on the effects of negative ions below 70 km where they are dominant; the spectral width is almost a direct measure of the relative abundance of negative ions.

Key words. Ionosphere (auroral ionosphere; ion chemistry and composition; particle precipitation.

Energetics of lithium ion battery failure

Energy Technology Data Exchange (ETDEWEB)

Lyon, Richard E., E-mail: richard.e.lyon@faa.gov; Walters, Richard N.

2016-11-15

Highlights: • First measure of anaerobic failure energy of lithium ion batteries. • Novel and simple bomb calorimeter method developed and demonstrated. • Four different cathode chemistries examined. • Full range of charged capacity used as independent variable. • Failure energy identified as primary safety hazard. - Abstract: The energy released by failure of rechargeable 18-mm diameter by 65-mm long cylindrical (18650) lithium ion cells/batteries was measured in a bomb calorimeter for 4 different commercial cathode chemistries over the full range of charge using a method developed for this purpose. Thermal runaway was induced by electrical resistance (Joule) heating of the cell in the nitrogen-filled pressure vessel (bomb) to preclude combustion. The total energy released by cell failure, ΔH{sub f}, was assumed to be comprised of the stored electrical energy E (cell potential × charge) and the chemical energy of mixing, reaction and thermal decomposition of the cell components, ΔU{sub rxn}. The contribution of E and ΔU{sub rxn} to ΔH{sub f} was determined and the mass of volatile, combustible thermal decomposition products was measured in an effort to characterize the fire safety hazard of rechargeable lithium ion cells.

Chemistry Division progress report for the period January 1, 1977 - December 31, 1980

International Nuclear Information System (INIS)

Moorthy, P.N.; Ramshesh, V.; Yakhmi, J.V.

1981-01-01

The research and development work of the Chemistry Division of the Bhabha Atomic Research Centre, Bombay, during the period 1977-1980 is reported in the form of individual summaries under the headings: basic research including radiation chemistry, photochemistry, kinetic and electrochemical studies, ion exchange and sorption behaviour, chemistry of metal complexes (in particular, of uranium complexes), radiation damage in solids, heterogeneous catalysts, studies in magnetism, physical properties, solid state studies, theoretical studies, reactor related programmes (including reactor chemistry, lubricants and sealants, surface studies, water chemistry), applied research and development (including materials development, purification and analytical techniques, apolied radiation chemistry etc.), and instrumentation. Work of service facilities such as workshop, analytical se services, and repair and maintenance of instruments is described. Lists of training programmes, staff publications and divisional seminars, are given. At the end a sectionwise list of staff members is also given. (M.G.B.)

SHS synthesis of Si-SiC composite powders using Mg and reactants from industrial waste

Science.gov (United States)

Chanadee, Tawat

2017-11-01

Si-SiC composite powders were synthesized by self-propagating high-temperature synthesis (SHS) using reactants of fly ash-based silica, sawdust-based activated carbon, and magnesium. Fly ash-based silica and sawdust-based activated carbon were prepared from coal mining fly ash and Para rubber-wood sawdust, respectively. The work investigated the effects of the synthesis atmosphere (air and Ar) on the phase and morphology of the SHS products. The SHS product was leached by a two-step acid leaching processes, to obtain the Si-SiC composite powder. The SHS product and SHS product after leaching were characterized by X-ray diffractometry, scanning electron microscopy and energy dispersive X-ray spectrometry. The results indicated that the SHS product synthesized in air consisted of Si, SiC, MgO, and intermediate phases (SiO2, Mg, Mg2SiO4, Mg2Si), whereas the SHS product synthesized in Ar consisted of Si, SiC, MgO and a little Mg2SiO4. The SiC content in the leached-SHS product was higher when Ar was used as the synthesis atmosphere. As well as affecting the purity, the synthesis atmospheres also affected the average crystalline sizes of the products. The crystalline size of the product synthesized in Ar was smaller than that of the product synthesized in air. All of the results showed that fly ash and sawdust could be effective waste-material reactants for the synthesis of Si-SiC composite powders.

An ICR study of ion-molecule reactions of PH(n)+ ions. [of importance to interstellar chemistry, using ion cyclotron resonance techniques

Science.gov (United States)

Thorne, L. R.; Anicich, V. G.; Huntress, W. T.

1983-01-01

The reactions of PH(n)+ ions (n = 0-3) were examined with a number of neutrals using ion-cyclotron-resonance techniques. The reactions examined have significance for the distribution of phosphorus in interstellar molecules. The results indicate that interstellar molecules containing the P-O bond are likely to be more abundant than those containing the P-H bond.

Suitability of the Nanophosphate LiFePO4/C Battery Chemistry for the Fully Electric Vehicle

DEFF Research Database (Denmark)

Swierczynski, Maciej Jozef; Stroe, Daniel Ioan; Stan, Ana-Irina

2014-01-01

, and intrinsic safety of the nanophosphate LiFePO4/C lithium ion chemistry make it possible to consider this chemistry for electric vehicle applications. This paper investigates the lifetime of the nanophosphate LiFePO4/C battery chemistry when it is used for full electrical vehicles. The investigation...... is used to study the capacity and power capability degradation behaviour of the tested nanophosphate LiFePO4/C battery for two electric vehicle operational scenarios....

Non-equilibrium chemistry and cooling in simulations of galaxy formation

NARCIS (Netherlands)

Richings, Alexander James

2015-01-01

In this thesis we used numerical simulations to explore the role that chemistry plays in galaxy formation. Simulations of galaxies often assume chemical equilibrium, where the chemical reactions between ions and molecules have reached a steady state. However, this assumption may not be valid if the

Advances in electron transfer chemistry

CERN Document Server

Mariano, Patrick S

1995-01-01

Advances in Electron Transfer Chemistry, Volume 4 presents the reaction mechanisms involving the movement of single electrons. This book discusses the electron transfer reactions in organic, biochemical, organometallic, and excited state systems. Organized into four chapters, this volume begins with an overview of the photochemical behavior of two classes of sulfonium salt derivatives. This text then examines the parameters that control the efficiencies for radical ion pair formation. Other chapters consider the progress in the development of parameters that control the dynamics and reaction p

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

Science.gov (United States)

NRMRL-CIN-1437 Jeselnik, M., Varma*, R.S., Polanc, S., and Kocevar, M. Catalyst-free Reactions under Solvent-fee Conditions: Microwave-assisted Synthesis of Heterocyclic Hydrazones below the Melting Point of Neat Reactants. Published in: Chemical Communications 18:1716-1717 (200...

Annual report of the Osaka Laboratory for Radiation Chemistry Japan Atomic Energy Research Institute, 21

International Nuclear Information System (INIS)

1990-03-01

This report describes research activities of Osaka Laboratory for Radiation Chemistry, JAERI during one year period from April 1, 1987 through March 31, 1988. Detailed descriptions of the activities are presented in the following subjects: (i) studies on surface phenomena under electron and ion irradiations and (ii) studies on radiation chemistry of high polymers and radiation dosimetry. (J.P.N.)

Relationships determining the toxicity of major ion mixtures to Ceriodaphnia dubia

Science.gov (United States)

Significant impacts to aquatic systems can occur due to increases in major ions (Na, K, Ca, Mg, Cl, SO4, HCO3) from various anthropogenic activities, these impacts varying with both the specific combination of ions that are elevated and the chemistry of the background water. A s...

Chemistry of the water in thermal power plants

International Nuclear Information System (INIS)

Freier, R.K.

1984-01-01

This textbook and practical manual gives a comprehensive review of the scientific knowledge of water as operating substance and of the chemistry of water in thermal power plants. The fundamentals of water chemistry and of the conventional and nuclear water/steam circuit are described. The contents of the chapters are: 1. The atom, 2. The chemical bond, 3. The dissolving capacity of water, 4. Operational parameters and their measurement, 5. Corrosion, 6. The water/steam coolant loop of conventional plants (WSC), 7. The pressurized water reactor (PWR), 8. The boiling water reactor (BWR), 9. The total and partial desalination properties of ion exchangers, 10. The cooling water, 11. The failure of Harrisburg in a simple presentation. (HK) [de

Extraterrestrial Radiation Chemistry and Molecular Astronomy

Science.gov (United States)

Hudson, Reggie L.; Moore, Marla H.

2009-01-01

Astronomical observations of both solar system and interstellar regions have revealed a rich chemical inventory that includes most classes of organic molecules and selected inorganics. For example, gas-phase ethylene glycol and SOz have been observed by astronomers, while solidphase detections include OCS, H2O2 , and the cyanate anion.' All of these are found in environments that are, by earthly standards, exceedingly hostile: temperatures of 10 - 100 K, miniscule densities, and near-ubiquitous ionizing-radiation fields. Beyond the simplest chemical species, these conditions have made it difficult-to-impassible to account for the observed molecular abundances using gas-phase chemistry, suggesting solid-phase reactions play an important role. In extraterrestrial environments, cosmic rays, UV photons, and magnetospheric radiation all drive chemical reactions, even at cryogenic temperatures. To study this chemistry, radiation astrochemists conduct experiments on icy materials, frozen under vacuum and exposed to sources such as keV electrons and MeV protons. Compositional changes usually are followed with IR spectroscopy and, in selected cases, more-sensitive mass-spectral techniques. This talk will review some recent results on known and suspected extraterrestrial molecules and ions. Spectra and reaction pathways will be presented, and predictions made for interstellar chemistry and the chemistry of selected solar system objects. Some past radiation-chemical contributions, and future needs, will be explored.

Detailed high-resolution three-dimensional simulations of OMEGA separated reactants inertial confinement fusion experiments

Energy Technology Data Exchange (ETDEWEB)

Haines, Brian M., E-mail: bmhaines@lanl.gov; Fincke, James R.; Shah, Rahul C.; Boswell, Melissa; Fowler, Malcolm M.; Gore, Robert A.; Hayes-Sterbenz, Anna C.; Jungman, Gerard; Klein, Andreas; Rundberg, Robert S.; Steinkamp, Michael J.; Wilhelmy, Jerry B. [Los Alamos National Laboratory, MS T087, Los Alamos, New Mexico 87545 (United States); Grim, Gary P. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Forrest, Chad J.; Silverstein, Kevin; Marshall, Frederic J. [Laboratory for Laser Energetics, University of Rochester, Rochester, New York 14623 (United States)

2016-07-15

We present results from the comparison of high-resolution three-dimensional (3D) simulations with data from the implosions of inertial confinement fusion capsules with separated reactants performed on the OMEGA laser facility. Each capsule, referred to as a “CD Mixcap,” is filled with tritium and has a polystyrene (CH) shell with a deuterated polystyrene (CD) layer whose burial depth is varied. In these implosions, fusion reactions between deuterium and tritium ions can occur only in the presence of atomic mix between the gas fill and shell material. The simulations feature accurate models for all known experimental asymmetries and do not employ any adjustable parameters to improve agreement with experimental data. Simulations are performed with the RAGE radiation-hydrodynamics code using an Implicit Large Eddy Simulation (ILES) strategy for the hydrodynamics. We obtain good agreement with the experimental data, including the DT/TT neutron yield ratios used to diagnose mix, for all burial depths of the deuterated shell layer. Additionally, simulations demonstrate good agreement with converged simulations employing explicit models for plasma diffusion and viscosity, suggesting that the implicit sub-grid model used in ILES is sufficient to model these processes in these experiments. In our simulations, mixing is driven by short-wavelength asymmetries and longer-wavelength features are responsible for developing flows that transport mixed material towards the center of the hot spot. Mix material transported by this process is responsible for most of the mix (DT) yield even for the capsule with a CD layer adjacent to the tritium fuel. Consistent with our previous results, mix does not play a significant role in TT neutron yield degradation; instead, this is dominated by the displacement of fuel from the center of the implosion due to the development of turbulent instabilities seeded by long-wavelength asymmetries. Through these processes, the long

Production of Endohedral Fullerenes by Ion Implantation

Energy Technology Data Exchange (ETDEWEB)

Diener, M.D.; Alford, J. M.; Mirzadeh, S.

2007-05-31

The empty interior cavity of fullerenes has long been touted for containment of radionuclides during in vivo transport, during radioimmunotherapy (RIT) and radioimaging for example. As the chemistry required to open a hole in fullerene is complex and exceedingly unlikely to occur in vivo, and conformational stability of the fullerene cage is absolute, atoms trapped within fullerenes can only be released during extremely energetic events. Encapsulating radionuclides in fullerenes could therefore potentially eliminate undesired toxicity resulting from leakage and catabolism of radionuclides administered with other techniques. At the start of this project however, methods for production of transition metal and p-electron metal endohedral fullerenes were completely unknown, and only one method for production of endohedral radiofullerenes was known. They therefore investigated three different methods for the production of therapeutically useful endohedral metallofullerenes: (1) implantation of ions using the high intensity ion beam at the Oak Ridge National Laboratory (ORNL) Surface Modification and Characterization Research Center (SMAC) and fullerenes as the target; (2) implantation of ions using the recoil energy following alpha decay; and (3) implantation of ions using the recoil energy following neutron capture, using ORNL's High Flux Isotope Reactor (HFIR) as a thermal neutron source. While they were unable to obtain evidence of successful implantation using the ion beam at SMAC, recoil following alpha decay and neutron capture were both found to be economically viable methods for the production of therapeutically useful radiofullerenes. In this report, the procedures for preparing fullerenes containing the isotopes {sup 212}Pb, {sup 212}Bi, {sup 213}Bi, and {sup 177}Lu are described. None of these endohedral fullerenes had ever previously been prepared, and all of these radioisotopes are actively under investigation for RIT. Additionally, the chemistry for

Characterizing Normal Groundwater Chemistry in Hawaii

Science.gov (United States)

Tachera, D.; Lautze, N. C.; Thomas, D. M.; Whittier, R. B.; Frazer, L. N.

2017-12-01

Hawaii is dependent on groundwater resources, yet how water moves through the subsurface is not well understood in many locations across the state. As marine air moves across the islands water evaporates from the ocean, along with trace amounts of sea-salt ions, and interacts with the anthropogenic and volcanic aerosols (e.g. sulfuric acid, ammonium sulfate, HCl), creating a slightly more acidic rain. When this rain falls, it has a chemical signature distinctive of past processes. As this precipitation infiltrates through soil it may pick up another distinctive chemical signature associated with land use and degree of soil development, and as it flows through the underlying geology, its chemistry is influenced by the host rock. We are currently conducting an investigation of groundwater chemistry in selected aquifer areas of Hawaii, having diverse land use, land cover, and soil development conditions, in an effort to investigate and document what may be considered a "normal" water chemistry for an area. Through this effort, we believe we better assess anomalies due to contamination events, hydrothermal alteration, and other processes; and we can use this information to better understand groundwater flow direction. The project has compiled a large amount of precipitation, soil, and groundwater chemistry data in the three focus areas distributed across in the State of Hawaii. Statistical analyses of these data sets will be performed in an effort to determine what is "normal" and what is anomalous chemistry for a given area. Where possible, results will be used to trace groundwater flow paths. Methods and preliminary results will be presented.

Institute of Nuclear Chemistry, Mainz University. Annual report 1991

International Nuclear Information System (INIS)

Denschlag, H.O.

1992-03-01

Brief reports summarise the 1991 achievements of the four departments of the Institute relating to the subject areas: chemistry of most heavy elements, fast separation methods, equipment development, decay properties and structures of nuclei, heavy ion reactions, environmental analytics. The list of publications and lectures of Institute members is given in an annex. (orig.) [de

Institute of Nuclear Chemistry, Mainz University. Annual report 1992

International Nuclear Information System (INIS)

Denschlag, H.O.

1993-03-01

Brief reports summarise the 1992 achievements of the four departments of the Institute relating to the subject areas: Chemistry of most heavy elements, fast separation methods, equipment development, decay properties and structures of nuclei, heavy ion reactions, environmental analytics. The list of publications and lectures of Institute members is given in an annex. (orig.) [de

A Model for Negative Ion Chemistry in Titan’s Ionosphere

Science.gov (United States)

Mukundan, Vrinda; Bhardwaj, Anil

2018-04-01

We developed a one-dimensional photochemical model for the dayside ionosphere of Titan for calculating the density profiles of negative ions under steady-state photochemical equilibrium condition. We concentrated on the T40 flyby of the Cassini orbiter and used the in situ measurements from instruments on board Cassini as input to the model. Using the latest available reaction rate coefficients and dissociative electron attachment cross sections, the densities of 10 anions are calculated. Our study shows CN‑ as the dominant anion, followed by C3N‑, which agrees with the results of previous calculations. We suggest that H‑ could be an important anion in Titan’s ionosphere and is the second most abundant anion at altitudes greater than 1200 km. The main production channel of the major ion CN‑ is the reaction of H‑ with HCN. The H‑ also play a major role in the production of anions C2H‑, C6H‑, and OH‑. We present a comparison of the calculated ion density profiles with the relative density profiles derived using recently reported Cassini CAPS/ELS observations.

Interactions of Native Cyclodextrins with Metal Ions and Inorganic Nanoparticles: Fertile Landscape for Chemistry and Materials Science.

Science.gov (United States)

Prochowicz, Daniel; Kornowicz, Arkadiusz; Lewiński, Janusz

2017-11-22

Readily available cyclodextrins (CDs) with an inherent hydrophobic internal cavity and hydrophilic external surface are macrocyclic entities that display a combination of molecular recognition and complexation properties with vital implications for host-guest supramolecular chemistry. While the host-guest chemistry of CDs has been widely recognized and led to their exploitation in a variety of important functions over the last five decades, these naturally occurring macrocyclic systems have emerged only recently as promising macrocyclic molecules to fabricate environmentally benign functional nanomaterials. This review surveys the development in the field paying special attention to the synthesis and emerging uses of various unmodified CD-metal complexes and CD-inorganic nanoparticle systems and identifies possible future directions. The association of a hydrophobic cavity of CDs with metal ions or various inorganic nanoparticles is a very appealing strategy for controlling the inorganic subunits properties in the very competitive water environment. In this review we provide the most prominent examples of unmodified CDs' inclusion complexes with organometallic guests and update the research in this field from the past decade. We discuss also the coordination flexibility of native CDs to metal ions in CD-based metal complexes and summarize the progress in the synthesis and characterization of CD-metal complexes and their use in catalysis and sensing as well as construction of molecular magnets. Then we provide a comprehensive overview of emerging applications of native CDs in materials science and nanotechnology. Remarkably, in the past few years CDs have appeared as attractive building units for the synthesis of carbohydrate metal-organic frameworks (CD-MOFs) in a combination of alkali-metal cations. The preparation of this new class of highly porous materials and their applications in the separation of small molecules, the loading of drug molecules, as well as

Combustion Chemistry of Fuels: Quantitative Speciation Data Obtained from an Atmospheric High-temperature Flow Reactor with Coupled Molecular-beam Mass Spectrometer.

Science.gov (United States)

Köhler, Markus; Oßwald, Patrick; Krueger, Dominik; Whitside, Ryan

2018-02-19

This manuscript describes a high-temperature flow reactor experiment coupled to the powerful molecular beam mass spectrometry (MBMS) technique. This flexible tool offers a detailed observation of chemical gas-phase kinetics in reacting flows under well-controlled conditions. The vast range of operating conditions available in a laminar flow reactor enables access to extraordinary combustion applications that are typically not achievable by flame experiments. These include rich conditions at high temperatures relevant for gasification processes, the peroxy chemistry governing the low temperature oxidation regime or investigations of complex technical fuels. The presented setup allows measurements of quantitative speciation data for reaction model validation of combustion, gasification and pyrolysis processes, while enabling a systematic general understanding of the reaction chemistry. Validation of kinetic reaction models is generally performed by investigating combustion processes of pure compounds. The flow reactor has been enhanced to be suitable for technical fuels (e.g. multi-component mixtures like Jet A-1) to allow for phenomenological analysis of occurring combustion intermediates like soot precursors or pollutants. The controlled and comparable boundary conditions provided by the experimental design allow for predictions of pollutant formation tendencies. Cold reactants are fed premixed into the reactor that are highly diluted (in around 99 vol% in Ar) in order to suppress self-sustaining combustion reactions. The laminar flowing reactant mixture passes through a known temperature field, while the gas composition is determined at the reactors exhaust as a function of the oven temperature. The flow reactor is operated at atmospheric pressures with temperatures up to 1,800 K. The measurements themselves are performed by decreasing the temperature monotonically at a rate of -200 K/h. With the sensitive MBMS technique, detailed speciation data is acquired and

The emerging chemistry of sodium ion batteries for electrochemical energy storage.

Science.gov (United States)

Kundu, Dipan; Talaie, Elahe; Duffort, Victor; Nazar, Linda F

2015-03-09

Energy storage technology has received significant attention for portable electronic devices, electric vehicle propulsion, bulk electricity storage at power stations, and load leveling of renewable sources, such as solar energy and wind power. Lithium ion batteries have dominated most of the first two applications. For the last two cases, however, moving beyond lithium batteries to the element that lies below-sodium-is a sensible step that offers sustainability and cost-effectiveness. This requires an evaluation of the science underpinning these devices, including the discovery of new materials, their electrochemistry, and an increased understanding of ion mobility based on computational methods. The Review considers some of the current scientific issues underpinning sodium ion batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigating the flow dynamics and chemistry of an expanding thermal plasma through CH(A-X) emission spectra

NARCIS (Netherlands)

Hansen, T. A. R.; Colsters, P. G. J.; M. C. M. van de Sanden,; Engeln, R.

2011-01-01

The gas flow in a linear plasma reactor and the plasma chemistry during hydrogenated amorphous carbon and graphite etching are investigated via time and spatially resolved measurements of the ion density and CH emission. A convolution of the ion and hydrocarbon density shows the importance of charge

Lithium ion battery energy storage system for augmented wind power plants

DEFF Research Database (Denmark)

Swierczynski, Maciej Jozef

with Battery Energy Storage Systems (BESSs) into the so called Virtual Power Plants (VPP). Relatively new energy storage technologies based on Lithium ion (Li-ion) batteries are constantly improving their performance and are becoming attractive for stationary energy storage applications due...... to their characteristics such as high power, high efficiency, low self-discharge, and long lifetime. The family of the Li-ion batteries is wide and the selection of the most appropriate Liion chemistries for VPPs is one of the topics of this thesis, where different chemistries are compared and the most suitable ones...... if the batteries are able to meet several performance requirements, which are application dependent. Furthermore, for the VPP, the degradation or failure of the interconnected BESS can lead to costly downtime. Thus, an accurate estimation of the battery cells lifetime becomes mandatory. However, lifetime...

Lifetime Estimation of the Nanophosphate LiFePO4/C Battery Chemistry Used in Fully Electric Vehicles

DEFF Research Database (Denmark)

Swierczynski, Maciej Jozef; Stroe, Daniel Loan; Stroe, Ana-Irina

2015-01-01

, and intrinsic safety of the nanophosphate LiFePO4/C Li-ion chemistry make it possible to consider this chemistry for electric vehicle (EV) applications. This paper investigates the lifetime of the nanophosphate LiFePO4/C battery chemistry when it is used for full electrical vehicles. The investigation...... is used to study the capacity and power capability degradation behavior of the tested nanophosphate LiFePO4/C battery for two EV operational scenarios....

Poly(2-hydroxyethyl methacrylate) grafted halloysite nanotubes as a molecular host matrix for luminescent ions prepared by surface-initiated RAFT polymerization and coordination chemistry

Energy Technology Data Exchange (ETDEWEB)

Islam, Md. Rafiqul; Bach, Long Giang; Lim, Kwon Taek, E-mail: ktlim@pknu.ac.kr

2013-07-01

A fluorescent nanohybrid complex comprising of halloysite nanotubes (HNTs), poly(2-hydroxyethyl methacrylate) (PHEMA), and europium ions (Eu{sup 3+}) was synthesized by the combination of surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization and coordination chemistry. Initially, PHEMA was grafted from the HNTs by SI-RAFT and then reacted with succinic anhydride to provide carboxyl acid groups on the external layers of HNTs-g-PHEMA nanohybrids. The subsequent coordination of the nanohybrids with Eu{sup 3+} ions afforded photoluminescent Eu{sup 3+} tagged HNTs-g-PHEMA nanohybrid complexes (HNTs-g-PHEMA-Eu{sup 3+}). The structure, morphology, and fluorescence properties of the Eu{sup 3+} coordinated nanohybrid complexes were investigated by respective physical and spectral studies. FT-IR, XPS, and EDS analyses suggested the formation of the HNTs-g-PHEMA-Eu{sup 3+} nanohybrids. FE-SEM images indicated the immobilization of polymer layers on HNTs. TGA scans further demonstrated the grafting of PHEMA onto HNTs surface. The optical properties of HNTs-g-PHEMA-Eu{sup 3+} nanohybrid complexes were investigated by photoluminescence spectroscopy.

Marcoule institute for separation chemistry - ICSM. Scientific report 2007 - 2010

International Nuclear Information System (INIS)

2010-01-01

the future. The fourth generation including better usage of resources is seen as an actor for sustainable development compatible with limited resources and chemical preservation of the atmosphere. Separation chemistry, a branch of physical chemistry, is a key part of 'green chemistry'. The science required is the emerging 'Nano-science', as defined in the corresponding RST report of the French Academy by R. Corriu. Nano-science and physical chemistry, are the roots of modern chemistry considering also non-covalent and long-range interactions, and using these weak forces in separation processes. The perspective view of former published work by scientists at ICSM, as well as access to the laboratory ATALANTE are guarantees of important progresses of fundamental research in Chemistry at ICSM, as defined by the Haut commissaire a l'Energie Atomique at the launching of the project in July 2004. The report here gives an integrated picture of work published since 2007 (M. Leroy et al.) in the direction of the scientific open questions as defined and published by the French academy the same year. This initial definition of long terms tasks is included in this report. Nine teams have started to experiment, from synthesis to characterisation, with a strong input of modelling. The papers resulting from this work are grouped by teams. For each team, the objectives and competences are exposed together the driving force of the research and some crucial results are given in a simple format, with full references at the bottom of each page. Content: 1 - Chemistry and Physical-chemistry of the Actinides; 2 - Ions at Interfaces; 3 - Ion separation using supra-molecular self-assembled colloids; 4 - Sono-chemistry in Complex Fluids; 5 - Self Repairing Nano-materials; 6 - Surface of materials in rapid evolution; 7 - Scattering and diffraction; 8 - Microscopies; 9 - Mesoscopic Modelling and Theoretical Chemistry

HI and Low Metal Ions at the Intersection of Galaxies and the CGM

Science.gov (United States)

Oppenheimer, Benjamin

2017-08-01

Over 1000 COS orbits have revealed a surprisingly complex picture of circumgalactic gas flows surrounding the diversity of galaxies in the evolved Universe. Cosmological hydrodynamic simulations have only begun to confront the vast amount of galaxy formation physics, chemistry, and dynamics revealed in the multi-ion CGM datasets. We propose the next generation of EAGLE zoom simulations, called EAGLE Cosmic Origins, to model HI and low metal ions (C II, Mg II, & Si II) throughout not just the CGM but also within the galaxies themselves. We will employ a novel, new chemistry solver, CHIMES, to follow time-dependent ionization, chemistry, and cooling of 157 ionic and molecular species, and include multiple ionization sources from the extra-galactic background, episodic AGN, and star formation. Our aim is to understand the complete baryon cycle of inflows, outflows, and gas recycling traced over 10 decades of HI column densities as well as the complex kinematic information encoded low ion absorption spectroscopy. This simulation project represents a pilot program for a larger suite of zoom simulations, which will be publicly released and lead to additional publications.

Organic decontamination by ion exchange

International Nuclear Information System (INIS)

Wilson, T.R.

1994-01-01

This study has successfully identified ion exchanger media suitable for decontaminating the 5500-gallon organic layer in Tank 241-C-103. Decontamination of radionuclides is necessary to meet shipping, incinerator site storage, and incineration feed requirements. The exchanger media were identified through a literature search and experiments at the Russian Institute for Physical Chemistry. The principal radionuclides addressed are Cs-137 and Sr-90. Recommendations for an experimental program plan conclude the discussion. The experimental program would provide the data necessary for plant design specifications for a column and for ion exchange media to be used in decontaminating the organic layer

Ion beam effects in organic molecular solids and polymers

International Nuclear Information System (INIS)

Venkatesan, T.; Calcagno, L.; Elman, B.S.; Foti, G.

1987-01-01

In general ion implantation leads to irreversible changes in organic films and hence it is important to understand the damage mechanisms in these solids. Most of the technology based on irradiation effects in organics must somehow make use of the fact that the chemistry of the organic films is easily changed. This chapter is organized to explore the various ion induced chemical changes in the organic films followed by a description of the optical and electrical property changes produced in the films due to the ion irradiation

The Crossed-Beam Scattering Method in Studies of Ion-Molecule Reaction Dynamics

Czech Academy of Sciences Publication Activity Database

Herman, Zdeněk

2001-01-01

Roč. 212, - (2001), s. 413-443 ISSN 1387-3806 R&D Projects: GA ČR GA203/00/0632 Institutional research plan: CEZ:AV0Z4040901 Keywords : ion-molecule reaction dynamics * ion scattering * experimental methods Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.176, year: 2001

Major ion chemistry and quality assessment of groundwater in Haripur area

International Nuclear Information System (INIS)

Akram, W.; Tariq, J.A.; Ahmad, M.

2011-07-01

Study was conducted for investigating chemical composition of groundwater, identifying the compositional types of groundwater, delineating the processes controlling the groundwater chemistry and assessing the groundwater quality for drinking / irrigation uses. Groundwater samples collected from shallow (hand pumps, open well, motor pumps) and deep (tube wells) aquifers were analyzed for major cations (Na/sup +/,K/sup +, Ca/sup 2+/, Mg/sup 2+/) and anions (HCO/sub 3/, Cl/sup '/, SO/sub 4/). The data indicated that Ca/sub 2/ is the dominant cation in most of the samples followed by Mg/sup 2+/ whereas HCO/sub 3/ is the most abundant anion in all samples. Hydrochemistry provides a clear indication of active recharge of shallow and deep aquifers by modern meteoric water. Carbonate dissolution was found to be the prevailing process controlling the groundwater chemistry. Chemical quality was assessed for drinking purpose by comparing with WHO, Indian and national standards, and for irrigation purpose using empirical indices such as SAR and RSC. The results show that groundwater meets the norms of good quality drinking water and can be safely used for irrigation. (author)

Redox flow batteries with serpentine flow fields: Distributions of electrolyte flow reactant penetration into the porous carbon electrodes and effects on performance

Science.gov (United States)

Ke, Xinyou; Prahl, Joseph M.; Alexander, J. Iwan D.; Savinell, Robert F.

2018-04-01

Redox flow batteries with flow field designs have been demonstrated to boost their capacities to deliver high current density and power density in medium and large-scale energy storage applications. Nevertheless, the fundamental mechanisms involved with improved current density in flow batteries with serpentine flow field designs have been not fully understood. Here we report a three-dimensional model of a serpentine flow field over a porous carbon electrode to examine the distributions of pressure driven electrolyte flow penetrations into the porous carbon electrodes. We also estimate the maximum current densities associated with stoichiometric availability of electrolyte reactant flow penetrations through the porous carbon electrodes. The results predict reasonably well observed experimental data without using any adjustable parameters. This fundamental work on electrolyte flow distributions of limiting reactant availability will contribute to a better understanding of limits on electrochemical performance in flow batteries with serpentine flow field designs and should be helpful to optimizing flow batteries.

A selected ion flow tube study of the ion molecule association reactions of protonated (MH+), nitrosonated (MNO+) and dehydroxidated (M-OH)(+) carboxylic acids (M) with H2O

Czech Academy of Sciences Publication Activity Database

Brůhová Michalčíková, R.; Španěl, Patrik

2014-01-01

Roč. 368, JUL 2014 (2014), s. 15-22 ISSN 1387-3806 R&D Projects: GA ČR GA13-28882S Institutional support: RVO:61388955 Keywords : ion molecule reactions * proton transfer * selected ion flow tube mass spectrometry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.972, year: 2014

Cluster ions and van der Waals molecules

CERN Document Server

Smirnov, Boris M

1992-01-01

This review discusses current ideas in the physics and chemistry of cluster ions and Van der Waals molecules as well as presenting numerical data on their parameters and the processes involving them. It is also a detailed reference on basic data relating to many species.

Beyond the Hofmeister Series: Ion-Specific Effects on Proteins and Their Biological Functions

Czech Academy of Sciences Publication Activity Database

Okur, H. I.; Hladílková, Jana; Rembert, K. B.; Cho, Y.; Heyda, J.; Dzubiella, J.; Cremer, P. S.; Jungwirth, Pavel

2017-01-01

Roč. 121, č. 9 (2017), s. 1997-2014 ISSN 1520-6106 R&D Projects: GA ČR(CZ) GA16-01074S Institutional support: RVO:61388963 Keywords : Hofmeister series * ions * proteins * molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 3.177, year: 2016

Kinetic energy and charge distributions of multiply charged ions produced by heavy ions and by synchrotron radiation

International Nuclear Information System (INIS)

Levin, J.C.; Biedermann, C.; Cederquist, H.; Liljeby, L.; Short, R.T.; Sellin, I.A.

1989-01-01

This paper contrasts two methods of production of multiply charged ions which may have application in future hot-atom chemistry experiments. Interest in extending the study of ion-atom collisions from MeV to keV to eV energies has grown rapidly in the last decade as previously inaccessible astrophysical, fusion, and spectroscopic problems have been addressed. One of these methods involves highly charged secondary beams formed from ions created in dilute gas samples irradiated by fast (MeV), high-charge-state, heavy ions. The measurements show, however, that such ions often have mean recoil energies two orders of magnitude higher than kinetic energies of ions in similar charge states resulting from vacancy cascades of atomic inner shells photoionized by synchrotron x rays. These results may be applicable to development of a cold source of highly charged ions featuring low energy spread and good angular definition. Results from other laboratories (Grandin et al at Ganil, Ullrich et al in Frankfurt, and Watson et al at Texas A ampersand M) will also be discussed

Replacing Chlorine with Hydrogen Chloride as a Possible Reactant for Synthesis of Titanium Carbide Derived Carbon Powders for High-Technology Devices

International Nuclear Information System (INIS)

Tallo, Indrek; Thomberg, Thomas; Jänes, Alar; Lust, Enn

2013-01-01

Micro- and mesoporous carbide-derived carbons were synthesized from titanium carbide (TiC) powder via gas phase reaction by using different reactants (Cl 2 and HCl) within the temperature range from 700 to 1100 °C. Analysis of XRD results show that TiC-derived carbons (TiC-CDC) consist mainly of graphitic crystallites. The first-order Raman spectra showed the graphite-like absorption peaks at ∼1577 cm 1 and the disorder-induced peaks at ∼1338 cm- 1 . The energy-related properties of supercapacitors based on 1 M (C 2 H 5 ) 3 CH 3 NBF 4 in acetonitrile and carbide-derived carbons (TiC-CDC (Cl 2 ) and TiC-CDC (HCl)) as electrode materials were also investigated using cyclic voltammetry, electrochemical impedance spectroscopy, galvanostatic charge/discharge and constant power methods. The Ragone plots for carbide-derived carbons prepared by using different reactants (Cl 2 , HCl) are quite similar and at high power loads TiC-CDC (Cl 2 ) material synthesized at 900 °C, i.e. materials with optimal porous structure, deliver higher power at constant energy

David J. Triggle: Medicinal chemistry, to pharmacology, calcium channels, and beyond.

Science.gov (United States)

Walker, Michael J A

2015-11-15

David Triggle's scientific career began as a chemist, went through medicinal chemistry into pharmacology, and finally on to somewhat more philosophical interests in later years. It was a career marked by many contributions to all of those aspects of science. Chief amongst his many contributions, in addition to those in medicinal chemistry, was his work on the drugs known as calcium ion channel blockers or (calcium antagonists). In the calcium ion channel field he was a particularly instrumental figure in sorting out the mechanisms, actions and roles of the class of calcium channel blockers, known chemical and pharmacologically as the dihydropyridines (DHPs) in particular, as well as other calcium blockers of diverse structures. During the course of a long career, and extensive journeys into medicinal chemistry and pharmacology, he published voluminously in terms of papers, reviews, conference proceedings and books. Notably, many of his papers often had limited authorship where, as senior author it reflected his deep involvement in all aspects of the reported work. His work always helped clarify the field while his incisive reviews, together with his role in coordinating and running scientific meetings, were a great help in clarifying and organizing various fields of study. He has had a long and illustrious career, and is wellknown in the world of biomedical science; his contributions are appreciated, and well recognized everywhere. The following article attempts to chart a path through his work and contributions to medicinal chemistry, pharmacology, science, academia and students. Copyright © 2015 Elsevier Inc. All rights reserved.

Substantial difference in target surface chemistry between reactive dc and high power impulse magnetron sputtering

Science.gov (United States)

Greczynski, G.; Mráz, S.; Schneider, J. M.; Hultman, L.

2018-02-01

The nitride layer formed in the target race track during the deposition of stoichiometric TiN thin films is a factor 2.5 thicker for high power impulse magnetron sputtering (HIPIMS), compared to conventional dc processing (DCMS). The phenomenon is explained using x-ray photoelectron spectroscopy analysis of the as-operated Ti target surface chemistry supported by sputter depth profiles, dynamic Monte Carlo simulations employing the TRIDYN code, and plasma chemical investigations by ion mass spectrometry. The target chemistry and the thickness of the nitride layer are found to be determined by the implantation of nitrogen ions, predominantly N+ and N2+ for HIPIMS and DCMS, respectively. Knowledge of this method-inherent difference enables robust processing of high quality functional coatings.

Third Chemistry Conference on Recent Trends in Chemistry

International Nuclear Information System (INIS)

Saeed, M.M.; Wheed, S.

2011-01-01

The third chemistry conference 2011 on recent trends in chemistry was held from October 17-19, 2001 at Islamabad, Pakistan. More than 65 papers and oral presentation. The scope of the conference was wide open and provides and opportunity for participation of broad spectrum of chemists. This forum provided a platform for the dissemination of the latest research followed by discussion pertaining to new trends in chemistry. This con fence covered different aspects of subjects including analytical chemistry, environmental chemistry, polymer chemistry, industrial chemistry, biochemistry and nano chemistry etc. (A.B.)

Ionic liquids: radiation chemistry, solvation dynamics and reactivity patterns

International Nuclear Information System (INIS)

Wishart, J.F.; Funston, A.M.; Szreder, T.

2006-01-01

Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of energy production, chemical industry and environmental applications. Pulse radiolysis of [R 4 N][NTf 2 ] [R 4 N][N(CN) 2 ], and [R 4 P][N(CN) 2 ] ionic liquids produces solvated electrons that absorb over a broad range in the near infrared and persisting for hundreds of nanoseconds. Systematic cation variation shows that solvated electron's spectroscopic properties depend strongly on the lattice structure of the ionic liquid. Very early in our radiolysis studies it became evident that

Methylene-transfer reactions of benzylium/tropylium ions with neutral toluene studied by means of ion-trap mass spectrometry

Czech Academy of Sciences Publication Activity Database

Zins, E. L.; Pepe, C.; Schröder, Detlef

2010-01-01

Roč. 145, - (2010), s. 157-169 E-ISSN 1364-5498 Grant - others: ERC (XE) HORIZOMS AdG226373 Institutional research plan: CEZ:AV0Z40550506 Keywords : benzylium * electrospray ionization * infrared spectroscopy * ion trap * tropylium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.538, year: 2010

Constitutional dynamic chemistry: bridge from supramolecular chemistry to adaptive chemistry.

Science.gov (United States)

Lehn, Jean-Marie

2012-01-01

Supramolecular chemistry aims at implementing highly complex chemical systems from molecular components held together by non-covalent intermolecular forces and effecting molecular recognition, catalysis and transport processes. A further step consists in the investigation of chemical systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, thus behaving as programmed chemical systems. Supramolecular chemistry is intrinsically a dynamic chemistry in view of the lability of the interactions connecting the molecular components of a supramolecular entity and the resulting ability of supramolecular species to exchange their constituents. The same holds for molecular chemistry when the molecular entity contains covalent bonds that may form and break reversibility, so as to allow a continuous change in constitution by reorganization and exchange of building blocks. These features define a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels.CDC introduces a paradigm shift with respect to constitutionally static chemistry. The latter relies on design for the generation of a target entity, whereas CDC takes advantage of dynamic diversity to allow variation and selection. The implementation of selection in chemistry introduces a fundamental change in outlook. Whereas self-organization by design strives to achieve full control over the output molecular or supramolecular entity by explicit programming, self-organization with selection operates on dynamic constitutional diversity in response to either internal or external factors to achieve adaptation.The merging of the features: -information and programmability, -dynamics and reversibility, -constitution and structural diversity, points to the emergence of adaptive and evolutive chemistry, towards a chemistry of complex matter.

What is the fundamental ion-specific series for anions and cations? Ion specificity in standard partial molar volumes of electrolytes and electrostriction in water and non-aqueous solvents.

Science.gov (United States)

Mazzini, Virginia; Craig, Vincent S J

2017-10-01

The importance of electrolyte solutions cannot be overstated. Beyond the ionic strength of electrolyte solutions the specific nature of the ions present is vital in controlling a host of properties. Therefore ion specificity is fundamentally important in physical chemistry, engineering and biology. The observation that the strengths of the effect of ions often follows well established series suggests that a single predictive and quantitative description of specific-ion effects covering a wide range of systems is possible. Such a theory would revolutionise applications of physical chemistry from polymer precipitation to drug design. Current approaches to understanding specific-ion effects involve consideration of the ions themselves, the solvent and relevant interfaces and the interactions between them. Here we investigate the specific-ion effects trends of standard partial molar volumes and electrostrictive volumes of electrolytes in water and eleven non-aqueous solvents. We choose these measures as they relate to bulk properties at infinite dilution, therefore they are the simplest electrolyte systems. This is done to test the hypothesis that the ions alone exhibit a specific-ion effect series that is independent of the solvent and unrelated to surface properties. The specific-ion effects trends of standard partial molar volumes and normalised electrostrictive volumes examined in this work show a fundamental ion-specific series that is reproduced across the solvents, which is the Hofmeister series for anions and the reverse lyotropic series for cations, supporting the hypothesis. This outcome is important in demonstrating that ion specificity is observed at infinite dilution and demonstrates that the complexity observed in the manifestation of specific-ion effects in a very wide range of systems is due to perturbations of solvent, surfaces and concentration on the underlying fundamental series. This knowledge will guide a general understanding of specific-ion

Specific ion effects on membrane potential and the permselectivity of ion exchange membranes.

Science.gov (United States)

Geise, Geoffrey M; Cassady, Harrison J; Paul, Donald R; Logan, Bruce E; Hickner, Michael A

2014-10-21

Membrane potential and permselectivity are critical parameters for a variety of electrochemically-driven separation and energy technologies. An electric potential is developed when a membrane separates electrolyte solutions of different concentrations, and a permselective membrane allows specific species to be transported while restricting the passage of other species. Ion exchange membranes are commonly used in applications that require advanced ionic electrolytes and span technologies such as alkaline batteries to ammonium bicarbonate reverse electrodialysis, but membranes are often only characterized in sodium chloride solutions. Our goal in this work was to better understand membrane behaviour in aqueous ammonium bicarbonate, which is of interest for closed-loop energy generation processes. Here we characterized the permselectivity of four commercial ion exchange membranes in aqueous solutions of sodium chloride, ammonium chloride, sodium bicarbonate, and ammonium bicarbonate. This stepwise approach, using four different ions in aqueous solution, was used to better understand how these specific ions affect ion transport in ion exchange membranes. Characterization of cation and anion exchange membrane permselectivity, using these ions, is discussed from the perspective of the difference in the physical chemistry of the hydrated ions, along with an accompanying re-derivation and examination of the basic equations that describe membrane potential. In general, permselectivity was highest in sodium chloride and lowest in ammonium bicarbonate solutions, and the nature of both the counter- and co-ions appeared to influence measured permselectivity. The counter-ion type influences the binding affinity between counter-ions and polymer fixed charge groups, and higher binding affinity between fixed charge sites and counter-ions within the membrane decreases the effective membrane charge density. As a result permselectivity decreases. The charge density and polarizability

Preorganized and Immobilized Ligands for Metal Ion Separations

Energy Technology Data Exchange (ETDEWEB)

Paine, Robert T. [Univ. of New Mexico, Albuquerque, NM (United States)

2015-07-01

The research project, in the period 2003-2015, was focused on the discovery of fundamental new principles in f-element ion coordination chemistry and the application of the new knowledge to the development of advanced detection/separations reagents and methods for these ions. The findings relate to the Nation's efforts to safely and efficiently process nuclear materials. In addition, the project provided training for young scientists needed to maintain the Nation's preeminence in nuclear science.

Dissociative properties of 1,1,1,2-tetrafluoroethane obtained by computational chemistry

Science.gov (United States)

Hayashi, Toshio; Ishikawa, Kenji; Sekine, Makoto; Hori, Masaru

2018-06-01

The electronic properties and dissociative channels of the alternative to the CCl2F2 (CFC-12) refrigerant, 1,1,1,2-tetrafluoroethane (HFC-134a) with a low global warming potential (GWP, 1430), were revealed by computational chemistry. The results show that CF3 + and CHF2 + ions are mainly produced by ionization. The CF3CH2 + ion is produced by ion pair formation and by direct ionization in the energy region higher than approximately 15 eV, but also in small amounts by the ionization of the dissociated CF3CH2 radical. This information is useful for etching process engineers in leading-edge semiconductor manufacturing.

Exploring Ion-Ion Interactions in Aqueous Solutions by a Combination of Molecular Dynamics and Neutron Scattering

Czech Academy of Sciences Publication Activity Database

Kohagen, Miriam; Pluhařová, E.; Mason, Philip E.; Jungwirth, Pavel

2015-01-01

Roč. 6, č. 9 (2015), s. 1563-1567 ISSN 1948-7185 R&D Projects: GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : ion pairing * molecular dynamics * neutron scattering Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 8.539, year: 2015 http://pubs.acs.org/doi/pdf/10.1021/acs.jpclett.5b00060

Unraveling the Reaction Chemistry of Icy Ocean World Surfaces

Science.gov (United States)

Hudson, R.; Loeffler, M. J.; Gerakines, P.

2017-12-01

The diverse endogenic chemistry of ocean worlds can be divided among interior, surface, and above-surface process, with contributions from exogenic agents such as solar, cosmic, and magnetospheric radiation. Bombardment from micrometeorites to comets also can influence chemistry by both delivering new materials and altering pre-existing ones, and providing energy to drive reactions. Geological processes further complicate the chemistry by transporting materials from one environment to another. In this presentation the focus will be on some of the thermally driven and radiation-induced changes expected from icy materials, primarily covalent and ionic compounds. Low-temperature conversions of a few relatively simple molecules into ions possessing distinct infrared (IR) features will be covered, with an emphasis on such features as might be identified through either orbiting spacecraft or landers. The low-temperature degradation of a few bioorganic molecules, such as DNA nucleobases and some common amino acids, will be used as examples of the more complex, and potentially misleading, chemistry expected for icy moons of the outer solar system. This work was supported by NASA's Emerging Worlds and Outer Planets Research programs, as well as the NASA Astrobiology Institute's Goddard Center for Astrobiology.

Clearcutting affects stream chemistry in the White Mountains of New Hampshire

Science.gov (United States)

C. Wayne Martin; Robert S. Pierce; Gene E. Likens; F. Herbert Bormann; F. Herbert Bormann

1986-01-01

Commercial clearcutting of northern hardwood forests changed the chemistry of the streams that drained from them. By the second year after cutting, specific conductance doubled, nitrate increased tenfold, calcium tripled, and sodium, magnesium, and potassium doubled. Chloride and ammonium did not change; sulfate decreased. Concentrations of most ions returned to...

Radiation chemistry

International Nuclear Information System (INIS)

Rodgers, F.; Rodgers, M.A.

1987-01-01

The contents of this book include: Interaction of ionizing radiation with matter; Primary products in radiation chemistry; Theoretical aspects of radiation chemistry; Theories of the solvated electron; The radiation chemistry of gases; Radiation chemistry of colloidal aggregates; Radiation chemistry of the alkali halides; Radiation chemistry of polymers; Radiation chemistry of biopolymers; Radiation processing and sterilization; and Compound index

Investigation of the drastic change in the sputter rate of polymers at low ion fluence

International Nuclear Information System (INIS)

Zekonyte, J.; Zaporojtchenko, V.; Faupel, F.

2005-01-01

The polymer sputter rate dependence on ion fluence and ion chemistry (Ar, N 2 , O 2 ) at 1 keV energy was investigated using a quartz crystal microbalance (QCM) which allowed to do real time etch rate measurements and to study kinetics of sputtering. The obtained sputter rates differed drastically from polymer to polymer showing, that the chemical structure of polymer is an important factor in the polymer etch yield. A decrease in the sputter rate was observed up to ion fluence of 5 x 10 14 -5 x 10 15 cm -2 (depending on the polymer type and ion chemistry) followed by the saturation in the rate at prolonged ion bombardment. Polymer removal was accompanied by the formation of degradation products, cross-linking or branching, modification of the surface chemical structure, which was studied in situ using XPS. The dependence of the surface glass transition temperature, T gs on the ion fluence was studied using the method based on the embedding of metallic nanoparticles. The correlation between chemical yield data and ablation rate is discussed

Paper-Based Heavy Metal Sensors from the Concise Synthesis of an Anionic Porphyrin: A Practical Application of Organic Synthesis to Environmental Chemistry

Science.gov (United States)

Prabpal, Jutamat; Vilaivan, Tirayut; Praneenararat, Thanit

2017-01-01

Tetrakis(4-sulfonatophenyl)porphyrin (TSPP) was immobilized on patterned paper and used as a sensor for heavy metal ions in an advanced organic chemistry course. The resulting sensor could detect Hg[superscript 2+] and Cd[superscript 2+] ions colorimetrically, while Cu[superscript 2+] ion resulted in fluorescence quenching, thus demonstrating a…

Enrichment of lithium isotope .sup.6./sup.Li by ion exchange resin with specific particle size

Czech Academy of Sciences Publication Activity Database

Mikeš, J.; Ďurišová, Jana; Jelínek, L.

2017-01-01

Roč. 312, č. 1 (2017), s. 13-18 ISSN 0236-5731 Institutional support: RVO:67985831 Keywords : lithium * isotope separation * elution chromatography * ion exchange chromatography Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Inorganic and nuclear chemistry Impact factor: 1.282, year: 2016

Solution chemistry techniques in SYNROC preparation

International Nuclear Information System (INIS)

Dosch, R.G.; Lynch, A.W.

1981-07-01

Investigations of titanate-based ceramic forms for radioactive waste immobilization are underway at Sandia National Laboratories (SNLA) and at Lawrence Livermore National Laboratory (LLNL). Although the waste forms differ as to overall product composition, the waste-containing phases in both ceramic products have similar crystalline structure types. These include metallic phases along with oxides with structure types of the mineral analogues perovskite, zirconolite, and hollandite. Significant differences also exist in the area of processing. More conventional ceramic processing methods are used at LLNL to produce SYNROC while solution chemistry techniques involving metal alkoxide chemistry and ion exchange have been developed at SNLA to prepare calcium titanate-based waste ceramics. The SNLA techniques were recently modified and applied to producing SYNROC (compositions C and D) as part of an interlaboratory information exchange between SNLA and LLNL. This report describes the methods used in preparing SYNROC including the solution interaction, and hot-pressing methods used to obtain fully dense SYNROC monoliths

Surface ligand controls silver ion release of nanosilver and its antibacterial activity against Escherichia coli

Directory of Open Access Journals (Sweden)

Long Y

2017-04-01

Full Text Available Yan-Min Long,1,2 Li-Gang Hu,1,3 Xue-Ting Yan,1,3 Xing-Chen Zhao,1,3 Qun-Fang Zhou,1,3 Yong Cai,2,4 Gui-Bin Jiang1,3 1State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Beijing, China; 2Institute of Environment and Health, Jianghan University, Wuhan, Hubei, China; 3College of Resources and Environment, University of Chinese Academy of Sciences, Beijing, China; 4Department of Chemistry and Biochemistry, Southeast Environmental Research Center, Florida International University, Miami, FL, USA Abstract: Understanding the mechanism of nanosilver-dependent antibacterial activity against microorganisms helps optimize the design and usage of the related nanomaterials. In this study, we prepared four kinds of 10 nm-sized silver nanoparticles (AgNPs with dictated surface chemistry by capping different ligands, including citrate, mercaptopropionic acid, mercaptohexanoic acid, and mercaptopropionic sulfonic acid. Their surface-dependent chemistry and antibacterial activities were investigated. Owing to the weak bond to surface Ag, short carbon chain, and low silver ion attraction, citrate-coated AgNPs caused the highest silver ion release and the strongest antibacterial activity against Escherichia coli, when compared to the other tested AgNPs. The study on the underlying antibacterial mechanisms indicated that cellular membrane uptake of Ag, NAD+/NADH ratio increase, and intracellular reactive oxygen species (ROS generation were significantly induced in both AgNP and silver ion exposure groups. The released silver ions from AgNPs inside cells through a Trojan-horse-type mechanism were suggested to interact with respiratory chain proteins on the membrane, interrupt intracellular O2 reduction, and induce ROS production. The further oxidative damages of lipid peroxidation and membrane breakdown caused the lethal effect on E. coli. Altogether, this study demonstrated that AgNPs exerted

Shutdown Chemistry Process Development for PWR Primary System

Energy Technology Data Exchange (ETDEWEB)

Sung, K.B. [Korea Electric Power Research Institute, Taejeon (Korea, Republic of)

1997-12-31

This study report presents the shutdown chemistry of PWR primary system to reduce and remove the radioactive corrosion products which were deposited on the nuclear fuel rods surface and the outside of core like steam generator channel head, RCS pipings etc. The major research results are the follows ; the deposition radioactive mechanism of corrosion products, the radiochemical composition, the condition of coolant chemistry to promote the dissolution of radioactive cobalt and nickel ferrite, the control method of dissolved hydrogen concentration in the coolant by the mechanical and chemical methods. The another part of study is to investigate the removal characteristics of corrosion product ions and particles by the demineralization system to suggest the method which the system could be operate effectively in shut-down purification period. (author). 19 refs., 25 figs., 48 tabs.

Theoretical chemistry periodicities in chemistry and biology

CERN Document Server

Eyring, Henry

1978-01-01

Theoretical Chemistry: Periodicities in Chemistry and Biology, Volume 4 covers the aspects of theoretical chemistry. The book discusses the stably rotating patterns of reaction and diffusion; the chemistry of inorganic systems exhibiting nonmonotonic behavior; and population cycles. The text also describes the mathematical modeling of excitable media in neurobiology and chemistry; oscillating enzyme reactions; and oscillatory properties and excitability of the heart cell membrane. Selected topics from the theory of physico-chemical instabilities are also encompassed. Chemists, mechanical engin

f-Element Ion Chelation in Highly Basic Media

International Nuclear Information System (INIS)

Paine, R.T.

2000-01-01

A large body of data has been collected over the last fifty years on the chemical behavior of f-element ions. The ions undergo rapid hydrolysis reactions in neutral or basic aqueous solutions that produce poorly understood oxide-hydroxide species; therefore, most of the fundamental f-element solution chemistry has allowed synthetic and separations chemists to rationally design advanced organic chelating ligands useful for highly selective partitioning and separation of f-element ions from complex acidic solution matrices. These ligands and new examples under development allow for the safe use and treatment of solutions containing highly radioactive species. This DOE/EMSP project was undertaken to address the following fundamental objectives: (1) study the chemical speciation of Sr and lanthanide (Ln) ions in basic aqueous media containing classical counter anions found in waste matrices; (2) prepare pyridine N-oxide phosphonates and phosphonic acids that might act as selective chelators for Ln ions in model basic pH waste streams; (3) study the binding of the new chelators toward Ln ions and (4) examine the utility of the chelators as decontamination and dissolution agents under basic solution conditions. The project has been successful in attacking selected aspects of the very difficult problems associated with basic pH solution f-element waste chemistry. In particular, the project has (1) shed additional light on the initial stages of Ln ion sol-gel-precipitate formulation under basic solution conditions; (2) generated new families of pyridine phosphonic acid chelators; (3) characterized the function of the chelators and (4) examined their utility as oxide-hydroxide dissolution agents. These findings have contributed significantly to an improved understanding of the behavior of Ln ions in basic media containing anions found in typical waste sludges as well as to the development of sludge dissolution agents. The new chelating reagents are easily made and could be

Adiabatic Cooling for Rovibrational Spectroscopy of Molecular Ions

DEFF Research Database (Denmark)

Fisher, Karin

2017-01-01

The field of cold molecular ions is a fast growing one, with applications in high resolution spectroscopy and metrology, the search for time variations of fundamental constants, cold chemistry and collisions, and quantum information processing, to name a few. The study of single molecular ions...... is attractive as it enables one to push the limits of spectroscopic accuracy. Non-destructive spectroscopic detection of molecular ions can be achieved by co-trapping with an easier to detect atomic ion. The ion chain has coupled motion, and transitions which change both the internal and motional states...... to the measured heating rates, almost perfectly fitting existing heating rate theory. Further, the same model successfully predicted the heating rates of the in-phase mode of a two-ion crystal, indicating that we can use it to predict the heating rates in experiments on molecule-atom chains. Adiabatic cooling...

Physical chemistry of portland-cement hydrate, radioactive-waste hosts: Final report, January 16, 1987--December 31, 1987

International Nuclear Information System (INIS)

Grutzeck, M.W.

1989-01-01

This is a final report summarizing the results of a study of the physical and crystal chemistry of potential hydroxylated radioactive waste hosts compatible with portland cement. Research has focussed on the identification and evaluation of hydrated host phases for four ions: cesium, strontium, iodine and boron. These ions were chosen because they are among the most long lived of the radioactive waste ions as well as the most difficult to immobilize with cement-based materials. Results show that such phases do indeed exist, and that they are excellent host phases for the above ions

Spatial atomic layer deposition on flexible porous substrates: ZnO on anodic aluminum oxide films and Al2O3 on Li ion battery electrodes

International Nuclear Information System (INIS)

Sharma, Kashish; Routkevitch, Dmitri; Varaksa, Natalia; George, Steven M.

2016-01-01

Spatial atomic layer deposition (S-ALD) was examined on flexible porous substrates utilizing a rotating cylinder reactor to perform the S-ALD. S-ALD was first explored on flexible polyethylene terephthalate polymer substrates to obtain S-ALD growth rates on flat surfaces. ZnO ALD with diethylzinc and ozone as the reactants at 50 °C was the model S-ALD system. ZnO S-ALD was then performed on nanoporous flexible anodic aluminum oxide (AAO) films. ZnO S-ALD in porous substrates depends on the pore diameter, pore aspect ratio, and reactant exposure time that define the gas transport. To evaluate these parameters, the Zn coverage profiles in the pores of the AAO films were measured using energy dispersive spectroscopy (EDS). EDS measurements were conducted for different reaction conditions and AAO pore geometries. Substrate speeds and reactant pulse durations were defined by rotating cylinder rates of 10, 100, and 200 revolutions per minute (RPM). AAO pore diameters of 10, 25, 50, and 100 nm were utilized with a pore length of 25 μm. Uniform Zn coverage profiles were obtained at 10 RPM and pore diameters of 100 nm. The Zn coverage was less uniform at higher RPM values and smaller pore diameters. These results indicate that S-ALD into porous substrates is feasible under certain reaction conditions. S-ALD was then performed on porous Li ion battery electrodes to test S-ALD on a technologically important porous substrate. Li 0.20 Mn 0.54 Ni 0.13 Co 0.13 O 2 electrodes on flexible metal foil were coated with Al 2 O 3 using 2–5 Al 2 O 3 ALD cycles. The Al 2 O 3 ALD was performed in the S-ALD reactor at a rotating cylinder rate of 10 RPM using trimethylaluminum and ozone as the reactants at 50 °C. The capacity of the electrodes was then tested versus number of charge–discharge cycles. These measurements revealed that the Al 2 O 3 S-ALD coating on the electrodes enhanced the capacity stability. This S-ALD process could be extended to roll-to-roll operation for

The influence of ion implantation on the surface properties of metals and alloys

International Nuclear Information System (INIS)

Grant, W.A.; Carter, G.

1975-10-01

The report falls into three sections: (1) annealing behaviour of high dose rare gas (Ne, Ar, Kr, Xe) implantations into silicon; (2) measurement of projected and lateral range parameters for low energy heavy ions (Ar, Cu, Kr, Cd, Xe, Cs, Dy, W, Au, Pb, Bi) in silicon by Rutherford backscattering; (3) surface chemistry of ion implanted solids (e.g. corrosion, catalysis, oxidation, synthesis of compounds in ion implanted layers). (U.K.)

The impact of ion exchange media and filters on LLW processing

International Nuclear Information System (INIS)

James, K.L.; Miller, C.C.

1992-01-01

Optimized ion exchange media at Diablo Canyon have steadily improved the treatment of radioactive liquid waste. The activity released to the environment has been reduced while simultaneously reducing the volume of solid radwaste generated from processing radioactive liquids. This has lowered the liquid waste processing costs and reduced the number of radioactive shipments from the plant. A cobalt treatment technique was identified and successfully implemented prior to reactor coolant chemistry alteration. A cesium treatment using zeolite has been successfully implemented. A cobalt removal treatment, combining series cation ion exchange with submicron filtration, has successfully removed cobalt after reactor coolant chemistry alteration. A new carbon-based material will be monitored to find a media to remove cobalt from high-conductivity liquids. (author)

Reaction of O+, CO+, and CH+ ions with atomic hydrogen

International Nuclear Information System (INIS)

Federer, W.; Villinger, H.; Howorka, F.; Lindinger, W.; Tosis, P.; Bassi, D.; Ferguson, E.

1984-01-01

Rate coefficients for reactions of the ions O + , CO + , and CH + with atomic hydrogen have been measured for the first time at 300 K. This provides basic data for the ion chemistry of planetary atmospheres, cometary atmospheres, and interstellar molecular clouds. The O + +H measurement supports quantal calculations of this reaction. The CO + +H reaction provides an example of partial spin nonconservation in a charge-transfer reaction occurring in a deep potential well. Reactions of the same ions with H 2 that have been measured elsewhere are also reported

Determination of the ion-exchange capacity of anion-selective membranes

Czech Academy of Sciences Publication Activity Database

Karas, F.; Hnát, J.; Paidar, M.; Schauer, Jan; Bouzek, K.

2014-01-01

Roč. 39, č. 10 (2014), s. 5054-5062 ISSN 0360-3199 Institutional support: RVO:61389013 Keywords : ion-exchange capacity * anion-selective membranes * titration Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.313, year: 2014

Ion irradiated graphite exposed to fusion-relevant deuterium plasma

International Nuclear Information System (INIS)

Deslandes, Alec; Guenette, Mathew C.; Corr, Cormac S.; Karatchevtseva, Inna; Thomsen, Lars; Ionescu, Mihail; Lumpkin, Gregory R.; Riley, Daniel P.

2014-01-01

Graphite samples were irradiated with 5 MeV carbon ions to simulate the damage caused by collision cascades from neutron irradiation in a fusion environment. The ion irradiated graphite samples were then exposed to a deuterium plasma in the linear plasma device, MAGPIE, for a total ion fluence of ∼1 × 10 24 ions m −2 . Raman and near edge X-ray absorption fine structure (NEXAFS) spectroscopy were used to characterize modifications to the graphitic structure. Ion irradiation was observed to decrease the graphitic content and induce disorder in the graphite. Subsequent plasma exposure decreased the graphitic content further. Structural and surface chemistry changes were observed to be greatest for the sample irradiated with the greatest fluence of MeV ions. D retention was measured using elastic recoil detection analysis and showed that ion irradiation increased the amount of retained deuterium in graphite by a factor of four

Magnetic relaxation in analytical, coordination and bioinorganic chemistry

International Nuclear Information System (INIS)

Mikhajlov, O.

1982-01-01

Nuclear magnetic relaxation is a special type of nuclear magnetic resonance in which the rate is measured of energy transfer between the excited nuclei and their molecular medium (spin-lattice relaxation) or the whole nuclear spin system (spin-spin relaxation). Nuclear magnetic relaxation relates to nuclei with a spin of 1/2, primarily H 1 1 , and is mainly measured in water solutions. It is suitable for (1) analytical chemistry because the relaxation time rapidly reduces in the presence of paramagnetic ions, (2) the study of complex compounds, (3) the study of biochemical reactions in the presence of different metal ions. It is also suitable for testing the composition of a flowing liquid. Its disadvantage is that it requires complex and expensive equipment. (Ha)

Fifty years of high energy chemistry. Current situation and perspectives of development in the Slovak Republic and the Czech Republic

International Nuclear Information System (INIS)

Kuruc, J.

2017-01-01

The paper describes the concepts of a new chemical science - High-Energy Chemistry (HECH). Under this concept, the field of science has been associated with chemical processes initiated by non-thermal energy carriers - ionizing radiation, light, electric, sound field etc. Since 1967, the journal of High Energy Chemistry (Russian Academy of Sciences) has been published, which is translated into the English language High Energy Chemistry (Pleiades Publishing, Ltd.). The common feature of HECH is the formation of ions and excited states at temperatures from the ambient temperature at which these particles cannot be generated due to equilibrium processes. The non-thermal energy carriers and chemical sciences are systematized that have been created by examining the impact of these energy carriers on substances. There are two groups of energy carriers: those that transmit an interaction energy substantially higher than kT (ionizing radiation, light, etc.) in one act, and those that transmit the energy of interaction is higher than kT in a single act but the flux of these energy carriers is so high that in this field, the formation of ions and electron-excited states and free radicals are observed. HECH processes consist of three stages: 1) Interaction of energy carriers with the substance in times of femtosecond with the formation of primary intermediates; 2) Conversion of primary intermediates proceed in times of picoseconds to nanoseconds to secondary and tertiary intermediates ( h ot spots ) because the energy distribution in the medium is inhomogeneous; intermediates unusual for thermal chemistry play an important role at this stage; 3) Chemical stage that takes place over a time exceeding the microsecond, excited states, ions, and radicals, also common for thermal chemistry are involved. In contrast with thermal reactions, the concentration of intermediates of many orders exceeds equilibrium in terms of Maxwell-Boltzmann distribution. High-energy chemistry includes

Fifty years of high energy chemistry. Current situation and perspectives of development in the Slovak Republic and the Czech Republic

International Nuclear Information System (INIS)

Kuruc, J.

2017-01-01

This presentation describes the concepts of a new chemical science - High-Energy Chemistry (HECH). Under this concept, the field of science has been associated with chemical processes initiated by non-thermal energy carriers - ionizing radiation, light, electric, sound field etc. Since 1967, the journal of High Energy Chemistry (Russian Academy of Sciences) has been published, which is translated into the English language High Energy Chemistry (Pleiades Publishing, Ltd.). The common feature of HECH is the formation of ions and excited states at temperatures from the ambient temperature at which these particles cannot be generated due to equilibrium processes. The non-thermal energy carriers and chemical sciences are systematized that have been created by examining the impact of these energy carriers on substances. There are two groups of energy carriers: those that transmit an interaction energy substantially higher than kT (ionizing radiation, light, etc.) in one act, and those that transmit the energy of interaction is higher than kT in a single act but the flux of these energy carriers is so high that in this field, the formation of ions and electron-excited states and free radicals are observed. HECH processes consist of three stages: 1) Interaction of energy carriers with the substance in times of femtosecond with the formation of primary intermediates; 2) Conversion of primary intermediates proceed in times of picoseconds to nanoseconds to secondary and tertiary intermediates ("hot spots") because the energy distribution in the medium is inhomogeneous; intermediates unusual for thermal chemistry play an important role at this stage; 3) Chemical stage that takes place over a time exceeding the microsecond, excited states, ions, and radicals, also common for thermal chemistry are involved. In contrast with thermal reactions, the concentration of intermediates of many orders exceeds equilibrium in terms of Maxwell-Boltzmann distribution. High-energy chemistry

Complex chemistry

International Nuclear Information System (INIS)

Kim, Bong Gon; Kim, Jae Sang; Kim, Jin Eun; Lee, Boo Yeon

2006-06-01

This book introduces complex chemistry with ten chapters, which include development of complex chemistry on history coordination theory and Warner's coordination theory and new development of complex chemistry, nomenclature on complex with conception and define, chemical formula on coordination compound, symbol of stereochemistry, stereo structure and isomerism, electron structure and bond theory on complex, structure of complex like NMR and XAFS, balance and reaction on solution, an organo-metallic chemistry, biology inorganic chemistry, material chemistry of complex, design of complex and calculation chemistry.

Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

Directory of Open Access Journals (Sweden)

Nicola H. Perry

2016-10-01

Full Text Available Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic, and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER, Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance.

Application of radiation chemistry in materials modification and environmental protection

International Nuclear Information System (INIS)

Chmielewski, A.G.

2007-01-01

Radiation chemistry is a part of the physical chemistry similarly like photo-chemistry, plasma-chemistry, ultrasonic-chemistry etc. Ionizing radiation produces abundant secondary electrons. Following these primary events, the ions, secondary electrons and excited molecules undergo further transformations, exchanging charges and energy and reacting with surrounding molecules, thereby producing free radicals and other reactive species which finally evolve into new stable products. Three main sources of radiation are applied for radiation processing. These are electron accelerators, gamma sources and X-ray unit based on e-/X conversion process. Radiation processing was used early on for polymer modification. The intermediates formed during material irradiation can follow several reaction paths that result in disproportion, hydrogen abstraction, arrangements and/or the formation of new bonds. Nowadays, the modification of polymers covers radiation cross-linking, radiation-induced polymerization (graft polymerization and curing) and the degradation of polymers. Some polymers predominantly undergo crosslinking other degradation. However new techniques allow crosslinking of polymers which were considered to be degradable only, like PTFE and cellulose derivatives. Regarding natural polymers the biggest application concerns rubber pre-crosslinking in tire industry. The processing of natural polymers is also being developed to elaborate new biodegradable materials. The radiation crosslinked wires and cables show excellent heat resistance (long-term thermal stability and short-term thermal stability) as well as abrasion resistance. Other big application is crosslinking of XLPE type pipes which are widely used for hot water and floor heating [30]. Polybutelene terephthalate (PBT), which is a plastic for electronic industry, can be crosslinked by radiation and lead free soldering materials can be applied in such a case. This method of crosslinking is also applied to manufacture

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

Science.gov (United States)

Cvitaš, Marko T; Althorpe, Stuart C

2013-08-14

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

A Regime Diagram for Autoignition of Homogeneous Reactant Mixtures with Turbulent Velocity and Temperature Fluctuations

KAUST Repository

Im, Hong G.

2015-04-02

A theoretical scaling analysis is conducted to propose a diagram to predict weak and strong ignition regimes for a compositionally homogeneous reactant mixture with turbulent velocity and temperature fluctuations. The diagram provides guidance on expected ignition behavior based on the thermo-chemical properties of the mixture and the flow/scalar field conditions. The analysis is an extension of the original Zeldovich’s analysis by combining the turbulent flow and scalar characteristics in terms of the characteristic Damköhler and Reynolds numbers of the system, thereby providing unified and comprehensive understanding of the physical and chemical mechanisms controlling ignition characteristics. Estimated parameters for existing experimental measurements in a rapid compression facility show that the regime diagram predicts the observed ignition characteristics with good fidelity.

A Regime Diagram for Autoignition of Homogeneous Reactant Mixtures with Turbulent Velocity and Temperature Fluctuations

KAUST Repository

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

2015-01-01

A theoretical scaling analysis is conducted to propose a diagram to predict weak and strong ignition regimes for a compositionally homogeneous reactant mixture with turbulent velocity and temperature fluctuations. The diagram provides guidance on expected ignition behavior based on the thermo-chemical properties of the mixture and the flow/scalar field conditions. The analysis is an extension of the original Zeldovich’s analysis by combining the turbulent flow and scalar characteristics in terms of the characteristic Damköhler and Reynolds numbers of the system, thereby providing unified and comprehensive understanding of the physical and chemical mechanisms controlling ignition characteristics. Estimated parameters for existing experimental measurements in a rapid compression facility show that the regime diagram predicts the observed ignition characteristics with good fidelity.

A time-dependent anisotropic plasma chemistry model of the Io plasma torus

Science.gov (United States)

Arridge, C. S.

2016-12-01

The physics of the Io plasma torus is typically modelled using one box neutral-plasma chemistry models, often referred to as neutral cloud theory models (e.g., Barbosa 1994; Delamere and Bagenal 2003). These models incorporate electron impact and photoionisation, charge exchange, molecular dissociation/recombination reactions, atomic radiatiative losses and Coulomb collisional heating. Isotropic Maxwellian distributions are usually assumed in the implementation of these models. Observationally a population of suprathermal electrons has been identified in the plasma torus and theoretically they have been shown to be important in reproducing the observed ionisation balance in the torus (e.g., Barbosa 1994). In this paper we describe an anisotropic plasma chemistry model for the Io torus that is inspired by ion cyclotron wave observations (Huddleston et al. 1994; Leisner et al. 2011), ion anisotropies due to pick up (Wilson et al. 2008), and theoretical ideas on the maintenance of the suprathermal electron population (Barbosa 1994). We present both steady state calculations and also time varying solutions (e.g., Delamere et al. 2004) where increases in the neutral source rate in the torus generates perturbations in ion anisotropies that subsequently decay over a timescale much longer than the duration of the initial perturbation. We also present a method for incorporating uncertainties in reaction rates into the model.

Ice Chemistry in Interstellar Dense Molecular Clouds, Protostellar Disks, and Comets

Science.gov (United States)

Sandford, Scott A.

2015-01-01

Despite the low temperatures (T less than 20K), low pressures, and low molecular densities found in much of the cosmos, considerable chemistry is expected to occur in many astronomical environments. Much of this chemistry happens in icy grain mantles on dust grains and is driven by ionizing radiation. This ionizing radiation breaks chemical bonds of molecules in the ices and creates a host of ions and radicals that can react at the ambient temperature or when the parent ice is subsequently warmed. Experiments that similar these conditions have demonstrated a rich chemistry associated with these environments that leads to a wide variety of organic products. Many of these products are of considerable interest to astrobiology. For example, the irradiation of simple ices has been shown to abiotically produce amino acids, nucleobases, quinones, and amphiphiles, all compounds that play key roles in modern biochemistry. This suggests extraterrestrial chemistry could have played a role in the origin of life on Earth and, by extension, do so on planets in other stellar systems.

Experimental and numerical investigation of ion signals in boosted HCCI combustion using cesium and potassium acetate additives

International Nuclear Information System (INIS)

Mack, J. Hunter; Butt, Ryan H.; Chen, Yulin; Chen, Jyh-Yuan; Dibble, Robert W.

2016-01-01

Highlights: • HCCI engine experiments show that CsOAc and KOAc additives increased the ion SNR. • The ion signal is more apparent at higher equivalence ratios. • An increase in intake pressure produces a decrease in the ion signal. • Use of metal acetates as additives yielded reductions in IMEP g and maximum ROHR. • A numerical model predicted peak ion signal, CA50, and p intake dependence. - Abstract: A sparkplug ion sensor can be used to measure the ion current in a homogeneous charge compression ignition (HCCI) engine, providing insight into the ion chemistry inside the cylinders during combustion. HCCI engines typically operate at lean equivalence ratios (ϕ) at which the ion current becomes increasingly indistinguishable from background noise. This paper investigates the effect of fuel additives on the ion signal at low equivalence ratios, determines side effects of metal acetate addition, and validates numerical model for ionization chemistry. Cesium acetate (CsOAc) and potassium acetate (KOAc) were used as additives to ethanol as the primary fuel. Concentration levels of 100, 200, and 400 mg/L of metal acetate-in-ethanol are investigated at equivalence ratios of 0.08, 0.20, and 0.30. The engine experiments were conducted at a boosted intake pressure of 1.8 bar absolute and compared to naturally aspirated results. Combustion timing was maintained at 2.5° after top-dead-center (ATDC), as defined by the crank angle degree (CAD) where 50% of the cumulative heat release occurs (CA50). CsOAc consistently produced the strongest ion signals at all conditions when compared to KOAc. The ion signal was found to decrease with increased intake pressure; an increase in the additive concentration increased the ion signal for all cases. However, the addition of the metal acetates decreased the gross indicated mean effective pressure (IMEP g ), maximum rate of heat release (ROHR), and peak cylinder pressure. Experimental results were used to validate ion chemistry

The chemistry of amine radical cations produced by visible light photoredox catalysis

Directory of Open Access Journals (Sweden)

Jie Hu

2013-10-01

Full Text Available Amine radical cations are highly useful reactive intermediates in amine synthesis. They have displayed several modes of reactivity leading to some highly sought-after synthetic intermediates including iminium ions, α-amino radicals, and distonic ions. One appealing method to access amine radical cations is through one-electron oxidation of the corresponding amines under visible light photoredox conditions. This approach and subsequent chemistries are emerging as a powerful tool in amine synthesis. This article reviews synthetic applications of amine radical cations produced by visible light photocatalysis.

Proceedings of the DAE-BRNS theme meeting on ion chromatography separations - state of art and perspectives

International Nuclear Information System (INIS)

Jeyakumar, S.; Ramakumar, K.L.

2012-01-01

Ion Chromatography (IC) plays a vital role in all disciplines of science and technology. In the field of trace separations and speciation studies, use of IC techniques becomes indispensable. In nuclear technology, IC plays a pivotal role in the reactor water chemistry, in the front end of fuel cycle especially in the characterization of nuclear materials including the reactor fuels, post irradiation examination, actinide speciation studies and in understanding the interaction and migration of actinide species in the geo environment. Ion chromatography is also useful in the studies related to waste management particularly for the separation and determination of fission products. The aim of this meeting is to provide a forum to all the researchers in the area of ion chromatography to discuss their recent findings and information, to learn from the mutual experiences and interests, and to promote cooperation both nationally and internationally. Ion chromatography techniques including Ion Chromatography Separations and Nuclear Materials, Speciation Studies by Ion chromatography, Hyphenated -IC Techniques, Reactor Water Chemistry and Ion Chromatography, Solid Phase Extraction and Sample Preparations for IC and Separation of Bio-molecules and Environmental aspects etc are discussed. Papers relevant to INIS are indexed separately

Non-equilibrium plasma chemistry at high pressure and its applications

International Nuclear Information System (INIS)

Bai Xiyao; Zhang Zhitao; Bai Mindong; Zhu Qiaoying

2000-01-01

A review is presented of research and development of gas discharge and non-equilibrium plasma including, new ideas of non-equilibrium plasma at high gas pressure. With special technology, strong electric fields (>400 Td) can be achieved by which electrons are accelerated suddenly, becoming high energy electrons (> 10 eV) at high pressure. On impact with the electrons, the gas molecules dissociate into ions, atomic ions, atoms and free radicals, and new substances or molecules can be synthesized through custom design. Chemical reaction difficult to achieve by conventional method can be realized or accelerated. Non-equilibrium plasma chemistry at high pressure has wide application prospects

Abstracts of the 2. Brazilian Meeting on Analytical Chemistry

International Nuclear Information System (INIS)

Curtius, A.J.

1983-01-01

Abstracts of theoretical and experimental works on Qualitative and Quantitative Analytical Chemistry are presented. Among the various analytical techniques used, emphasis is given to: neutron activation analysis, crystal doping and annealing, isotopic tracing, fission tracks detection, atomic absorption spectrophotometry, emission spectroscopy with induced coupled plasma, X-ray diffraction, nuclear magnetic resonance, mass spectrometry, polarography, ion exchange and/or thin-layer chromatography, electrodeposition, potentiometric titration and others. (C.L.B) [pt

Lithium-ion battery materials and engineering current topics and problems from the manufacturing perspective

CERN Document Server

Gulbinska, Malgorzata K

2014-01-01

Gaining public attention due, in part,  to their potential application as energy storage devices in cars, Lithium-ion batteries have encountered widespread demand, however, the understanding of lithium-ion technology has often lagged behind production. This book defines the most commonly encountered challenges from the perspective of a high-end lithium-ion manufacturer with two decades of experience with lithium-ion batteries and over six decades of experience with batteries of other chemistries. Authors with years of experience in the applied science and engineering of lithium-ion batterie

Polymeric Electrolyte Membrane Photoelectrochemical (PEM-PEC Cell with a Web of Titania Nanotube Arrays as Photoanode and Gaseous Reactants

Directory of Open Access Journals (Sweden)

Tsampas M.N.

2017-01-01

Photoanodes of titania nanotube arrays, TNTAs, were developed, for the first time, on a Ti-web of microfiber substrates, by electrochemical anodization. The performance of TNTAs/Ti-web photoanodes were evaluated in both gaseous and liquid reactants. Due to the presence of reliable reference electrode in gas phase direct comparison of the results was possible. Gas phase operation with He or Air as carrier gases and only 2.5% of water content exhibits very promising photoefficiency in comparison with conventional PEC cells.

Stream chemistry responses to four range management strategies in eastern Oregon.

Science.gov (United States)

A.R. Tiedemann; D.A. Higgins; T.M. Quigley; H.R. Sanderson

1989-01-01

Responses of stream chemistry parameters, nitrate-N (NO3-N), phosphate (PO4), calcium (Ca), magnesium (Mg), potassium (K), sodium (Na), and hydrogen ion activity (pH) were measured on 13 wildland watersheds managed at four different grazing strategies. Range management strategies tested were (A) no grazing, (B) grazing without control of livestock distribution (8.2 ha/...

Reducibility and Oxidation Activity of Cu Ions in Zeolites. Effect of Cu Ion Coordination and Zeolite Framework Composition

Czech Academy of Sciences Publication Activity Database

Bulánek, R.; Wichterlová, Blanka; Sobalík, Zdeněk; Tichý, J.

2001-01-01

Roč. 31, č. 1 (2001), s. 13-25 ISSN 0926-3373 R&D Projects: GA AV ČR IBS4040016 Grant - others:VW Stiftung(DE) 1/72937 Institutional research plan: CEZ:AV0Z4040901 Keywords : Cu ions * Cu-ZSM-5 * TPR by hydrogen Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.643, year: 2001

Molecular Mechanisms of Ion-Specific Effects on Proteins

Czech Academy of Sciences Publication Activity Database

Rembert, K. B.; Paterová, Jana; Heyda, Jan; Hilty, Ch.; Jungwirth, Pavel; Cremer, P. S.

2012-01-01

Roč. 134, č. 24 (2012), s. 10039-10046 ISSN 0002-7863 R&D Projects: GA ČR GA203/08/0114 Institutional research plan: CEZ:AV0Z40550506 Keywords : ions * proteins * molecular dynamics * NMR Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 10.677, year: 2012

Specific ion effects on membrane potential and the permselectivity of ion exchange membranes

KAUST Repository

Geise, Geoffrey M.

2014-08-26

© the Partner Organisations 2014. Membrane potential and permselectivity are critical parameters for a variety of electrochemically-driven separation and energy technologies. An electric potential is developed when a membrane separates electrolyte solutions of different concentrations, and a permselective membrane allows specific species to be transported while restricting the passage of other species. Ion exchange membranes are commonly used in applications that require advanced ionic electrolytes and span technologies such as alkaline batteries to ammonium bicarbonate reverse electrodialysis, but membranes are often only characterized in sodium chloride solutions. Our goal in this work was to better understand membrane behaviour in aqueous ammonium bicarbonate, which is of interest for closed-loop energy generation processes. Here we characterized the permselectivity of four commercial ion exchange membranes in aqueous solutions of sodium chloride, ammonium chloride, sodium bicarbonate, and ammonium bicarbonate. This stepwise approach, using four different ions in aqueous solution, was used to better understand how these specific ions affect ion transport in ion exchange membranes. Characterization of cation and anion exchange membrane permselectivity, using these ions, is discussed from the perspective of the difference in the physical chemistry of the hydrated ions, along with an accompanying re-derivation and examination of the basic equations that describe membrane potential. In general, permselectivity was highest in sodium chloride and lowest in ammonium bicarbonate solutions, and the nature of both the counter- and co-ions appeared to influence measured permselectivity. The counter-ion type influences the binding affinity between counter-ions and polymer fixed charge groups, and higher binding affinity between fixed charge sites and counter-ions within the membrane decreases the effective membrane charge density. As a result permselectivity decreases. The

RITRACKS: A Software for Simulation of Stochastic Radiation Track Structure, Micro and Nanodosimetry, Radiation Chemistry and DNA Damage for Heavy Ions

Science.gov (United States)

Plante, I; Wu, H

2014-01-01

The code RITRACKS (Relativistic Ion Tracks) has been developed over the last few years at the NASA Johnson Space Center to simulate the effects of ionizing radiations at the microscopic scale, to understand the effects of space radiation at the biological level. The fundamental part of this code is the stochastic simulation of radiation track structure of heavy ions, an important component of space radiations. The code can calculate many relevant quantities such as the radial dose, voxel dose, and may also be used to calculate the dose in spherical and cylindrical targets of various sizes. Recently, we have incorporated DNA structure and damage simulations at the molecular scale in RITRACKS. The direct effect of radiations is simulated by introducing a slight modification of the existing particle transport algorithms, using the Binary-Encounter-Bethe model of ionization cross sections for each molecular orbitals of DNA. The simulation of radiation chemistry is done by a step-by-step diffusion-reaction program based on the Green's functions of the diffusion equation]. This approach is also used to simulate the indirect effect of ionizing radiation on DNA. The software can be installed independently on PC and tablets using the Windows operating system and does not require any coding from the user. It includes a Graphic User Interface (GUI) and a 3D OpenGL visualization interface. The calculations are executed simultaneously (in parallel) on multiple CPUs. The main features of the software will be presented.

Water chemistry management of the spent-fuel pool in Thailand

International Nuclear Information System (INIS)

Suparit, Nitaya; Sukharn, Sumalee; Busamongkol, Arporn; Laoharojanaphand, Sirinart

1999-01-01

Water chemistry of the OAEP spent-fuel pool has been closely monitored without any pre-treatment for its conductivity, pH, temperature, chloride ion, sulfate ion, nitrate ion, phosphate ion, silver ion, and copper ion as well as its gamma activity of Cs-137. Conductivity, pH and temperature were measured using a portable pH and conductivity meter with built in temperature probe. Chloride ion was monitored by an automatic micro-titrator with silver nitrate as titrant and platinum indicator electrode. Nitrate, sulfate and phosphate were analysed by ion-exchange chromatographic method using an anion separator column and salicylate buffer as eluant. Gamma activity of Cs-137 was measured using a Canberra gamma spectrometer with HpGe detector. Silver and copper were analysed by ICP-AES technique within 6 hours after collection. During the study period from March 1996-September 1998, the conductivity was between l.25-4.80 μ/cm, pH in the range of 5-8.1, and temperature from 26.4-29.6 degree celsius. Chloride ion was found between 0.l-0.8 ppm. Silver, copper, nitrate, sulfate and phosphate ions were undetectable. Overall chemical composition of the water shows that the water is kept in standard condition recommended for safety storage. However, the presence of gamma activity of Cs-137 (average value of 138 Bq/l) indicates a slight leak of the spent fuel. (author)

Arrival time distributions of product ions reveal isomeric ratio of deprotonated molecules in ion mobility-mass spectrometry of hyaluronan-derived oligosaccharides

Czech Academy of Sciences Publication Activity Database

Hermanová, M.; Iordache, A.-M.; Slováková, K.; Havlíček, Vladimír; Pelantová, Helena; Lemr, Karel

2015-01-01

Roč. 50, č. 6 (2015), s. 854-863 ISSN 1076-5174 R&D Projects: GA ČR(CZ) GAP206/12/1150 Institutional support: RVO:61388971 Keywords : tyramine-based hyaluronan derivatives * isomer discrimination * ion mobility Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.541, year: 2015

Methods of gas purification and effect on the ion composition in an RF atmospheric pressure plasma jet investigated by mass spectrometry

International Nuclear Information System (INIS)

Grosse-Kreul, Simon; Huebner, Simon; Schneider, Simon; Keudell, Achim von; Benedikt, Jan

2016-01-01

The analysis of the ion chemistry of atmospheric pressure plasmas is essential to evaluate ionic reaction pathways during plasma-surface or plasma-analyte interactions. In this contribution, the ion chemistry of a radio-frequency atmospheric pressure plasma jet (μ-APPJ) operated in helium is investigated by mass spectrometry (MS). It is found, that the ion composition is extremely sensitive to impurities such as N 2 , O 2 and H 2 O. Without gas purification, protonated water cluster ions of the form H + (H 2 O) n are dominating downstream the positive ion mass spectrum. However, even after careful feed gas purification to the sub-ppm level using a molecular sieve trap and a liquid nitrogen trap as well as operation of the plasma in a controlled atmosphere, the positive ion mass spectrum is strongly influenced by residual trace gases. The observations support the idea that species with a low ionization energy serve as a major source of electrons in atmospheric pressure helium plasmas. Similarly, the neutral density of atomic nitrogen measured by MS in a He/N 2 mixture is varying up to a factor 3, demonstrating the significant influence of impurities on the neutral species chemistry as well. (orig.)

Methods of gas purification and effect on the ion composition in an RF atmospheric pressure plasma jet investigated by mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Grosse-Kreul, Simon; Huebner, Simon; Schneider, Simon; Keudell, Achim von; Benedikt, Jan [Ruhr-Universitaet Bochum, Institute for Experimental Physics II, Bochum (Germany)

2016-12-15

The analysis of the ion chemistry of atmospheric pressure plasmas is essential to evaluate ionic reaction pathways during plasma-surface or plasma-analyte interactions. In this contribution, the ion chemistry of a radio-frequency atmospheric pressure plasma jet (μ-APPJ) operated in helium is investigated by mass spectrometry (MS). It is found, that the ion composition is extremely sensitive to impurities such as N{sub 2}, O{sub 2} and H{sub 2}O. Without gas purification, protonated water cluster ions of the form H{sup +}(H{sub 2}O){sub n} are dominating downstream the positive ion mass spectrum. However, even after careful feed gas purification to the sub-ppm level using a molecular sieve trap and a liquid nitrogen trap as well as operation of the plasma in a controlled atmosphere, the positive ion mass spectrum is strongly influenced by residual trace gases. The observations support the idea that species with a low ionization energy serve as a major source of electrons in atmospheric pressure helium plasmas. Similarly, the neutral density of atomic nitrogen measured by MS in a He/N{sub 2} mixture is varying up to a factor 3, demonstrating the significant influence of impurities on the neutral species chemistry as well. (orig.)

Chemistry of ice: Migration of ions and gases by directional freezing of water

Directory of Open Access Journals (Sweden)

Umer Shafique

2016-09-01

Full Text Available Redistribution of anions and cations creates an electrical imbalance in ice grown from electrolyte solutions. Movement of acidic and basic ions in cooling solutions can permanently change the pH of frozen and unfrozen parts of the system, largely. The extent of pH change associated with freezing is determined by solute concentration and the extent of cooling. In the present work, redistribution of hydrogen, hydroxyl, carbonate, and bicarbonate ions was studied during directional freezing in batch aqueous systems. Controlled freezing was employed vertically as well as radially in acidic and basic solutions. In each case, the ions substantially migrated along with moving freezing front. Conductometry and pH-metry were employed to monitor the moving ions. Besides, some other experiments were carried out with molecular gases, such as oxygen, carbon dioxide, and chlorine and an azeotropic mixture like water–ethanol. Findings can be used to understand possible changes that can occur in preserving materials by freezing.

Hydrogen ion input to the Hubbard Brook Experimental Forest, New Hampshire, during the last decade

Science.gov (United States)

Gene E. Likens; F. Herbert Bormann; John S. Eaton; Robert S. Pierce; Noye M. Johnson

1976-01-01

Being downwind of eastern and midwestern industrial centers, the Hubbard Brook Experimental Forest offers a prime location to monitor long-term trends in atmospheric chemistry. Continuous measurements of precipitation chemistry during the last 10 years provide a measure of recent changes in precipitation inputs of hydrogen ion. The weighted average pH of precipitation...

Tailoring of the PS surface with low energy ions: Relevance to growth and adhesion of noble metals

International Nuclear Information System (INIS)

Zaporojtchenko, V.; Zekonyte, J.; Wille, S.; Schuermann, U.; Faupel, F.

2005-01-01

Ion-polymer interaction induces different phenomena in the near surface layer of polymers, and promotes its adhesion to metals. Using XPS, TEM and AFM, polystyrene surface was examined after 1 keV ion-beam treatments with oxygen, nitrogen and argon ions in the ion fluence range from 10 12 to 10 16 cm -2 to clarify the following points: chemical reaction after treatment in vacuum and after exposure to air, identification of adsorption-relevant species for metal atoms, formation of cross-links in the outermost polymer layer. The early stages of metal-polymer interface formation during metallization play a crucial role in the metal-polymer adhesion. Therefore, the influence of the ion fluence and ion chemistry on the condensation of noble metals, film growth and peel strength were measured. The peel strength showed a maximum at a certain fluence depending on ion chemistry. For example, the surface treatment with very low fluence of oxygen ions improved the adhesion between copper and polystyrene by two orders of magnitude without significantly increasing the surface roughness measured with AFM. The locus of failure changed at the same time from interfacial failure for untreated polymer surfaces to cohesive failure in the polymer for modified surfaces. A multilayer model of the metal-polymer interface after ion treatment is suggested

On the mechanism of water cluster-ion formation in carbon dioxide

International Nuclear Information System (INIS)

Warneck, P.; Rakshit, A.B.

1981-01-01

A drift chamber mass spectrometer has been used to study the formation of water cluster-ions in carbon dioxide containing traces of water vapour. The dominant reaction sequences were identified up to the fourth generation of daughter ions starting with CO 2 + . The subsequent reaction mechanism remains uncertain and several possibilities are discussed. The final ions are H 3 O + H 2 O and H 3 O + (H 2 O) 2 . The significance of the reaction schemes to the radiation chemistry of carbon dioxide is pointed out. (orig.)

Towards 31Mg-β-NMR resonance linewidths adequate for applications in magnesium chemistry

DEFF Research Database (Denmark)

Stachura, M.; McFadden, R. M. L.; Chatzichristos, A.

2017-01-01

The span of most chemical shifts recorded in conventional 25Mg-NMR spectroscopy is ~ 100 ppm. Accordingly, linewidths of ~ 10 ppm or better are desirable to achieve adequate resolution for applications in chemistry. Here we present first high-field 31Mg- β-NMR measurements of 31Mg+ ions implanted...

Uncertainty analysis in a real-time state-of-charge evaluation system for lithium-ion batteries

NARCIS (Netherlands)

Pop, V.; Regtien, P.P.L.; Bergveld, H.J.; Notten, P.H.L.; Op het Veld, B.

2006-01-01

Lithium-ion (Li-ion) is the most commonly used battery chemistry in portable applications nowadays. Accurate State-of-Charge (SoC) and remaining run-time (t,) calculation for portable devices is important for the user convenience and to prolong the lifetime of batteries. A new SoC algorithm for

An ion-neutral model to investigate chemical ionization mass spectrometry analysis of atmospheric molecules - application to a mixed reagent ion system for hydroperoxides and organic acids

Science.gov (United States)

Heikes, Brian G.; Treadaway, Victoria; McNeill, Ashley S.; Silwal, Indira K. C.; O'Sullivan, Daniel W.

2018-04-01

An ion-neutral chemical kinetic model is described and used to simulate the negative ion chemistry occurring within a mixed-reagent ion chemical ionization mass spectrometer (CIMS). The model objective was the establishment of a theoretical basis to understand ambient pressure (variable sample flow and reagent ion carrier gas flow rates), water vapor, ozone and oxides of nitrogen effects on ion cluster sensitivities for hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), formic acid (HFo) and acetic acid (HAc). The model development started with established atmospheric ion chemistry mechanisms, thermodynamic data and reaction rate coefficients. The chemical mechanism was augmented with additional reactions and their reaction rate coefficients specific to the analytes. Some existing reaction rate coefficients were modified to enable the model to match laboratory and field campaign determinations of ion cluster sensitivities as functions of CIMS sample flow rate and ambient humidity. Relative trends in predicted and observed sensitivities are compared as instrument specific factors preclude a direct calculation of instrument sensitivity as a function of sample pressure and humidity. Predicted sensitivity trends and experimental sensitivity trends suggested the model captured the reagent ion and cluster chemistry and reproduced trends in ion cluster sensitivity with sample flow and humidity observed with a CIMS instrument developed for atmospheric peroxide measurements (PCIMSs). The model was further used to investigate the potential for isobaric compounds as interferences in the measurement of the above species. For ambient O3 mixing ratios more than 50 times those of H2O2, O3-(H2O) was predicted to be a significant isobaric interference to the measurement of H2O2 using O2-(H2O2) at m/z 66. O3 and NO give rise to species and cluster ions, CO3-(H2O) and NO3-(H2O), respectively, which interfere in the measurement of CH3OOH using O2-(CH3OOH) at m/z 80. The CO3-(H2O

Highly reversible open framework nanoscale electrodes for divalent ion batteries.

Science.gov (United States)

Wang, Richard Y; Wessells, Colin D; Huggins, Robert A; Cui, Yi

2013-01-01

The reversible insertion of monovalent ions such as lithium into electrode materials has enabled the development of rechargeable batteries with high energy density. Reversible insertion of divalent ions such as magnesium would allow the creation of new battery chemistries that are potentially safer and cheaper than lithium-based batteries. Here we report that nanomaterials in the Prussian Blue family of open framework materials, such as nickel hexacyanoferrate, allow for the reversible insertion of aqueous alkaline earth divalent ions, including Mg(2+), Ca(2+), Sr(2+), and Ba(2+). We show unprecedented long cycle life and high rate performance for divalent ion insertion. Our results represent a step forward and pave the way for future development in divalent batteries.

"Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries.

Science.gov (United States)

Suo, Liumin; Borodin, Oleg; Gao, Tao; Olguin, Marco; Ho, Janet; Fan, Xiulin; Luo, Chao; Wang, Chunsheng; Xu, Kang

2015-11-20

Lithium-ion batteries raise safety, environmental, and cost concerns, which mostly arise from their nonaqueous electrolytes. The use of aqueous alternatives is limited by their narrow electrochemical stability window (1.23 volts), which sets an intrinsic limit on the practical voltage and energy output. We report a highly concentrated aqueous electrolyte whose window was expanded to ~3.0 volts with the formation of an electrode-electrolyte interphase. A full lithium-ion battery of 2.3 volts using such an aqueous electrolyte was demonstrated to cycle up to 1000 times, with nearly 100% coulombic efficiency at both low (0.15 coulomb) and high (4.5 coulombs) discharge and charge rates. Copyright © 2015, American Association for the Advancement of Science.

Nanomaterials for lithium-ion batteries fundamentals and applications

CERN Document Server

Yazami, Rachid

2013-01-01

""The book has good technical depth, yet is still very readable. It contains many photos, illustrations, tables, and graphs of data that provide the reader with the insight needed to understand the phenomena being described and the processes occurring in lithium battery chemistry. Researchers as well as students studying lithium-ion batteries will find this book well worth reading. It provides insight into many different avenues for potentially improving lithium-ion battery performance. The reader will learn about these new ideas and gain a better understanding of what currently limits batt

Energetics and Dynamics of Decaying Cluster Ions

Czech Academy of Sciences Publication Activity Database

Gluch, K.; Fedor, J.; Matt-Leubner, S.; Parajuli, R.; Mair, C.; Stamatovic, A.; Echt, O.; Lifshitz, C.; Harvey, J.; Hagelberg, F.; Herman, Zdeněk; Probst, M.; Scheier, P.; Märk, T. D.

2003-01-01

Roč. 24, 1/3 (2003), s. 131-136 ISSN 1434-6060 R&D Projects: GA ČR GA203/00/0632 Grant - others:European Commission(XE) Euroatom Institutional research plan: CEZ:AV0Z4040901 Keywords : surface-induced reactions * kinetics-energy release * polyatomic ions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.612, year: 2003

Radiological and Environmental Research Division annual report, October 1979-September 1980: fundamental molecular physics and chemistry

International Nuclear Information System (INIS)

1981-09-01

Research is reported on the physics and chemistry of atoms, ions, and molecules, especially their interactions with external agents such as photons and electrons. Individual items from the report were prepared separately for the data base

Guidelines on Lithium-ion Battery Use in Space Applications

Science.gov (United States)

Mckissock, Barbara; Loyselle, Patricia; Vogel, Elisa

2009-01-01

This guideline discusses a standard approach for defining, determining, and addressing safety, handling, and qualification standards for lithium-ion (Li-Ion) batteries to help the implementation of the technology in aerospace applications. Information from a variety of other sources relating to Li-ion batteries and their aerospace uses has been collected and included in this document. The sources used are listed in the reference section at the end of this document. The Li-Ion chemistry is highly energetic due to its inherent high specific energy and its flammable electrolyte. Due to the extreme importance of appropriate design, test, and hazard control of Li-ion batteries, it is recommended that all Government and industry users and vendors of this technology for space applications, especially involving humans, use this document for appropriate guidance prior to implementing the technology.

Communication: Reactivity borrowing in the mode selective chemistry of H + CHD3 → H2 + CD3

Science.gov (United States)

Ellerbrock, Roman; Manthe, Uwe

2017-12-01

Quantum state-resolved reaction probabilities for the H + CHD3 → H2 + CD3 reaction are calculated by accurate full-dimensional quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree approach and the quantum transition state concept. Reaction probabilities of various ro-vibrational states of the CHD3 reactant are investigated for vanishing total angular momentum. While the reactivity of the different vibrational states of CHD3 mostly follows intuitive patterns, an unusually large reaction probability is found for CHD3 molecules triply excited in the CD3 umbrella-bending vibration. This surprising reactivity can be explained by a Fermi resonance-type mixing of the single CH-stretch excited and the triple CD3 umbrella-bend excited vibrational states of CHD3. These findings show that resonant energy transfer can significantly affect the mode-selective chemistry of CHD3 and result in counter-intuitive reactivity patterns.

Chemistry and physics

International Nuclear Information System (INIS)

Broerse, J.J.; Barendsen, G.W.; Kal, H.B.; Kogel, A.J. van der

1983-01-01

This book contains the extended abstracts of the contributions of the poster workshop sessions on chemistry and physics of the 7th international congress of radiation research. They cover the following main topics: primary processes in radiation physics and chemistry, general chemistry in radiation chemistry, DNA and model systems in radiation chemistry, molecules of biological interest in radiation chemistry, techniques in radiation chemistry, hot atom chemistry. refs.; figs.; tabs

Ion beam analysis of PECVD silicon oxide thin films

International Nuclear Information System (INIS)

Fernandez-Lima, F.; Rodriguez, J.A.; Pedrero, E.; Fonseca Filho, H.D.; Llovera, A.; Riera, M.; Dominguez, C.; Behar, M.; Zawislak, F.C.

2006-01-01

A study of ion beam analysis techniques of plasma enhanced chemical vapor deposited (PECVD) silicon oxide thin films (1 μm thick) obtained from silane (SiH 4 ) and nitrous oxide (N 2 O) is reported. The film, elemental composition and surface morphology were determined as function of the reactant gas flow ratio, R = [N 2 O]/[SiH 4 ] in the 22-110 range using the Rutherford backscattering spectrometry, nuclear reaction analysis and atomic force microscopy techniques. The density of the films was determined by combining the RBS and thickness measurements. All the experiments were done at a deposition temperature of 300 deg. C. In all the cases almost stoichiometric oxides were obtained being the impurity content function of R. It was also observed that physical properties such as density, surface roughness and shape factor increase with R in the studied interval

Controlling the nanoscale morphology of organic films deposited by polyatomic ions

CERN Document Server

Hanley, L; Fuoco, E R; Ahu-Akin, F; Wijesundara, M B J; Li, Maozhen; Tikhonov, A; Schlossman, M

2003-01-01

Hyperthermal polyatomic ion beams can be used to fabricate thin film nanostructures with controlled morphology. Several experiments are described in which mass-selected and non-mass-selected polyatomic ion beams are used to create nanometer thick films with controlled surface and buried interface morphologies. Fluorocarbon and thiophenic films are grown on silicon wafers and/or polystyrene from 5 to 200 eV C sub 3 F sub 5 sup + or C sub 4 H sub 4 S sup + ions, respectively. X-ray photoelectron spectroscopy, atomic force microscopy, X-ray reflectivity, and scanning electron microscopy are utilized to analyze the morphology and chemistry of these films. Polyatomic ions are found to control film morphology on the nanoscale through variation of the incident ion energy, ion structure and/or substrate.

Inorganic ion-exchangers. Their role in chromatographic radionuclide generators for the decade 1993-2002

International Nuclear Information System (INIS)

Mushtaq, A.

2004-01-01

Ion-exchangers are found not only in water purification processes, the original major application, but also in analytical chemistry for the separation and isolation of elements, hydrometallurgy, inorganic chemistry and biochemistry, in food technology, and of course in many specialized fields related to the utilization of atomic energy. The use of organic ion-exchangers is limited by virtue of their limited stability under harsh conditions, whereas inorganic ion-exchangers possess important properties, which make them very useful for chemical separation and purification in intense radiation fields. The availability of short-lived radionuclides from radionuclide generators provides an inexpensive and convenient alternative to in-house radioisotope production facilities such as accelerators and cyclotrons. Due to their simplicity of operation, chromatographic based generators have been the method of choice, although generators based on solvent extraction and on volatilization and sublimation have also been developed, and are routinely used. In this paper use of inorganic ion-exchangers for the development of radionuclide generators for the decade 1993-2002 has been compiled. (author)

Chemistry control challenges in a supercritical water-cooled reactor

International Nuclear Information System (INIS)

Guzonas, David; Tremaine, Peter; Jay-Gerin, Jean-Paul

2009-01-01

The long-term viability of a supercritical water-cooled reactor (SCWR) will depend on the ability of designers to predict and control water chemistry to minimize corrosion and the transport of corrosion products and radionuclides. Meeting this goal requires an enhanced understanding of water chemistry as the temperature and pressure are raised beyond the critical point. A key aspect of SCWR water chemistry control will be mitigation of the effects of water radiolysis; preliminary studies suggest markedly different behavior than that predicted from simple extrapolations from conventional water-cooled reactor behavior. The commonly used strategy of adding excess hydrogen at concentrations sufficient to suppress the net radiolytic production of primary oxidizing species may not be effective in an SCWR. The behavior of low concentrations of impurities such as transition metal corrosion products, chemistry control agents, anions introduced via make-up water or from ion-exchange resins, and radionuclides (e.g., 60 Co) needs to be understood. The formation of neutral complexes increases with temperature, and can become important under near-critical and supercritical conditions; the most important region is from 300-450 C, where the properties of water change dramatically, and solvent compressibility effects exert a huge influence on solvation. The potential for increased transport and deposition of corrosion products (active and inactive), leading to (a) increased deposition on fuel cladding surfaces, and (b) increased out-of-core radiation fields and worker dose, must be assessed. There are also significant challenges associated with chemistry sampling and monitoring in an SCWR. The typical methods used in current reactor designs (grab samples, on-line monitors at the end of a cooled, depressurized sample line) will be inadequate, and in-situ measurements of key parameters will be required. This paper describes current Canadian activities in SCWR chemistry and chemistry

Contribution to the coordination chemistry of penta, hexa and heptavalent ions of 5f elements

International Nuclear Information System (INIS)

Musikas, Claude.

1978-01-01

This report has two main parts in which are discussed results dealing with: - aquo and hydroxo complexes of penta, hexa and heptavalent ions of 5f elements - pseuso halides complexes of these ions (SCN - , N 3 - , CN - ). It has been shown, by spectrophotometric and electrochemical measurements that U (V) possesses an aquo ion more acid than the known UO 2 + ion. This form is observed as insoluble hydroxid near pH 3.0 or as soluble polynuclear hydroxo complexes at lower pH. Hydroxo anionic complexes of U (VI) have been observed and one can precise the mecanism of hydrolysis of UO 2 ++ ions beyond he hydroxid UO 2 (OH) 2 . At pH 9 to 12, polynuclear species with low negative charge have been observed. At pH 13, others OH - ions enter in the coordination sphere of UO 2 ++ and mononuclear species are obtained. Reduction of polynuclear species leads to mixed hydroxo complexes of 'blue type'. Studies of hydrolysis of NpO 2 + allow to propose an hydrolysis mechanism similar to UO 2 ++ one. With electrochemical methods that in acidic media Np (VII) is present as NpO 3 + ions. Solubility product of NpO 3 OH has been measured. The second part is devoted to pseudohalides complexes of UO 2 ++ , UO 2 + and NpO 2 + ions [fr

Halonium Ions as Halogen Bond Donors in the Solid State [XL2]Y Complexes.

Science.gov (United States)

Rissanen, Kari; Haukka, Matti

2015-01-01

The utilization of halogen bonding interactions is one of the most rapidly developing areas of supramolecular chemistry. While the other weak non-covalent interactions and their influence on the structure and chemistry of various molecules, complexes, and materials have been investigated extensively, the understanding, utilizations, and true nature of halogen bonding are still relatively unexplored. Thus its final impact in chemistry in general and in materials science has not yet been fully established. Because of the polarized nature of a Z-X bond (Z=electron-withdrawing atom or moiety and X=halogen atom), such a moiety can act as halogen bond donor when the halogen is polarized enough by the atom/moiety Z. The most studied and utilized halogen bond donor molecules are the perfluorohalocarbons, where Z is a perfluorinated aryl or alkyl moiety and X is either iodine or bromine. Complementing the contemporary halogen bonding research, this chapter reviews the solid state structural chemistry of the most extremely polarized halogen atoms, viz. halonium ions, X+, and discussed them as halogen bond donors in the solid state [XL2]Y complexes (X=halonium ion, Y=any anion).

Triton's Ionosphere: Chemistry and Composition

Science.gov (United States)

Delitsky, Mona

2006-09-01

The ionosphere of Triton was observed by the Voyager spacecraft in 1989 to have a remarkably high electron density of 40,000/cc at its peak altitude. Delitsky et al. (1990) modeled this ionosphere using only N2 and CH4, the constituents of the atmosphere known at that time, and found that, at the extremely cold temperatures in the Triton atmosphere, cluster ions would form. These clusters are created when N+ or N2+ resulting from photolysis or radiolysis accrete neutral N2 molecules and form ions such as (N2+(N2)n). In these clusters, n can be very high, around 50-100, depending on temperature. Cluster ions easily sweep up electrons at the low altitudes where they form (keeping the e- content low) which leads to dissociative recombination. This neutralizes the cluster ions and releases the N2 molecules back into the atmosphere. In 1991, CO and CO2 were observed on Triton (Cruikshank et al. 1991). At Tritonian temperatures, CO will have a very high vapor pressure and could constitute up to 6% of the Triton atmosphere. Any N+ or N2+ will charge exchange with CO (and NO from chemistry) to yield CO+, NO+ and C+. These then become the core ions to the clusters (CO+(N2)n), (NO+(N2)n), or (C+(N2)n). (Delitsky et al. 1992, Delitsky, 1995). Clusters cannot form at higher altitudes and lower pressures and so at the peak altitude, the ionosphere is comprised almost totally of C+ ions. From modeling, CO + hv -> C+ (+ O) does not appear to be an important source of the C+ . Rather, the charge exchange reaction, CO+ + C -> C+ + CO produces the C+ which charge balances the electrons in the ionosphere. Ref: Cruikshank et al., BAAS, 23,1208 (1991);.. Delitsky et al. GRL, 17, 1725 (1990); ..Delitsky et al. Neptune conf, 1992; ..Delitsky, BAAS, 27, 1100 (1995)

Seasonal change in precipitation, snowpack, snowmelt, soil water and streamwater chemistry, northern Michigan

Science.gov (United States)

Stottlemyer, R.; Toczydlowski, D.

1999-01-01

We have studied weekly precipitation, snowpack, snowmelt, soil water and streamwater chemistry throughout winter for over a decade in a small (176 ha) northern Michigan watershed with high snowfall and vegetated by 60 to 80 year-old northern hardwoods. In this paper, we examine physical, chemical, and biological processes responsible for observed seasonal change in streamwater chemistry based upon intensive study during winter 1996-1997. The objective was to define the contributions made to winter and spring streamwater chemical concentration and flux by processes as snowmelt, over-winter forest floor and surface soil mineralization, immobilization, and exchange, and subsurface flowpath. The forest floor and soil were unfrozen beneath the snowpack which permitted most snowmelt to enter. Over-winter soil mineralization and other biological processes maintain shallow subsurface ion and dissolved organic carbon (DOC) reservoirs. Small, but steady, snowmelt throughout winter removed readily mobilized soil NO3- which resulted in high over-winter streamwater concentrations but little flux. Winter soil water levels and flowpaths were generally deep which increased soil water and streamwater base cation (C(B)), HCO3-, and Si concentrations. Spring snowmelt increased soil water levels and removal of ions and DOC from the biologically active forest floor and shallow soils. The snowpack solute content was a minor component in determining streamwater ion concentration or flux during and following peak snowmelt. Exchangeable ions, weakly adsorbed anions, and DOC in the forest floor and surface soils dominated the chemical concentration and flux in soil water and streamwater. Following peak snowmelt, soil microbial immobilization and rapidly increased plant uptake of limiting nutrients removed nearly all available nitrogen from soil water and streamwater. During the growing season high evapotranspiration increased subsurface flowpath depth which in turn removed weathering

Mathematical Chemistry

OpenAIRE

Trinajstić, Nenad; Gutman, Ivan

2002-01-01

A brief description is given of the historical development of mathematics and chemistry. A path leading to the meeting of these two sciences is described. An attempt is made to define mathematical chemistry, and journals containing the term mathematical chemistry in their titles are noted. In conclusion, the statement is made that although chemistry is an experimental science aimed at preparing new compounds and materials, mathematics is very useful in chemistry, among other things, to produc...

Primary circuit water chemistry during shutdown period at Kalinin NPP

International Nuclear Information System (INIS)

Gorbatenko, S.; Otchenashev, G.; Yurmanov, V.

2005-01-01

The primary circuit water chemistry feature at Kalinin NPP is using of special up-dated regime during the period of unit shutdown for refueling. The main objective of up-dated regime is removing from the circuit long time living corrosion products on SVO-2 ion exchange filters with the purpose of dose rates reduction from the equipment and in such a way reduction of maintenance personnel overexposure. (N.T.)

Measurements of Positively Charged Ions in Premixed Methane-Oxygen Atmospheric Flames

KAUST Repository

Alquaity, Awad; Han, Jie; Chahine, May; Selim, Hatem; Belhi, Memdouh; Sarathy, Mani; Bisetti, Fabrizio; Farooq, Aamir

2016-01-01

chemistry models are needed to understand and predict the effect of external electric fields on combustion plasmas. In this work, a molecular beam mass spectrometer (MBMS) is utilized to measure ion concentration profiles in premixed methane–oxygen argon

Water Chemistry and Chemistry Monitoring at Thermal and Nuclear Power Plants: Problems and Tasks (Based on Proceedings of Conferences)

Science.gov (United States)

Larin, B. M.

2018-02-01

In late May-early June 2017, two international science and technology conferences on problems of water chemistry and chemistry monitoring at thermal and nuclear power plants were held. The participants of both the first conference held at OAO VTI and the second conference that took place at NITI formulated the problems of the development of the regulatory base and implementation of promising water treatment technologies and outlined the ways of improving the water chemistry and chemistry monitoring at TPPs and NPPs for the near future. It was pointed out that the new amine-containing VTIAMIN agent developed by OAO VTI had been successfully tested on the power-generating units equipped with steam-gas plants to establish the minimum excess of the film-forming amine in the power-generating unit circuit that ensures the protection of the metal as 5-10 μg/dm3. A flow-injection technique for the analysis of trace concentrations of chlorides was proposed; the technique applied to the condensate of the 1000-MW steam turbine of the NPP power-generating unit yields the results comparable with the results obtained by the ion chromatography and the potentiometric method using the solver electrode. The participants of the conferences were demonstrated new Russian instruments to analyze the water media at the TPPs and NPPs, including the total organic carbon analyzer and the analyzer of mineral impurities in the condensate and feed water, that won a gold medal at the 45th International Exhibition of Inventions held in Geneva this April.

Ion energy/momentum effects during ion assisted growth of niobium nitride films

Science.gov (United States)

Klingenberg, Melissa L.

The research described herein was performed to better understand and discern ion energy vs. ion momentum effects during ion beam assisted (IBAD) film growth and their effects on residual stress, crystalline structure, morphology, and composition, which influence film tribological properties. NbxN y was chosen for this research because it is a refractory material that can possess a large number of crystalline structures, and it has been found to have good tribological properties. To separate the effects of momentum transfer per arriving atom (p/a), which considers bombarding species mass, energy, and ion-to-atom transport ratio, from those of energy deposition per arriving atom (E/a), a mass independent parameter, different inert ion beams (krypton, argon, and neon) were used to create a matrix of coatings formed using similar energy deposition, but different momentum transfer and vice versa. Deposition was conducted in a research-scale IBAD system using electron beam evaporation, a radio frequency ion source, and a neutral nitrogen gas backfill. Films were characterized using x-ray diffraction, atomic force microscopy, Rutherford backscattering spectrometry, and residual stress analysis. Direct and quantifiable effects of bombardment were observed; however, energy deposition and momentum transfer effects could not be completely separated, confirming that thin film processes are complex. Complexities arose from ion-specific interactions (ion size, recoil energy, per cent reflected neutrals, Penning ionization, etc.) and chemistry effects that are not considered by the simple models. Overall, it can be stated that bombardment promoted nitride formation, nanocrystallinity, and compressive stress formation; influenced morphology (which influenced post-deposition oxygen uptake) and stress evolution; increased lattice parameter; modified crystalline phase and texture; and led to inert gas incorporation. High stress levels correlated strongly with material disorder and

Electrical conductivity of conductive carbon blacks: influence of surface chemistry and topology

International Nuclear Information System (INIS)

Pantea, Dana; Darmstadt, Hans; Kaliaguine, Serge; Roy, Christian

2003-01-01

Conductive carbon blacks from different manufacturers were studied in order to obtain some insight into the relation between their electrical conductivity and their surface properties. The surface chemistry was studied by X-ray photoelectron spectroscopy (XPS) and static secondary ion mass spectroscopy (SIMS), whereas the topology of the carbon black surface was investigated using low-pressure nitrogen adsorption. All these techniques yield information on the graphitic character of the surface. In general, the electrical conductivity of the conductive blacks increases with the graphitic character of the surface. For low surface area conductive blacks, the electrical conductivity correlates well with the surface chemistry. In the case of the XPS and SIMS data, this correlation is also valid when other types of carbon blacks such as thermal and furnace blacks are included, confirming the determining influence of the carbon black surface chemistry on the electrical conductivity

Fragmentation of pure and hydrated clusters of 5Br-uracil by low energy carbon ions: observation of hydrated fragments

Czech Academy of Sciences Publication Activity Database

Castrovilli, M. C.; Markush, P.; Bolognesi, P.; Rousseau, P.; Maclot, S.; Cartoni, A.; Delaunay, R.; Domaracka, A.; Kočišek, Jaroslav; Huber, B. A.; Avaldi, L.

2017-01-01

Roč. 19, č. 30 (2017), s. 19807-19814 ISSN 1463-9076 Institutional support: RVO:61388955 Keywords : fragmentation * nano-hydrated 5BrU clusters * low energy carbon ions Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.123, year: 2016

Switching from Reactant to Substrate Engineering in the Selective Synthesis of Graphene Nanoribbons.

Science.gov (United States)

Merino-Díez, Néstor; Lobo-Checa, Jorge; Nita, Pawel; Garcia-Lekue, Aran; Basagni, Andrea; Vasseur, Guillaume; Tiso, Federica; Sedona, Francesco; Das, Pranab K; Fujii, Jun; Vobornik, Ivana; Sambi, Mauro; Pascual, José Ignacio; Ortega, J Enrique; de Oteyza, Dimas G

2018-04-27

The challenge of synthesizing graphene nanoribbons (GNRs) with atomic precision is currently being pursued along a one-way road, based on the synthesis of adequate molecular precursors that react in predefined ways through self-assembly processes. The synthetic options for GNR generation would multiply by adding a new direction to this readily successful approach, especially if both of them can be combined. We show here how GNR synthesis can be guided by an adequately nanotemplated substrate instead of by the traditionally designed reactants. The structural atomic precision, unachievable to date through top-down methods, is preserved by the self-assembly process. This new strategy's proof-of-concept compares experiments using 4,4''-dibromo-para-terphenyl as a molecular precursor on flat Au(111) and stepped Au(322) substrates. As opposed to the former, the periodic steps of the latter drive the selective synthesis of 6 atom-wide armchair GNRs, whose electronic properties have been further characterized in detail by scanning tunneling spectroscopy, angle resolved photoemission, and density functional theory calculations.

f-Element Ion Chelation in Highly Basic Media - Final Report

International Nuclear Information System (INIS)

Paine, R.T.

2000-01-01

A large body of data has been collected over the last fifty years on the chemical behavior of f-element ions. The ions undergo rapid hydrolysis reactions in neutral or basic aqueous solutions that produce poorly understood oxide-hydroxide species; therefore, most of the fundamental f-element solution chemistry has allowed synthetic and separations chemists to rationally design advanced organic chelating ligands useful for highly selective partitioning and separation of f-element ions from complex acidic solution matrices. These ligands and new examples under development allow for the safe use and treatment of solutions containing highly radioactive species. This DOE/EMSP project was undertaken to address the following fundamental objectives: (1) study the chemical speciation of Sr and lanthanide (Ln) ions in basic aqueous media containing classical counter anions found in waste matrices; (2) prepare pyridine N-oxide phosphonates and phosphonic acids that might act as selective chelator s for Ln ions in model basic pH waste streams; (3) study the binding of the new chelators toward Ln ions and (4) examine the utility of the chelators as decontamination and dissolution agents under basic solution conditions. The project has been successful in attacking selected aspects of the very difficult problems associated with basic pH solution f-element waste chemistry. In particular, the project has (1) shed additional light on the initial stages of Ln ion sol-gel-precipitate formulation under basic solution conditions; (2) generated new families of pyridine phosphonic acid chelators; (3) characterized the function of the chelators and (4) examined their utility as oxide-hydroxide dissolution agents. These findings have contributed significantly to an improved understanding of the behavior of Ln ions in basic media containing anions found in typical waste sludges as well as to the development of sludge dissolution agents. The new chelating reagents are easily made and could be

Poisoning of liquid membrane carriers in extraction of metal ions

International Nuclear Information System (INIS)

Wang, Yuchun; Wang, Dexian

1992-01-01

As means of effective separation and preconcentration, emulsion liquid membranes (ELMs) have found application in many fields including biochemical separation, wastewater treatment, hydrometallurgy, and preconcentration in analytical chemistry. In the extraction of desired metal (scandium, mixed rare earths) ions using chelating extractants (TTA, HDEHP) as liquid membrane carriers, the carriers will become poisoned owing to the presence of even minute quantity of certain high ionic potential ions in the feed solution. The reason for the poisoning of carriers is that those ions have so much greater affinity than the desired ions for the membrane carrier that the ion-carrier coordination compound cannot be stripped at the interior interface of the membrane and gradually no more free carrier transports any metal ions across the membrane. The calculated results are in agreement with the experiments, and methods to avoid the poisoning are given in the paper

Exploring Cryogenic Focused Ion Beam Milling as a Group III-V Device Fabrication Tool

Science.gov (United States)

2013-09-01

boiling, triple , and critical points of the elements” in CRC Handbook of Chemistry and Physics, 92nd ed., Boca Raton, FL: CRC press, 2011-2012, p. 4...The most widely used ion source in FIB instruments is a gallium (Ga) liquid metal ion source (LMIS) [4]. Gallium is attractive as an ion source...Figure 3b. EDS spectra were captured at different points across the patterned region of the room temperature milled sample, as indicated in Figure 4