WorldWideScience

Sample records for reactant ion chemistries

  1. Gas phase ion chemistry

    CERN Document Server

    Bowers, Michael T

    1979-01-01

    Gas Phase Ion Chemistry, Volume 1 covers papers on the advances of gas phase ion chemistry. The book discusses the advances in flow tubes and the measurement of ion-molecule rate coefficients and product distributions; the ion chemistry of the earth's atmosphere; and the classical ion-molecule collision theory. The text also describes statistical methods in reaction dynamics; the state selection by photoion-photoelectron coincidence; and the effects of temperature and pressure in the kinetics of ion-molecule reactions. The energy distribution in the unimolecular decomposition of ions, as well

  2. Gas phase ion chemistry

    CERN Document Server

    Bowers, Michael T

    1979-01-01

    Gas Phase Ion Chemistry, Volume 2 covers the advances in gas phase ion chemistry. The book discusses the stabilities of positive ions from equilibrium gas-phase basicity measurements; the experimental methods used to determine molecular electron affinities, specifically photoelectron spectroscopy, photodetachment spectroscopy, charge transfer, and collisional ionization; and the gas-phase acidity scale. The text also describes the basis of the technique of chemical ionization mass spectrometry; the energetics and mechanisms of unimolecular reactions of positive ions; and the photodissociation

  3. Metal Palladium Dispersed Inside Macroporous Ion-Exchange Resins: Textural Characterization and Accessibility to Gaseou Reactants

    Czech Academy of Sciences Publication Activity Database

    Biffis, A.; Jeřábek, Karel; D'Archivio, A. A.; Galantini, L.; Corain, B.

    2000-01-01

    Roč. 130, - (2000), s. 2327-2332 ISSN 0167-2991. [International Congress on Catalysis /12./. Granada, 09.07.2000-14.07.2000] Institutional research plan: CEZ:AV0Z4072921 Keywords : metal palladium * dispersed * ion-exchange resins Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.513, year: 2000

  4. Laboratory studies of ion-molecule reactions and interstellar chemistry

    International Nuclear Information System (INIS)

    Koyano, Inosuke

    1989-01-01

    Several types of laboratory studies have been performed on ion-molecule reactions relevant to the formation of the interstellar molecules. Special emphasis is placed on the formation, structure, and reactivity of the C 3 H 3 + ions, which are believed to play a key role in interstellar chemistry. When these ions are produced by the reaction of C 3 H 4+ with C 3 H 4 in a beam-gas arrangement, their times-of-flight (TOF) show abnormally broad distributions regardless of the sources of the reactant C 3 H 4 + ion (photoionization of allene, propyne, the cyclopropene) and the nature of the neutral reactant, while all other product ions from the same reaction show sharp TOF distributions. On the other hand, all C 3 H 3 + ions produced by unimolecular decomposition of energetic C 3 H 4 + ions show sharp TOF distribution. The peculiarity of the C 3 H 3 + ions manifested in these and other experiments is discussed in conjunction with interstellar chemistry

  5. 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.)

  6. 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

  7. Major ion chemistry of the Son River, India

    Indian Academy of Sciences (India)

    The chemistry of major ions in the surface water of the Son River was studied in detail to determine various source(s) and processes controlling its water chemistry, seasonal and spatial variations in water chemistry, dissolved fluxes and chemical denudation rate (CDR). The study shows that Ca2+, Mg2+ and HCO 3 − are ...

  8. The difference between the metal ion extracted from the R.F. ion source by applying plasma chemistry reaction and by non-plasma range chemistry reaction

    International Nuclear Information System (INIS)

    Bai Gui Bin

    1987-01-01

    The paper introduced the difference between using plasma chemistry reaction draw metal ion and non-plasma range chemistry reaction in the R.F. ion source. By using of the plasma chemistry reaction draw metal ion higher percentage than non-plasma range chemistry reaction in the R.F. ion source. The authors plasma chemistry reaction to R.F. ion source and implanter successfully. The effect is very well, it has its own characteristic

  9. Ion-molecule reactions: their role in radiation chemistry

    International Nuclear Information System (INIS)

    Lias, S.G.; Ausloos, P.

    1975-01-01

    A comprehensive review of ion--molecule reactions is presented, including information from mass spectrometric, organic chemistry, and NMR studies, from theoretical calculations, and from gas and liquid phase radiation chemistry. Special emphasis is placed on interpreting the role of ion--molecule reactions in systems under high energy irradiation. The discussion is presented under the following chapter headings: ion--molecule reactions and their role in radiation chemistry; unimolecular processes: the nature and structure of ionic intermediates in radiolysis; ion lifetimes and the fate of unreactive ions; kinetics and mechanisms of ion--molecule reactions; proton transfer reactions; negative atom and two-atom transfer reactions; condensation reactions; and, association or clustering reactions

  10. GAS PHASE ION CHEMISTRY OF COUMARINS: AB INITIO ...

    African Journals Online (AJOL)

    B. S. Chandravanshi

    The gas phase ion chemistry of coumarins using electron ionization (EI), positive chemical ionization (PCI) and ... Figure 1. Generic chemical structures of the coumarins in this study. ..... Part of this work was conducted using the resources of ...

  11. From transistor to trapped-ion computers for quantum chemistry.

    Science.gov (United States)

    Yung, M-H; Casanova, J; Mezzacapo, A; McClean, J; Lamata, L; Aspuru-Guzik, A; Solano, E

    2014-01-07

    Over the last few decades, quantum chemistry has progressed through the development of computational methods based on modern digital computers. However, these methods can hardly fulfill the exponentially-growing resource requirements when applied to large quantum systems. As pointed out by Feynman, this restriction is intrinsic to all computational models based on classical physics. Recently, the rapid advancement of trapped-ion technologies has opened new possibilities for quantum control and quantum simulations. Here, we present an efficient toolkit that exploits both the internal and motional degrees of freedom of trapped ions for solving problems in quantum chemistry, including molecular electronic structure, molecular dynamics, and vibronic coupling. We focus on applications that go beyond the capacity of classical computers, but may be realizable on state-of-the-art trapped-ion systems. These results allow us to envision a new paradigm of quantum chemistry that shifts from the current transistor to a near-future trapped-ion-based technology.

  12. Characterization of reactants, reaction mechanisms, and reaction products in atmospheric water droplets: fog, cloud, dew, and rain water chemistry. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Hoffmann, M.R.; Jacob, D.J.; Waldman, J.M.; Munger, J.W.; Flagan, R.C.

    1985-04-01

    Analyses of ground-based fogwater collected by inertial impaction in the Los Angeles basin, the San Gabriel Mountains, and the San Joaquin Valley revealed very high concentrations of NO3 SO4 S, NH4 , and other ions, often coupled with very high acidities. Fogs and strata in the Los Angeles basin typically had pH values ranging from 2 to 4. Acidities were not as high in the San Joaquin Valley, mostly because of scavenging by the fogs of ammonia from agricultural sources. Deposition of fogwater was observed to be an important pollutant sink during stagnation episodes in the San Joaquin Valley, and may also be an important source of acid input to surfaces in some areas. Kinetic experiments showed that H2O2 is important in the oxidation of S(IV) to S(VI) at low pH. Metal-catalyzed autoxidation could also be an important source of sulfate. However, the extreme acidities observed in fogs (below pH 3) require condensation on preexistent acidic nuclei and scavenging of gaseous nitric acid. Stabilization of S(IV) in the fog was observed, and this was attributed to the formation of S(IV)-aldehyde adducts.

  13. 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.)

  14. 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 ...

  15. Electrolytes and interphasial chemistry in Li ion devices

    Energy Technology Data Exchange (ETDEWEB)

    Xu, K. [Electrochemistry Branch, Sensors and Electron Devices Directorate, U. S. Army Research Laboratory, Adelphi, Maryland, 20783-1197 (United States)

    2010-07-01

    Since its appearance in 1991, the Li ion battery has been the major power source driving the rapid digitalisation of our daily life; however, much of the processes and mechanisms underpinning this newest battery chemistry remains poorly understood. As in any electrochemical device, the major challenge comes from the electrolyte/electrode interfaces, where the discontinuity in charge distribution and extreme disequality in electric forces induce diversified processes that eventually determine the kinetics of Li{sup +} intercalation chemistry. This article will summarize the most recent efforts on the fundamental understanding of the interphases in Li ion devices. Emphasis will be placed on the formation chemistry of the so-called 'SEI' on graphitic anode, the effect of solvation sheath structure of Li{sup +} on the intercalation energy barrier, and the feasibility of tailoring a desired interphase. Biologically inspired approaches to an ideal interphase will also be briefly discussed. (author)

  16. Electrolytes and Interphasial Chemistry in Li Ion Devices

    Directory of Open Access Journals (Sweden)

    Kang Xu

    2010-01-01

    Full Text Available Since its appearance in 1991, the Li ion battery has been the major power source driving the rapid digitalization of our daily life; however, much of the processes and mechanisms underpinning this newest battery chemistry remains poorly understood. As in any electrochemical device, the major challenge comes from the electrolyte/electrode interfaces, where the discontinuity in charge distribution and extreme disequality in electric forces induce diversified processes that eventually determine the kinetics of Li+ intercalation chemistry. This article will summarize the most recent efforts on the fundamental understanding of the interphases in Li ion devices. Emphasis will be placed on the formation chemistry of the so-called “SEI” on graphitic anode, the effect of solvation sheath structure of Li+ on the intercalation energy barrier, and the feasibility of tailoring a desired interphase. Biologically inspired approaches to an ideal interphase will also be briefly discussed.

  17. New insights into methane-oxygen ion chemistry

    KAUST Repository

    Alquaity, Awad B.S.; Chen, Bingjie; Han, Jie; Selim, Hatem; Belhi, Memdouh; Karakaya, Yasin; Kasper, Tina; Sarathy, Mani; Bisetti, Fabrizio; Farooq, Aamir

    2016-01-01

    External electric fields may reduce emissions and improve combustion efficiency by active control of combustion processes. In-depth, quantitative understanding of ion chemistry in flames enables predictive models to describe the effect of external electric fields on combustion plasma. This study presents detailed cation profile measurements in low-pressure, burner-stabilized, methane/oxygen/argon flames. A quadrupole molecular beam mass spectrometer (MBMS) coupled to a low-pressure (P =30Torr) combustion chamber was utilized to measure ion signals as a function of height above the burner. Lean, stoichiometric and rich flames were examined to evaluate the dependence of ion chemistry on flame stoichiometry. Additionally, for the first time, cataloging of flame cations is performed using a high mass resolution time-of-flight mass spectrometer (TOF-MS) to distinguish ions with the same nominal mass. In the lean and stoichiometric flames, the dominant ions were HO, CHO , CHO, CHO and CHO, whereas large signals were measured for HO, CH and CHO in the rich flame. The spatial distribution of cations was compared with results from numerical simulations constrained by thermocouple-measured flame temperatures. Across all flames, the predicted HO decay rate was noticeably faster than observed experimentally. Sensitivity analysis showed that the mole fraction of HO is most sensitive to the rate of chemi-ionization CH+O↔CHO +E. To our knowledge, this work represents the first detailed measurements of positive ions in canonical low-pressure methane flames.

  18. New insights into methane-oxygen ion chemistry

    KAUST Repository

    Alquaity, Awad B.S.

    2016-06-15

    External electric fields may reduce emissions and improve combustion efficiency by active control of combustion processes. In-depth, quantitative understanding of ion chemistry in flames enables predictive models to describe the effect of external electric fields on combustion plasma. This study presents detailed cation profile measurements in low-pressure, burner-stabilized, methane/oxygen/argon flames. A quadrupole molecular beam mass spectrometer (MBMS) coupled to a low-pressure (P =30Torr) combustion chamber was utilized to measure ion signals as a function of height above the burner. Lean, stoichiometric and rich flames were examined to evaluate the dependence of ion chemistry on flame stoichiometry. Additionally, for the first time, cataloging of flame cations is performed using a high mass resolution time-of-flight mass spectrometer (TOF-MS) to distinguish ions with the same nominal mass. In the lean and stoichiometric flames, the dominant ions were HO, CHO , CHO, CHO and CHO, whereas large signals were measured for HO, CH and CHO in the rich flame. The spatial distribution of cations was compared with results from numerical simulations constrained by thermocouple-measured flame temperatures. Across all flames, the predicted HO decay rate was noticeably faster than observed experimentally. Sensitivity analysis showed that the mole fraction of HO is most sensitive to the rate of chemi-ionization CH+O↔CHO +E. To our knowledge, this work represents the first detailed measurements of positive ions in canonical low-pressure methane flames.

  19. 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.

  20. Ion-enhanced gas-surface chemistry: The influence of the mass of the incident ion

    International Nuclear Information System (INIS)

    Gerlach-Meyer, U.; Coburn, J.W.; Kay, E.

    1981-01-01

    There are many examples of situations in which a gas-surface reaction rate is increased when the surface is simultaneously subjected to energetic particle bombardment. There are several possible mechanisms which could be involved in this radiation-enhanced gas-surface chemistry. In this study, the reaction rate of silicon, as determined from the etch yield, is measured during irradiation of the Si surface with 1 keV He + , Ne + , and Ar + ions while the surface is simultaneously subjected to fluxes of XeF 2 or Cl 2 molecules. Etch yields as high as 25 Si atoms/ion are observed for XeF 2 and Ar + on Si. A discussion is presented of the extent to which the results clarify the mechanisms responsible for ion-enhanced gas-surface chemistry. (orig.)

  1. 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)

  2. 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.

  3. 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 AxK1–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 Fe2+/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.

  4. 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

  5. Reactions of PO(x)Cl(y)-ions with O(2)(a1-delta-g), H(2)O, and Cl(2) at 298 K

    Science.gov (United States)

    2008-03-10

    have also been studied to assess the chemistry that would occur if trace amounts of these species reached the flow tube. Most of the POxCly " ions...secondary ion-molecule chemistry [25]. P02~ and PO3" were generated from dimethyl phosphite (Ventron, 99%). The reactant ion of interest was selected

  6. 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 (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.

  7. 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.

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

    Science.gov (United States)

    Prentice, Boone M; McLuckey, Scott A

    2013-02-01

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

  9. 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 )]

  10. 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

  11. 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...

  12. 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.)

  13. 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.

  14. 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 ...

  15. 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.

  16. 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)

  17. 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.

  18. 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

  19. 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.

  20. 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

  1. 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.

  2. Atmospheric Pressure Chemical Ionization Sources Used in The Detection of Explosives by Ion Mobility Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Waltman, Melanie J. [New Mexico Inst. of Mining and Technology, Socorro, NM (United States)

    2010-05-01

    Explosives detection is a necessary and wide spread field of research. From large shipping containers to airline luggage, numerous items are tested for explosives every day. In the area of trace explosives detection, ion mobility spectrometry (IMS) is the technique employed most often because it is a quick, simple, and accurate way to test many items in a short amount of time. Detection by IMS is based on the difference in drift times of product ions through the drift region of an IMS instrument. The product ions are created when the explosive compounds, introduced to the instrument, are chemically ionized through interactions with the reactant ions. The identity of the reactant ions determines the outcomes of the ionization process. This research investigated the reactant ions created by various ionization sources and looked into ways to manipulate the chemistry occurring in the sources.

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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

  13. 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

  14. 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

  15. 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.

  16. 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

  17. D-region ion-neutral coupled chemistry (Sodankylä Ion Chemistry, SIC) within the Whole Atmosphere Community Climate Model (WACCM 4) - WACCM-SIC and WACCM-rSIC

    Science.gov (United States)

    Kovács, Tamás; Plane, John M. C.; Feng, Wuhu; Nagy, Tibor; Chipperfield, Martyn P.; Verronen, Pekka T.; Andersson, Monika E.; Newnham, David A.; Clilverd, Mark A.; Marsh, Daniel R.

    2016-09-01

    This study presents a new ion-neutral chemical model coupled into the Whole Atmosphere Community Climate Model (WACCM). The ionospheric D-region (altitudes ˜ 50-90 km) chemistry is based on the Sodankylä Ion Chemistry (SIC) model, a one-dimensional model containing 307 ion-neutral and ion recombination, 16 photodissociation and 7 photoionization reactions of neutral species, positive and negative ions, and electrons. The SIC mechanism was reduced using the simulation error minimization connectivity method (SEM-CM) to produce a reaction scheme of 181 ion-molecule reactions of 181 ion-molecule reactions of 27 positive and 18 negative ions. This scheme describes the concentration profiles at altitudes between 20 km and 120 km of a set of major neutral species (HNO3, O3, H2O2, NO, NO2, HO2, OH, N2O5) and ions (O2+, O4+, NO+, NO+(H2O), O2+(H2O), H+(H2O), H+(H2O)2, H+(H2O)3, H+(H2O)4, O3-, NO2-, O-, O2, OH-, O2-(H2O), O2-(H2O)2, O4-, CO3-, CO3-(H2O), CO4-, HCO3-, NO2-, NO3-, NO3-(H2O), NO3-(H2O)2, NO3-(HNO3), NO3-(HNO3)2, Cl-, ClO-), which agree with the full SIC mechanism within a 5 % tolerance. Four 3-D model simulations were then performed, using the impact of the January 2005 solar proton event (SPE) on D-region HOx and NOx chemistry as a test case of four different model versions: the standard WACCM (no negative ions and a very limited set of positive ions); WACCM-SIC (standard WACCM with the full SIC chemistry of positive and negative ions); WACCM-D (standard WACCM with a heuristic reduction of the SIC chemistry, recently used to examine HNO3 formation following an SPE); and WACCM-rSIC (standard WACCM with a reduction of SIC chemistry using the SEM-CM method). The standard WACCM misses the HNO3 enhancement during the SPE, while the full and reduced model versions predict significant NOx, HOx and HNO3 enhancements in the mesosphere during solar proton events. The SEM-CM reduction also identifies the important ion-molecule reactions that affect the partitioning of

  18. 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.

  19. 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.

  20. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1975-01-01

    The chemical research and development efforts related to the design and ultimate operation of molten-salt breeder reactor systems are concentrated on fuel- and coolant-salt chemistry, including the development of analytical methods for use in these systems. The chemistry of tellurium in fuel salt is being studied to help elucidate the role of this element in the intergranular cracking of Hastelloy N. Studies were continued of the effect of oxygen-containing species on the equilibrium between dissolved UF 3 and dissolved UF 4 , and, in some cases, between the dissolved uranium fluorides and graphite, and the UC 2 . Several aspects of coolant-salt chemistry are under investigation. Hydroxy and oxy compounds that could be formed in molten NaBF 4 are being synthesized and characterized. Studies of the chemistry of chromium (III) compounds in fluoroborate melts were continued as part of a systematic investigation of the corrosion of structural alloys by coolant salt. An in-line voltammetric method for determining U 4+ /U 3+ ratios in fuel salt was tested in a forced-convection loop over a six-month period. (LK)

  1. 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

  2. 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

  3. 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

  4. 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.

  5. 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.

  6. 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).

  7. 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)

  8. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1976-01-01

    Research progress is reported in programs on fuel-salt chemistry, properties of compounds in the Li--Te system, Te spectroscopy UF 4 --H equilibria, porous electrode studies of molten salts, fuel salt-coolant salt reactions, thermodynamic properties of transition-metal fluorides, and properties of sodium fluoroborate. Developmental work on analytical methods is summarized including in-line analysis of molten MSBR fuel, analysis of coolant-salts for tritium, analysis of molten LiF--BeF 2 --ThF 4 for Fe and analysis of LiF--BeF--ThF 4 for Te

  9. 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.

  10. 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)

  11. 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.

  12. 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

  13. 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.

  14. [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

  15. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1975-01-01

    Research and development activities dealing with the chemical problems related to design and ultimate operation of molten-salt reactor systems are described. An experimental test stand was constructed to expose metallurgical test specimens to Te 2 vapor at defined temperatures and deposition rates. To better define the chemistry of fluoroborate coolant, several aspects are being investigated. The behavior of hydroxy and oxy compounds in molten NaBF 4 is being investigated to define reactions and compounds that may be involved in corrosion and/or could be involved in methods for trapping tritium. Two corrosion products of Hastelloy N, Na 3 CrF 6 and Na 5 Cr 3 F 14 , were identified from fluoroborate systems. The evaluation of fluoroborate and alternate coolants continued. Research on the behavior of hydrogen and its isotopes is summarized. The solubilities of hydrogen, deuterium, and helium in Li 2 BeF 4 are very low. The sorption of tritium on graphite was found to be significant (a few milligrams of tritium per kilogram of graphite), possibly providing a means of sequestering a portion of the tritium produced. Development of analytical methods continued with emphasis on voltammetric and spectrophotometric techniques for the in-line analysis of corrosion products such as Fe 2+ and Cr 3+ and the determination of the U 3+ /U 4+ ratio in MSBR fuel salt. Similar studies were conducted with the NaBF 4 --NaF coolant salt. Information developed during the previous operation of the CSTF has been assessed and used to formulate plans for evaluation of in-line analytical methods in future CSTF operations. Electroanalytical and spectrophotometric research suggests that an electroactive protonic species is present in molten NaBF 4 --NaF, and that this species rapidly equilibrates with a volatile proton-containing species. Data obtained from the CSTF indicated that tritium was concentrated in the volatile species. (JGB)

  16. 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

  17. 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.

  18. 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).

  19. 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.

  20. 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.

  1. 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.)

  2. The Acute Toxicity of Major Ion Salts to Ceriodaphnia dubia: I. Influence of background water chemistry.

    Data.gov (United States)

    U.S. Environmental Protection Agency — This dataset provides concentration-response data and associated general chemistry conditions for 26 experiments consisting of 149 tests regarding the acute toxicity...

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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.)

  10. 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.

  11. 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.

  12. 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.

  13. 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. ^

  14. 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.

  15. 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 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

  16. 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

  17. 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.

  18. 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 - .

  19. 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.

  20. Applications of secondary ion mass spectrometry in catalysis and surface chemistry

    NARCIS (Netherlands)

    Borg, H.J.; Niemantsverdriet, J.W.; Spivey, J.J.; Agarwal, S.K.

    1994-01-01

    A review with 182 refs. is given on phys. phenomena such as sputtering, ion emission, ionization and neutralization which are involved in SIMS. Applications of SIMS in catalysis and obtaining information about catalysts interactions with gases promoters and poisons are described. Also applications

  1. 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

  2. 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)

  3. "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.

  4. 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.

  5. 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.

  6. 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.

  7. Stereognostic coordination chemistry. 1. The design and synthesis of chelators for the uranyl ion

    International Nuclear Information System (INIS)

    Franczyk, T.S.; Czerwinski, K.R.; Raymond, K.N.

    1992-01-01

    A new approach to the molecular recognition of metal oxo cations is introduced based on a ligand design strategy that provides at least one hydrogen bond donor for interaction with oxo group(s) as well as conventional electron pair donor ligands for coordination to the metal center. This concept of stereognostic coordination of oxo metal ions is exemplified in the design of four tripodal ligands-tris[2-(2-carboxyphenoxy)ethyl]amine[NEB],tris[3-(2-carboxyphenoxy)propyl]amine[NPB], tris[3-(2-carboxynaphthyl-3-oxy)propyl]amine [NPN], and tris[3-(2-carboxy=4octadecylphenoxy)propyl]amine[NPodB] - for sequestration of the uranyl ion. The ligands NEB, NPB, and NPN form 1:1 complexes with UO 2 2+ . The bidentate coordination of carboxyl groups of these compounds is indicated by the infrared spectra, which offer some support for the presence of a hydrogen bond to the uranyl group. Mass spectral data corroborate CPK model predictions that more than five intervening atoms between the tertiary nitrogen atom and the carboxylate groups are required for metal ion incorporation and monomeric complex formation. Solvent extractions of aqueous UO 2 2+ into chloroform solutions of the ligands have shown them to be powerful extractants. In the case of the very hydrophobic ligand NPodB the stoichiometry of the complexation reaction is shown to be 1:1 UO 2 /ligand complex formed by the release of 3 protons. The extraction is quantitative at pH 2.5, and an effective extraction coefficient of about 10 11 is estimated for neutral aqueous solutions of UO 2 2+ . 81 refs., 13 figs., 2 tabs

  8. 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.)

  9. Highly dispersive ion exchangers in the analytical chemistry of uranium, particularly regarding separation methods

    International Nuclear Information System (INIS)

    Schoening, R.

    1975-01-01

    The reaction of water-insoluble polyvinyl pyrrolidon with uranium VI was investigated and a determination method for uranium was worked out in which the polyvinyl pyrrolidon was used as specific exchanger. Good separations of uranium from numerous transition metal ions were achieved here. The application of this exchanger for a fast and simple elution and determination method was of particular importance. A possible sorption mechanism was suggested based on the capacity curve of uranium with polyvinyl pyrrolidon and nitrogen and chloride content at maximum load. The sorption occurs by coordination of the carbonyl oxygen of single pyrrolidon rings with the protons of the complex acides and uranium. This assumption is supported by IR investigations. The sorbability of other inorganic acids was also investigated and possible structures were formulated for the sorption mechanism. In addition to this, ion exchangers were prepared based on cellulose by converting cellulose powder with aziridine and tris-1-aziridinyl-phosphine oxide. A polyethylene imine cellulose of high capacity was obtained in the conversion of cellulose powder with aziridine. This exchanger absorbs cobalt III very strongly. The exchanger loaded with cobalt III was used to separate the uranium as cyanato complex. The exchanger obtained in converting chlorated cellulose with tris-1-aziridinyl phosphine oxide also absorbs uranium VI very strongly. Thus a separation method of high specifity and selectivity was developed. (orig.) [de

  10. Numerical simulation of advective-dispersive multisolute transport with sorption, ion exchange and equilibrium chemistry

    Science.gov (United States)

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

    1986-01-01

    A model was developed that can simulate the effect of certain chemical and sorption reactions simultaneously among solutes involved in advective-dispersive transport through porous media. The model is based on a methodology that utilizes physical-chemical relationships in the development of the basic solute mass-balance equations; however, the form of these equations allows their solution to be obtained by methods that do not depend on the chemical processes. The chemical environment is governed by the condition of local chemical equilibrium, and may be defined either by the linear sorption of a single species and two soluble complexation reactions which also involve that species, or binary ion exchange and one complexation reaction involving a common ion. Partial differential equations that describe solute mass balance entirely in the liquid phase are developed for each tenad (a chemical entity whose total mass is independent of the reaction process) in terms of their total dissolved concentration. These equations are solved numerically in two dimensions through the modification of an existing groundwater flow/transport computer code. (Author 's abstract)

  11. Ion chemistry in germane/fluorocompounds gaseous mixtures: a mass spectrometric and theoretical study.

    Science.gov (United States)

    Antoniotti, Paola; Rabezzana, Roberto; Turco, Francesca; Borocci, Stefano; Giordani, Maria; Grandinetti, Felice

    2008-10-01

    The ion-molecule reactions occurring in GeH(4)/NF(3), GeH(4)/SF(6), and GeH(4)/SiF(4) gaseous mixtures have been investigated by ion trap mass spectrometry and ab initio calculations. While the NF(x)(+) (x=1-3) react with GeH(4) mainly by the exothermic charge transfer, the open-shell Ge(+) and GeH(2)(+) undergo the efficient F-atom abstraction from NF(3) and form GeF(+) and F-GeH(2)(+) as the only ionic products. The mechanisms of these two processes are quite similar and involve the formation of the fluorine-coordinated complexes Ge-F-NF(2)(+) and H(2)Ge-F-NF(2)(+), their subsequent crossing to the significantly more stable isomers FGe-NF(2)(+) and F-GeH(2)-NF(2)(+), and the eventual dissociation of these ions into GeF(+) (or F-GeH(2)(+)) and NF(2). The closed-shell GeH(+) and GeH(3)(+) are instead much less reactive towards NF(3), and the only observed process is the less efficient formation of GeF(+) from GeH(+). The theoretical investigation of this unusual H/F exchange reaction suggests the involvement of vibrationally-hot GeH(+). Passing from NF(3) to SF(6) and SiF(4), the average strength of the M-F bond increases from 70 to 79 and 142 kcal mol(-1), and in fact the only process observed by reacting GeH(n)(+) (n=0-3) with SF(6) and SiF(4) is the little efficient F-atom abstraction from SF(6) by Ge(+). Irrespective of the experimental conditions, we did not observe any ionic product of Ge-N, Ge-S, or Ge-Si connectivity. This is in line with the previously observed exclusive formation of GeF(+) from the reaction between Ge(+) and C-F compounds such as CH(3)F. Additionally observed processes include in particular the conceivable formation of the elusive thiohypofluorous acid FSH from the reaction between SF(+) and GeH(4).

  12. A Combustion Chemistry Analysis of Carbonate Solvents in Li-Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Harris, S J; Timmons, A; Pitz, W J

    2008-11-13

    Under abusive conditions Li-ion batteries can rupture, ejecting electrolyte and other flammable gases. In this paper we consider some of the thermochemical properties of these gases that will determine whether they ignite and how energetically they burn. We show that flames of carbonate solvents are fundamentally less energetic than those of conventional hydrocarbons. An example of this difference is given using a recently developed mechanism for dimethyl carbonate (DMC) combustion, where we show that a diffusion flame burning DMC has only half the peak energy release rate of an analogous propane flame. We find a significant variation among the carbonate solvents in the factors that are important to determining flammability, such as combustion enthalpy and vaporization enthalpy. This result suggests that thermochemical and kinetic factors might well be considered when choosing solvent mixtures.

  13. 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

  14. A combustion chemistry analysis of carbonate solvents used in Li-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Harris, Stephen J.; Timmons, Adam [General Motors R and D Center, MC 480-102-000, Warren, MI 48090-9055 (United States); Pitz, William J. [Lawrence Livermore National Laboratory, Livermore, CA 94551 (United States)

    2009-09-05

    Under abusive conditions Li-ion cells can rupture, ejecting electrolyte and other flammable gases. In this paper we consider some of the thermochemical and combustion properties of these gases that determine whether they ignite and how energetically they burn. We find a significant variation among the carbonate solvents in the factors that are important to determining flammability, such as combustion enthalpy and vaporization enthalpy. We also show that flames of carbonate solvents are fundamentally less energetic than those of conventional hydrocarbons. An example of this contrast is given using a recently developed mechanism for dimethyl carbonate (DMC) combustion, where we show that a diffusion flame burning DMC has only half the peak heat release rate of an analogous propane flame. Interestingly, peak temperatures differ by only 25%. We argue that heat release rate is a more useful parameter than temperature when evaluating the likelihood that a flame in one cell will ignite a neighboring cell. Our results suggest that thermochemical and combustion property factors might well be considered when choosing solvent mixtures when flammability is a concern. (author)

  15. Spraying mode effect on droplet formation and ion chemistry in electrosprays.

    Science.gov (United States)

    Nemes, Peter; Marginean, Ioan; Vertes, Akos

    2007-04-15

    Depending on the spraying conditions and fluid properties, a variety of electrospray regimes exists. Here we explore the changes in ion production that accompany the transitions among the three axial spraying modes, the burst mode, the pulsating Taylor cone mode, and the cone-jet mode. Spray current oscillation and phase Doppler anemometry measurements, fast imaging of the electrified meniscus, and mass spectrometry are utilized to study the formation, size, velocity, and chemical composition of droplets produced in the three modes. High-speed images indicate that the primary droplets are produced by varicose waves and lateral kink instabilities on the liquid jet emerging from the Taylor cone, whereas secondary droplets are formed by fission. Dramatic changes in the droplet size distributions result from the various production and breakup mechanisms observed at different emitter voltages and liquid flow rates. We demonstrate that droplet fission can be facilitated by space charge effects along the liquid jet and in the plume. Compared to the other two regimes, a significantly enhanced signal-to-noise ratio, a lower degree of analyte oxidation, and milder fragmentation are observed for the cone-jet mode.

  16. 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

  17. 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.

  18. 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…

  19. 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.

  20. Characterizing interactions between surface water and groundwater in the Jialu River basin using major ion chemistry and stable isotopes

    Directory of Open Access Journals (Sweden)

    L. Yang

    2012-11-01

    Full Text Available The Jialu River, a secondary tributary of the Huaihe River, has been severely contaminated from major contaminant sources, such as a number of untreated or lightly treated sewage waste in some cities. Groundwater along the river is not an isolated component of the hydrologic system, but is instead connected with the surface water. This study aims to investigate temporal and spatial variations in water chemistry affected by humans and to characterize the relationships between surface water (e.g. reservoirs, lakes and rivers and groundwater near the river in the shallow Quaternary aquifer. Concentration of Cl in north Zhengzhou City increased prominently due to the discharge of a large amount of domestic water. Nitrate and potassium show maximum concentrations in groundwater in Fugou County. These high levels can be attributed to the use of a large quantity of fertilizer over this region. Most surface water appeared to be continuously recharged from the surrounding groundwater (regional wells based on comparison surface water with groundwater levels, stable-isotopes and major ion signatures. However, the groundwater of a transitional well (location SY3 seemed to be recharged by river water via bank infiltration in September 2010. Fractional contributions of river water to the groundwater were calculated based on isotopic and chemical data using a mass-balance approach. Results show that the groundwater was approximately composed of 60–70% river water. These findings should be useful for a better understanding of hydrogeological processes at the river-aquifer interface and ultimately benefit water management in the future.

  1. 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'

  2. 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.

  3. Mass spectrometric studies of bimolecular reactions in a selected ion flow tube (SIFT)

    International Nuclear Information System (INIS)

    Shul, R.J.; Upschulte, B.L.; Passarella, R.; Keesee, R.G.; Castleman, A.W.

    1985-01-01

    The rate coefficients for a number of thermal energy charge transfer reactions have been obtained with a selected ion flow tube (SIFT). The reactions studied involve Ar + and Ar 2 + with a variety of neutral molecules including: O 2 , CS 2 , CO 2 , SO 2 , H 2 S, NH 3 , and SF 6 . Such reactions have been of long-standing interest in the field of gas-phase ion-molecule chemistry from both a practical and fundamental point of view. Consideration of charge transfer reactions as possible sources of chemical lasers and their role in ionospheric and interstellar chemistry account for much of the interest. Fundamentally, the mechanism involved in these reactions has yet to be definitively established. The consumption deposition of energy into internal modes and translational degrees of freedom in such reactions has also been a topic of considerable debate. The apparatus consists of five main components: an ion source, SIFT quadrupole, ion injector, flow tube, and a mass spectrometer detection system. Ions formed in a high pressure source leak into a SIFT quadrupole where they are mass selected. The primary ion of interest is then injected into the flow tube where reactions are studied. Once in the flow tube the ions are carried downstream by an inert buffer gas, either argon, nitrogen, or helium in the present study. Neutral reactant gas is added through a reactant gas inlet (RGI) at an appropriate location downstream in the flow tube, and allowed to react with the injected ions. Ions on the flow tube axis are sampled through a 1 mm orifice where they are mass analyzed by a second quadrupole mass spectrometer and detected with a channeltron electron multiplier

  4. 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.

  5. 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.)

  6. 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...

  7. 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...

  8. 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.

  9. 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)

  10. 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

  11. 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....

  12. 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

  13. 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.

  14. 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

  15. An experimental study of the ion chemistry and thermal balance in the E- and F-regions above Wallops Island

    Science.gov (United States)

    Brace, L. H.; Mayr, H. G.; Pharo, M. W., III; Scott, L. R.; Taylor, H. A., Jr.

    1971-01-01

    E and F region positive ion composition, electron concentration and thermal balance vertical profile, discussing ionizing radiation spectrum, plasma cooling, primary chemical reaction rates and ionospheric formation

  16. 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

  17. 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...

  18. 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.)

  19. Thermodynamics of Small Alkali Metal Halide Cluster Ions: Comparison of Classical Molecular Simulations with Experiment and Quantum Chemistry

    Czech Academy of Sciences Publication Activity Database

    Vlček, L.; Uhlík, F.; Moučka, F.; Nezbeda, Ivo; Chialvo, L.

    2015-01-01

    Roč. 119, č. 3 (2015), s. 488-500 ISSN 1089-5639 Institutional support: RVO:67985858 Keywords : monte-carlo simulations * molecular-dynamic simulations * classical drude oscillators Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.883, year: 2015

  20. High-throughput bioconjugation for enhanced 193 nm photodissociation via droplet phase initiated ion/ion chemistry using a front-end dual spray reactor.

    Science.gov (United States)

    Cotham, Victoria C; Shaw, Jared B; Brodbelt, Jennifer S

    2015-09-15

    Fast online chemical derivatization of peptides with an aromatic label for enhanced 193 nm ultraviolet photodissociation (UVPD) is demonstrated using a dual electrospray reactor implemented on the front-end of a linear ion trap (LIT) mass spectrometer. The reactor facilitates the intersection of protonated peptides with a second population of chromogenic 4-formyl-1,3-benzenedisulfonic acid (FBDSA) anions to promote real-time formation of ion/ion complexes at atmospheric pressure. Subsequent collisional activation of the ion/ion intermediate results in Schiff base formation generated via reaction between a primary amine in the peptide cation and the aldehyde moiety of the FBDSA anion. Utilizing 193 nm UVPD as the subsequent activation step in the MS(3) workflow results in acquisition of greater primary sequence information relative to conventional collision induced dissociation (CID). Furthermore, Schiff-base-modified peptides exhibit on average a 20% increase in UVPD efficiency compared to their unmodified counterparts. Due to the efficiency of covalent labeling achieved with the dual spray reactor, we demonstrate that this strategy can be integrated into a high-throughput LC-MS(n) workflow for rapid derivatization of peptide mixtures.

  1. 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.

  2. New field of actinides solution chemistry; electrochemical study on actinide ion transfer at the interface of two immiscible electrolyte solutions

    Energy Technology Data Exchange (ETDEWEB)

    Kitatsuji, Yoshihiro; Yoshida, Zenko [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Kudo, Hiroshi [Tohoku Univ., Graduate School of Science, Sendai, Miyagi (Japan); Kihara, Sorin [Kyoto Inst. of Technolgy, Dept. of Chemistry, Kyoto (Japan)

    2002-04-01

    A novel electrochemical method on the basis of a controlled electrolysis has been developed for the study of the ion transfer at the interface of two immiscible electrolyte solutions (ITIES). The controlled-potential electrolysis for ITIES (CPEITIES) was applied to the transfer of actinide ions, and Gibbs energies for the transfer of UO{sub 2}{sup 2+} and Am{sup 3+} from aqueous solution (w) to nitrobenzene solution (nb) were determined to be 71.7 and 113 kJ mol{sup -1}, respectively. The ion transfer potentials for the facilitated transfer of UO{sub 2{sup +}} and Am{sup 3+} from w to nb in the presence of bis(diphenylphosphoryl)methane were determined, from which the stability constants of UO{sub 2}(BDPPM){sub 3}{sup 2+} and Am(BDPPM){sub 3}{sup 3+} complexes involved in the facilitated ion transfer reaction, were calculated to be 10{sup 23.9} and 10{sup 27.5}, respectively. On the basis of the results of CPEITIES, a feasibility of a new separation method, i.e., an electrolytic ion transfer separation, of actinide ions is evaluated. (author)

  3. Basic principles of electrolyte chemistry for microfluidic electrokinetics. Part II: Coupling between ion mobility, electrolysis, and acid-base equilibria.

    Science.gov (United States)

    Persat, Alexandre; Suss, Matthew E; Santiago, Juan G

    2009-09-07

    We present elements of electrolyte dynamics and electrochemistry relevant to microfluidic electrokinetics experiments. In Part I of this two-paper series, we presented a review and introduction to the fundamentals of acid-base chemistry. Here, we first summarize the coupling between acid-base equilibrium chemistry and electrophoretic mobilities of electrolytes, at both infinite and finite dilution. We then discuss the effects of electrode reactions on microfluidic electrokinetic experiments and derive a model for pH changes in microchip reservoirs during typical direct-current electrokinetic experiments. We present a model for the potential drop in typical microchip electrophoresis device. The latter includes finite element simulation to estimate the relative effects of channel and reservoir dimensions. Finally, we summarize effects of electrode and electrolyte characteristics on potential drop in microfluidic devices. As a whole, the discussions highlight the importance of the coupling between electromigration and electrophoresis, acid-base equilibria, and electrochemical reactions.

  4. 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.

  5. Gaseous anion chemistry. Hydrogen-deuterium exchange in mono- and dialcohol alkoxide ions: ionization reactions in dialcohols

    International Nuclear Information System (INIS)

    Lloyd, J.R.; Agosta, W.C.; Field, F.H.

    1980-01-01

    The subject of this work is H-D exchange in certain gaseous anions using D 2 as the exchanging agent. The anions involved are produced from ethylene glycol, 1,3-propanediol, 1,4-butanediol, ethanol, 1-propanol, and 1-butanol. Spectra and postulated ionization reactions for these mono- and dialcohols are given. Hydrogen-deuterium exchange occurs in the (M - 1) - and (2M - 1) - ions of ethylene glycol, 1,3-propanediol, and 1,4-butanediol. The amount of exchange occurring is 3-8 times greater in (2M - 1) - than in (M - 1) - . The amount of H-D exchange occurring in ethanol, 1-propanol, and 1-butanol is small or zero in the (2M - 1) - ions and in the (M - 1) - ion for 1-butanol [the only (M - 1) - ion which could be examined experimentally]. The amount of exchange occurring in the (2M - 1) - and (M - 1) - ions from ethylene glycol is not affected by the total pressure or composition of the reaction mixture in the ionization chamber of the mass spectrometer. A novel hydrogen-bridging mechanism is suggested to account for the observed exchange occurring in the dialcohols

  6. 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.

  7. Chemistry of radio-frequency source of negative hydrogen ions; Chemia radio-frekvencneho zdroja negativnych ionov vodika

    Energy Technology Data Exchange (ETDEWEB)

    Skoviera, J.; Cernusak, I. [Univerzita Komenskeho, Prirodovedecka fakulta, Katedra fyzikalnej a teoretickej chemie, 84215 Bratislava (Slovakia)

    2013-04-16

    International Thermonuclear Experimental Reactor (ITER) is a prototype of nuclear fusion reactor Tokamak currently build in Cadarache. It will use as one of primary plasma heating components a radiofrequency driven negative ion source of deuterium. The purpose of cesium evaporated in the part of this ion source is to react with free electrons which can incidentally destroy generated hydrogen ions and are co-extracted with the hydrogen beam. Goal of this work is to investigate majority of processes which might have impact on hydrogen anion in either formative or destructive way associated with cesium. Generally the caesium dynamics is very complex in such sources and the interplay of the individual contributions and their control to establish optimum caesium coverage of the plasma grid is still an open issue. (authors)

  8. 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

  9. Measuring Gas-Phase Basicities of Amino Acids Using an Ion Trap Mass Spectrometer: A Physical Chemistry Laboratory Experiment

    Science.gov (United States)

    Sunderlin, Lee S.; Ryzhov, Victor; Keller, Lanea M. M.; Gaillard, Elizabeth R.

    2005-01-01

    An experiment is performed to measure the relative gas-phase basicities of a series of five amino acids to compare the results to literature values. The experiments use the kinetic method for deriving ion thermochemistry and allow students to perform accurate measurements of thermodynamics in a relatively short time.

  10. Ion beam nanopatterning of III-V semiconductors: consistency of experimental and simulation trends within a chemistry-driven theory.

    Science.gov (United States)

    El-Atwani, O; Norris, S A; Ludwig, K; Gonderman, S; Allain, J P

    2015-12-16

    Several proposed mechanisms and theoretical models exist concerning nanostructure evolution on III-V semiconductors (particularly GaSb) via ion beam irradiation. However, making quantitative contact between experiment on the one hand and model-parameter dependent predictions from different theories on the other is usually difficult. In this study, we take a different approach and provide an experimental investigation with a range of targets (GaSb, GaAs, GaP) and ion species (Ne, Ar, Kr, Xe) to determine new parametric trends regarding nanostructure evolution. Concurrently, atomistic simulations using binary collision approximation over the same ion/target combinations were performed to determine parametric trends on several quantities related to existing model. A comparison of experimental and numerical trends reveals that the two are broadly consistent under the assumption that instabilities are driven by chemical instability based on phase separation. Furthermore, the atomistic simulations and a survey of material thermodynamic properties suggest that a plausible microscopic mechanism for this process is an ion-enhanced mobility associated with energy deposition by collision cascades.

  11. 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

  12. 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)

  13. 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…

  14. 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.

  15. 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.

  16. 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.

  17. Ion chemistry and individual particle analysis of atmospheric aerosols over Mt. Bogda of eastern Tianshan Mountains, Central Asia.

    Science.gov (United States)

    Zhao, Shuhui; Li, Zhongqin; Zhou, Ping

    2011-09-01

    Aerosol samples were collected during the scientific expedition to Mt. Bogda in July-August, 2009. The major inorganic ions (Na( + ), NH⁺₄, K( + ), Mg(2 + ), Ca(2 + ), Cl( - ), SO²⁻₄, and NO⁻₃) of the aerosols were determined by ion chromatography. SO²⁻₄, NO⁻₃, and Ca(2 + ) were the dominate ions, with the mean concentrations of 0.86, 0.56, and 0.28 μg m⁻³, respectively. These mean ion concentrations were generally comparable with the background conditions in remote site of Xinjiang, while much lower than those in Ürümqi. Morphology and elemental compositions of 1,500 particles were determined by field emission scanning electron microscopy equipped with an energy dispersive X-ray spectrometer. Based on the morphology and elemental compositions, particles were classed into four major groups: soot (15.1%), fly ash (4.7%), mineral particles (78.9%), and little other matters (0.8% Fe-rich particles and 0.5% unrecognized particles). Presence of soot and fly ash particles indicated the influence of anthropogenic pollutions, while abundance mineral particles suggested that natural processes were the primary source of aerosols over this region, coinciding with the ionic analysis. Backward air mass trajectory analysis suggested that Ürümqi may contribute some anthropogenic pollution to this region, while the arid and semi-arid regions of Central Asia were the primary source.

  18. Thermodynamics of Small Alkali Metal Halide Cluster Ions: Comparison of Classical Molecular Simulations with Experiment and Quantum Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Vlcek, Lukas [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Uhlik, Filip [Charles Univ., Prague (Czech Republic); Moucka, Filip [Purkinje Univ. (Czech Republic); Nezbeda, Ivo [Purkinje Univ. (Czech Republic); Academy of Sciences of the Czech Republic (ASCR), Prague (Czech Republic); Chialvo, Ariel A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-12-16

    We evaluate the ability of selected classical molecular models to describe the thermodynamic and structural aspects of gas-phase hydration of alkali halide ions and the formation of small water clusters. To understand the effect of many-body interactions (polarization) and charge penetration effects on the accuracy of a force field, we perform Monte Carlo simulations with three rigid water models using different functional forms to account for these effects: (i) point charge non-polarizable SPC/E, (ii) Drude point charge polarizable SWM4- DP, and (iii) Drude Gaussian charge polarizable BK3. Model predictions are compared with experimental Gibbs free energies and enthalpies of ion hydration, and with microscopic structural properties obtained from quantum DFT calculations. We find that all three models provide comparable predictions for pure water clusters and cation hydration, but differ significantly in their description of anion hydration. None of the investigated classical force fields can consistently and quantitatively reproduce the experimental gas phase hydration thermodynamics. The outcome of this study highlights the relation between the functional form that describes the effective intermolecular interactions and the accuracy of the resulting ion hydration properties.

  19. 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

  20. 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)

  1. 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.

  2. 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.

  3. 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.

  4. 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.)

  5. Evaluation of leachable behavior from ion exchange resins effects of organic impurities on BWR water chemistry. 1

    International Nuclear Information System (INIS)

    Igarashi, Hiroo; Nishimura, Yusaku; Ohsumi, Katsumi; Uchida, Shunsuke; Matsui, Tsuneo

    1999-01-01

    The elution rate of leachables from ion exchange resin, which is used in condensate demineralizers and is one of several major sources of organic compounds in BWR cooling water, was measured. Properties of the leachables and elution rate depended on the kind of ion exchange resin and the years of use. The organic compounds elution rate of cation exchange resin was constant for 5 years and the molecular weight of these leachables was low. After 5 years, the elution rate increased and leachables consisted of organic compounds of high molecular weights of several thousand. The elution rate of anion exchange resin decreased yearly. The difference in the elution behavior was attributed to a dependence on oxidation degradation promoted by transition metal catalysis. The cation exchange resin included absorbed transition metal, while the anion exchange resin did not. An empirical formula showing the time dependence of the elution rate of organic compounds was derived. The formula was judged to be appropriate based on simulations of an actual BWR plant and comparisons of impurity concentrations with actual reactor water data. (author)

  6. 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

  7. On-line ion chemistry for the AMS analysis of {sup 90}Sr and {sup 135,137}Cs

    Energy Technology Data Exchange (ETDEWEB)

    Eliades, J. [IsoTrace Laboratory, University of Toronto, 60 St. George St., Toronto, ON, M5S 1A7 (Canada); Zhao, X.-L. [Department of Physics, University of Ottawa, 150 Louis Pasteur, Ottawa, ON, K1N 6N5 (Canada); Litherland, A.E. [IsoTrace Laboratory, University of Toronto, 60 St. George St., Toronto, ON, M5S 1A7 (Canada); Kieser, W.E., E-mail: liam.kieser@utoronto.ca [Department of Physics, University of Ottawa, 150 Louis Pasteur, Ottawa, ON, K1N 6N5 (Canada)

    2013-01-15

    The analysis of {sup 90}Sr by AMS has so far required the use of very large tandem accelerators in order to separate the isobar {sup 90}Zr by the rate-of-energy-loss method. The analysis of {sup 135,137}Cs by AMS has never been attempted as the separation of the isobars {sup 135,137}Ba by the traditional method requires even higher energies, so that this approach would become prohibitively expensive for routine analysis. Following the successful demonstration of Cl{sup -}-S{sup -} separation by the Isobar Separator, the same apparatus was used to test the separation of other pairs of isobars. Surprisingly effective results were obtained with NO{sub 2} gas in the cases of SrF{sub 3}{sup -}-ZrF{sub 3}{sup -} and CsF{sub 2}{sup -}-BaF{sub 2}{sup -} separations. Reduction factors of {approx}4 Multiplication-Sign 10{sup -6} for ZrF{sub 3}{sup -}/SrF{sub 3}{sup -} and {approx}2 Multiplication-Sign 10{sup -5} for BaF{sub 2}{sup -}/CsF{sub 2}{sup -} were measured. SrF{sub 3}{sup -} and CsF{sub 2}{sup -} are both super-halogen anions and are preferentially produced in the ion source rather than ZrF{sub 3}{sup -} and BaF{sub 2}{sup -} when using the PbF{sub 2} matrix-assisted method. Reduction factors for ion source production with such targets of {approx}3 Multiplication-Sign 10{sup -5} for ZrF{sub 3}{sup -}-SrF{sub 3}{sup -} and {approx}5 Multiplication-Sign 10{sup -4} for BaF{sub 2}{sup -}-CsF{sub 2}{sup -} were found. The combined methods would suggest a theoretical detection sensitivity for {sup 90}Sr/Sr {approx}6 Multiplication-Sign 10{sup -16}, {sup 135}Cs/Cs {approx}7 Multiplication-Sign 10{sup -15} and {sup 137}Cs/Cs {approx}1 Multiplication-Sign 10{sup -14}, assuming 10 ppm Zr and Ba contamination in the AMS targets. In addition to the earlier Cl{sup -}-S{sup -} separation work, these measurements further illustrate the potential of on-line ion chemical methods for broadening the analytical scope of small AMS systems.

  8. Activation of CH4 by Th(+) as studied by guided ion beam mass spectrometry and quantum chemistry.

    Science.gov (United States)

    Cox, Richard M; Armentrout, P B; de Jong, Wibe A

    2015-04-06

    The reaction of atomic thorium cations with CH4 (CD4) and the collision-induced dissociation (CID) of ThCH4(+) with Xe are studied using guided ion beam tandem mass spectrometry. In the methane reactions at low energies, ThCH2(+) (ThCD2(+)) is the only product; however, the energy dependence of the cross-section is inconsistent with a barrierless exothermic reaction as previously assumed on the basis of ion cyclotron resonance mass spectrometry results. The dominant product at higher energies is ThH(+) (ThD(+)), with ThCH3(+) (ThCD3(+)) having a similar threshold energy. The latter product subsequently decomposes at still higher energies to ThCH(+) (ThCD(+)). CID of ThCH4(+) yields atomic Th(+) as the exclusive product. The cross-sections of all product ions are modeled to provide 0 K bond dissociation energies (in eV) of D0(Th(+)-H) ≥ 2.25 ± 0.18, D0(Th(+)-CH) = 6.19 ± 0.16, D0(Th(+)-CH2) ≥ 4.54 ± 0.09, D0(Th(+)-CH3) = 2.60 ± 0.30, and D0(Th(+)-CH4) = 0.47 ± 0.05. Quantum chemical calculations at several levels of theory are used to explore the potential energy surfaces for activation of methane by Th(+), and the effects of spin-orbit coupling are carefully considered. When spin-orbit coupling is explicitly considered, a barrier for C-H bond activation that is consistent with the threshold measured for ThCH2(+) formation (0.17 ± 0.02 eV) is found at all levels of theory, whereas this barrier is observed only at the BHLYP and CCSD(T) levels otherwise. The observation that the CID of the ThCH4(+) complex produces Th(+) as the only product with a threshold of 0.47 eV indicates that this species has a Th(+)(CH4) structure, which is also consistent with a barrier for C-H bond activation. This barrier is thought to exist as a result of the mixed ((4)F,(2)D) electronic character of the Th(+) J = (3)/2 ground level combined with extensive spin-orbit effects.

  9. 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.

  10. 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.

  11. 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.

  12. The trace ion module for the Monte Carlo code Eirene, a unified approach to plasma chemistry in the ITER divertor

    International Nuclear Information System (INIS)

    Seebacher, J.; Reiter, D.; Borner, P.

    2007-01-01

    Modelling of kinetic transport effects in magnetic fusion devices is of great importance for understanding the physical processes in both the core and and the scrape off layer (SOL) plasma. For SOL simulation the EIRENE code is a well established tool for modelling of neutral, impurities and radiation transport. Recently a new trace ion transport module (tim), has been developed and incorporated into EIRENE. The tim essentially consists of two parts: 1) A trajectory integrator tracing the deterministic motion of a guiding centre particle in general 3D electric and magnetic fields. 2) A stochastic representation of the Fokker Planck collision operator in suitable guiding centre coordinates treating Coulomb collisions with the plasma background species. The TIM enables integrated SOL simulation packages such as B2-EIRENE, EDGE2D-EIRENE (2D) or EMC3-EIRENE (3D) to treat the physical and chemical processes near the divertor targets and in the bulk of the SOL in greater detail than before, and in particular on a kinetic rather than a fluid level. One of the physics applications is the formation and transport of hydrocarbon molecules and ions in the divertor in tokamaks, where the tritium co deposition via hydrocarbons remains a serious issue for next generation fusion devices like ITER. Real tokamak modelling scenarios will be discussed with the code packages B2-EIRENE (2D) and EMC3-EIRENE (3D). A brief overview of the theoretical basis of the tim will be given including code verification studies of the basic physics properties. Applications to hydrocarbon transport studies in TEXTOR and ITER, comparing present (fluid) approximations in edge modelling with the new extended kinetic model, will be presented. (Author)

  13. 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...

  14. Mutagenesis of the redox-active disulfide in mercuric ion reductase: Catalysis by mutant enzymes restricted to flavin redox chemistry

    International Nuclear Information System (INIS)

    Distefano, M.D.; Au, K.G.; Walsh, C.T.

    1989-01-01

    Mercuric reductase, a flavoenzyme that possesses a redox-active cystine, Cys 135 Cys 140 , catalyzes the reduction of Hg(II) to Hg(0) by NADPH. As a probe of mechanism, the authors have constructed mutants lacking a redox-active disulfide by eliminating Cys 135 (Ala 135 Cys 140 ), Cys 14 (Cys 135 Ala 140 ), or both (Ala 135 Ala 140 ). Additionally, they have made double mutants that lack Cys 135 (Ala 135 Cys 139 Cys 140 ) or Cys 140 (Cys 135 Cys 139 Ala 140 ) but introduce a new Cys in place of Gly 139 with the aim of constructing dithiol pairs in the active site that do not form a redox-active disulfide. The resulting mutant enzymes all lack redox-active disulfides and are hence restricted to FAD/FADH 2 redox chemistry. Each mutant enzyme possesses unique physical and spectroscopic properties that reflect subtle differences in the FAD microenvironment. Preliminary evidence for the Ala 135 Cys 139 Cys 14 mutant enzyme suggests that this protein forms a disulfide between the two adjacent Cys residues. Hg(II) titration experiments that correlate the extent of charge-transfer quenching with Hg(II) binding indicate that the Ala 135 Cys 140 protein binds Hg(II) with substantially less avidity than does the wild-type enzyme. All mutant mercuric reductases catalyze transhydrogenation and oxygen reduction reactions through obligatory reduced flavin intermediates at rates comparable to or greater than that of the wild-type enzyme. In multiple-turnover assays which monitored the production of Hg(0), two of the mutant enzymes were observed to proceed through at least 30 turnovers at rates ca. 1000-fold slower than that of wild-type mercuric reductase. They conclude that the Cys 135 and Cys 140 thiols serve as Hg(II) ligands that orient the Hg(II) for subsequent reduction by a reduced flavin intermediate

  15. 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.

  16. 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.

  17. A Selected Ion Flow Tube, SIFT, Study of the Ion Chemistry of H3O+, NO+ and O2+ Ions with Several Nitroalkanes in the Presence of Water Vapour

    Czech Academy of Sciences Publication Activity Database

    Dryahina, Kseniya; Polášek, Miroslav; Španěl, Patrik

    2004-01-01

    Roč. 239, č. 1 (2004), s. 57-65 ISSN 1387-3806 R&D Projects: GA ČR GA203/02/0737; GA ČR GA202/03/0827 Institutional research plan: CEZ:AV0Z4040901 Keywords : SIFT * nitropropane * nitromethane Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.235, year: 2004

  18. 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…

  19. Interface chemistry engineering for stable cycling of reduced GO/SnO2 nanocomposites for lithium ion battery.

    Science.gov (United States)

    Wang, Lei; Wang, Dong; Dong, Zhihui; Zhang, Fengxing; Jin, Jian

    2013-04-10

    From the whole anode electrode of view, we report in this work a system-level strategy of fabrication of reduced graphene oxide (RGO)/SnO2 composite-based anode for lithium ion battery (LIB) to enhance the capacity and cyclic performance of SnO2-based electrode materials. RGO/SnO2 composite was first coated by a nanothick polydopamine (PD) layer and the PD-coated RGO/SnO2 composite was then cross-linked with poly(acrylic acid) (PAA) that was used as a binder to accomplish a whole anode electrode. The cross-link reaction between PAA and PD produced a robust network in the anode system to stabilize the whole anode during cycling. As a result, the designed anode exhibits an outstanding energy capacity up to 718 mAh/g at current density of 100 mA/g after 200 cycles and a good rate performance of 811, 700, 641, and 512 mAh/g at current density of 100, 250, 500, and 1000 mA/g, respectively. Fourier transform IR spectra confirm the formation of cross-link reaction and the stability of the robust network after long-term cycling. Our results indicate the importance of designing interfaces in anode system on achieving improved performance of electrode of LIBs.

  20. Studies on coordination chemistry and bioactivity of complexes of a tridentate ONS Schiff base with some heavier transition metal ions

    International Nuclear Information System (INIS)

    Tarafder, M.T.H.; Tan Mei Lin; Ali, A.M.

    2003-09-01

    A tridentate Schiff base, S-benzyl-β-N-(2-hydroxyphenyl)methylenedithiocarbazate, (HONSH), with a donor sequence of ONS, was synthesized from the condensation of S-benzyldithiocarbazate (SBDTC) with an equimolar amount of 2-hydroxybenzaldehyde in absolute ethanol. The reactions of HONSH with metal ions [La(III), Ce(IV) and Th(IV)] yielded complexes of compositions, [La(ONS)NO 3 .2H 2 O], [Ce(ONS)(NO 3 ) 2 ] and [Th(ONS) 2 ]. The ligands and the complexes were characterized from elemental analyses and spectroscopic measurements. The metal complexes were found to be active against colon cancer cell lines with the CD 50 values of 27.5, 28.4 and 19.3 μg/ml for the La(III), Ce(FV) and Th(IV) complexes, respectively. The La(IH) complex was found to be very active against leukemic cell lines with the CD 50 value of 6.8 μg/ml. (author)

  1. Ion collision-induced chemistry in pure and mixed loosely bound clusters of coronene and C60 molecules.

    Science.gov (United States)

    Domaracka, Alicja; Delaunay, Rudy; Mika, Arkadiusz; Gatchell, Michael; Zettergren, Henning; Cederquist, Henrik; Rousseau, Patrick; Huber, Bernd A

    2018-05-23

    Ionization, fragmentation and molecular growth have been studied in collisions of 22.5 keV He2+- or 3 keV Ar+-projectiles with pure loosely bound clusters of coronene (C24H12) molecules or with loosely bound mixed C60-C24H12 clusters by using mass spectrometry. The heavier and slower Ar+ projectiles induce prompt knockout-fragmentation - C- and/or H-losses - from individual molecules and highly efficient secondary molecular growth reactions before the clusters disintegrate on picosecond timescales. The lighter and faster He2+ projectiles have a higher charge and the main reactions are then ionization by ions that are not penetrating the clusters. This leads mostly to cluster fragmentation without molecular growth. However, here penetrating collisions may also lead to molecular growth but to a much smaller extent than with 3 keV Ar+. Here we present fragmentation and molecular growth mass distributions with 1 mass unit resolution, which reveals that the same numbers of C- and H-atoms often participate in the formation and breaking of covalent bonds inside the clusters. We find that masses close to those with integer numbers of intact coronene molecules, or with integer numbers of both intact coronene and C60 molecules, are formed where often one or several H-atoms are missing or have been added on. We also find that super-hydrogenated coronene is formed inside the clusters.

  2. Bad chemistry

    OpenAIRE

    Petsko, Gregory A

    2004-01-01

    General chemistry courses haven't changed significantly in forty years. Because most basic chemistry students are premedical students, medical schools have enormous influence and could help us start all over again to create undergraduate chemistry education that works.

  3. 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)

  4. 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

  5. Structure formation and surface chemistry of ionic liquids on model electrode surfaces—Model studies for the electrode | electrolyte interface in Li-ion batteries

    Science.gov (United States)

    Buchner, Florian; Uhl, Benedikt; Forster-Tonigold, Katrin; Bansmann, Joachim; Groß, Axel; Behm, R. Jürgen

    2018-05-01

    decomposition products was found to sensitively change the equilibrium between surface Li and Li+ intercalated in the bulk, leading to a deintercalation from lithiated HOPG in the presence of an adsorbed IL adlayer at >230 K. Overall, these results provide detailed insights into the surface chemistry at the solid | electrolyte interface and the initial stages of SEI formation at electrode surfaces in the absence of an applied potential, which is essential for the further improvement of future Li-ion batteries.

  6. 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.

  7. 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.

  8. 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.

  9. 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...

  10. 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 ...

  11. 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

  12. Characterization of major-ion chemistry and nutrients in headwater streams along the Appalachian National Scenic Trail and within adjacent watersheds, Maine to Georgia

    Science.gov (United States)

    Argue, Denise M.; Pope, Jason P.; Dieffenbach, Fred

    2012-01-01

    concentrations of major ions. The geology in discrete portions of these two ecosections was classified as containing carbonate minerals which has likely influenced the chemical character of the streamwater. Specific conductance, pH, ANC, and concentrations of major ions (calcium, chloride, magnesium, sodium, and sulfate) were all positively correlated with percentages of developed and agricultural land uses at the lower elevations of the central region of the Appalachian Trail (including the Green-Taconic-Berkshire Mountains, Lower New England, Hudson Valley, and Northern Ridge and Valley ecosections). The distinctly different chemical character of the streams in the central sections of the Appalachian Trail is likely related to the lower elevations, the presence of carbonate minerals in the geology, higher percentages of developed and agricultural land uses, and possibly the higher inputs of sulfate and nitrate from atmospheric deposition. Acid deposition of sulfate and nitrate are important influences on the acid-base chemistry of the surface waters of the Appalachian Trail. Atmospheric deposition estimates are consistently high (more than 18 kilograms per hectare (kg/ha) for sulfate, and more than 16 kg/ha for nitrate) at both the highest and lowest elevations. However, the lowest elevation (Green-Taconic-Berkshire Mountains, Lower New England, Hudson Valley, Northern Glaciated Allegheny Plateau, and Northern Ridge and Valley ecosections) included the largest spatial area of sustained high estimates of atmospheric deposition. Calcium-bicarbonate was the most frequently calculated water type in the Lower New England and Hudson Valley ecosections. In the northern and southern sections of the Appalachian Trail mix-cation water types were most prevalent and sulfate was the predominate anion. The predominance of the sulfate anion in the surface waters of the northern and southern ecosections likely reflects the influence of sulfate deposition. Although the central portion of the

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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)

  18. Chemistry Notes

    Science.gov (United States)

    School Science Review, 1976

    1976-01-01

    Described are eight chemistry experiments and demonstrations applicable to introductory chemistry courses. Activities include: measure of lattice enthalpy, Le Chatelier's principle, decarboxylation of soap, use of pocket calculators in pH measurement, and making nylon. (SL)

  19. Chemistry Dashboard

    Science.gov (United States)

    The Chemistry Dashboard is part of a suite of dashboards developed by EPA to help evaluate the safety of chemicals. The Chemistry Dashboard provides access to a variety of information on over 700,000 chemicals currently in use.

  20. 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.

  1. Water chemistry

    International Nuclear Information System (INIS)

    Hofstetter, K.J.; Baston, V.F.

    1986-01-01

    Prior to the accident, the coolants in the primary and secondary systems were within normal chemistry specifications for an operating pressurized water reactor with once-through steam generators. During and immediately after the accident, additional boric acid and sodium hydroxide were added to the primary coolant for control of criticality and radioiodine solubility. A primary to secondary leak developed contaminating the water in one steam generator. For about 5 years after the accident, the primary coolant was maintained at 3800 +. 100 ppm boron and 1000 +. 100 ppm sodium concentrations. Dissolved oxygen was maintained 7.5, corrosion caused by increased dissolved oxygen levels (up to 8 ppm) and higher chloride ion content (up to 5 ppm) is minimized. Chemical control of dissolved oxygen was discontinued and the coolant was processed. Prior to removal of the reactor vessel head, the boron concentration in the coolant was increased to ≅ 5000 ppm to support future defueling operations. Decontamination of the accident generated water is described in terms of contaminated water management. In addition, the decontamination and chemical lay-up conditions for the secondary system are presented along with an overview of chemical management at TMI-2

  2. Migration chemistry

    International Nuclear Information System (INIS)

    Carlsen, L.

    1992-05-01

    Migration chemistry, the influence of chemical -, biochemical - and physico-chemical reactions on the migration behaviour of pollutants in the environment, is an interplay between the actual natur of the pollutant and the characteristics of the environment, such as pH, redox conditions and organic matter content. The wide selection of possible pollutants in combination with varying geological media, as well as the operation of different chemical -, biochemical - and physico-chemical reactions compleactes the prediction of the influence of these processes on the mobility of pollutants. The report summarizes a wide range of potential pollutants in the terrestrial environment as well as a variety of chemical -, biochemical - and physico-chemical reactions, which can be expected to influence the migration behaviour, comprising diffusion, dispersion, convection, sorption/desorption, precipitation/dissolution, transformations/degradations, biochemical reactions and complex formation. The latter comprises the complexation of metal ions as well as non-polar organics to naturally occurring organic macromolecules. The influence of the single types of processes on the migration process is elucidated based on theoretical studies. The influence of chemical -, biochemical - and physico-chemical reactions on the migration behaviour is unambiguous, as the processes apparently control the transport of pollutants in the terrestrial environment. As the simple, conventional K D concept breaks down, it is suggested that the migration process should be described in terms of the alternative concepts chemical dispersion, average-elution-time and effective retention. (AB) (134 refs.)

  3. Combinatorial chemistry

    DEFF Research Database (Denmark)

    Nielsen, John

    1994-01-01

    An overview of combinatorial chemistry is presented. Combinatorial chemistry, sometimes referred to as `irrational drug design,' involves the generation of molecular diversity. The resulting chemical library is then screened for biologically active compounds.......An overview of combinatorial chemistry is presented. Combinatorial chemistry, sometimes referred to as `irrational drug design,' involves the generation of molecular diversity. The resulting chemical library is then screened for biologically active compounds....

  4. Aquatic Chemistry

    International Nuclear Information System (INIS)

    Kim, Dong Yeun; Kim, Oh Sik; Kim, Chang Guk; Park, Cheong Gil; Lee, Gwi Hyeon; Lee, Cheol Hui

    1987-07-01

    This book deals aquatic chemistry, which treats water and environment, chemical kinetics, chemical balance like dynamical characteristic, and thermodynamics, acid-base chemistry such as summary, definition, kinetics, and PH design for mixture of acid-base chemistry, complex chemistry with definition, and kinetics, precipitation and dissolution on summary, kinetics of precipitation and dissolution, and balance design oxidation and resolution with summary, balance of oxidation and resolution.

  5. Positronium chemistry

    CERN Document Server

    Green, James

    1964-01-01

    Positronium Chemistry focuses on the methodologies, reactions, processes, and transformations involved in positronium chemistry. The publication first offers information on positrons and positronium and experimental methods, including mesonic atoms, angular correlation measurements, annihilation spectra, and statistical errors in delayed coincidence measurements. The text then ponders on positrons in gases and solids. The manuscript takes a look at the theoretical chemistry of positronium and positronium chemistry in gases. Topics include quenching, annihilation spectrum, delayed coincidence

  6. 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.

  7. Rapid Screening of Carboxylic Acids from Waste and Surface Waters by ESI-MS/MS Using Barium Ion Chemistry and On-Line Membrane Sampling

    Science.gov (United States)

    Duncan, Kyle D.; Volmer, Dietrich A.; Gill, Chris G.; Krogh, Erik T.

    2016-03-01

    Negative ion tandem mass spectrometric analysis of aliphatic carboxylic acids often yields only non-diagnostic ([M - H]-) ions with limited selective fragmentation. However, carboxylates cationized with Ba2+ have demonstrated efficient dissociation in positive ion mode, providing structurally diagnostic product ions. We report the application of barium adducts followed by collision induced dissociation (CID), to improve selectivity for rapid screening of carboxylic acids in complex aqueous samples. The quantitative MS/MS method presented utilizes common product ions of [M - H + Ba]+ precursor ions. The mechanism of product ion formation is investigated using isotopically labeled standards and a series of structurally related carboxylic acids. The results suggest that hydrogen atoms in the β and γ positions yield common product ions ([BaH]+ and [BaOH]+). Furthermore, the diagnostic product ion at m/z 196 serves as a qualifying ion for carboxylate species. This methodology has been successfully used in conjunction with condensed phase membrane introduction mass spectrometry (CP-MIMS), with barium acetate added directly to the methanol acceptor phase. The combination enables rapid screening of carboxylic acids directly from acidified water samples (wastewater effluent, spiked natural waters) using a capillary hollow fiber PDMS membrane immersion probe. We have applied this technique for the direct analysis of complex naphthenic acid mixtures spiked into natural surface waters using CP-MIMS. Selectivity at the ionization and tandem mass spectrometry level eliminate isobaric interferences from hydroxylated species present within the samples, which have been observed in negative electrospray ionization.

  8. Rapid Screening of Carboxylic Acids from Waste and Surface Waters by ESI-MS/MS Using Barium Ion Chemistry and On-Line Membrane Sampling.

    Science.gov (United States)

    Duncan, Kyle D; Volmer, Dietrich A; Gill, Chris G; Krogh, Erik T

    2016-03-01

    Negative ion tandem mass spectrometric analysis of aliphatic carboxylic acids often yields only non-diagnostic ([M - H](-)) ions with limited selective fragmentation. However, carboxylates cationized with Ba(2+) have demonstrated efficient dissociation in positive ion mode, providing structurally diagnostic product ions. We report the application of barium adducts followed by collision induced dissociation (CID), to improve selectivity for rapid screening of carboxylic acids in complex aqueous samples. The quantitative MS/MS method presented utilizes common product ions of [M - H + Ba](+) precursor ions. The mechanism of product ion formation is investigated using isotopically labeled standards and a series of structurally related carboxylic acids. The results suggest that hydrogen atoms in the β and γ positions yield common product ions ([BaH](+) and [BaOH](+)). Furthermore, the diagnostic product ion at m/z 196 serves as a qualifying ion for carboxylate species. This methodology has been successfully used in conjunction with condensed phase membrane introduction mass spectrometry (CP-MIMS), with barium acetate added directly to the methanol acceptor phase. The combination enables rapid screening of carboxylic acids directly from acidified water samples (wastewater effluent, spiked natural waters) using a capillary hollow fiber PDMS membrane immersion probe. We have applied this technique for the direct analysis of complex naphthenic acid mixtures spiked into natural surface waters using CP-MIMS. Selectivity at the ionization and tandem mass spectrometry level eliminate isobaric interferences from hydroxylated species present within the samples, which have been observed in negative electrospray ionization.

  9. 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...

  10. Non-OH Chemistry in Oxidation Flow Reactors for the Study of Atmospheric Chemistry Systematically Examined by Modeling

    Science.gov (United States)

    Peng, Zhe; Day, Douglas A.; Ortega, Amber M.; Palm, Brett B.; Hu, Weiwei; Stark, Harald; Li, Rui; Tsigaridis, Kostas; Brune, William H.; Jimenez, Jose L.

    2016-01-01

    Oxidation flow reactors (OFRs) using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D), O(3P), and O3. In this study, we investigate the relative importance of other reactants to OH for the fate of reactant species in OFR under a wide range of conditions via box modeling. The relative importance of non-OH species is less sensitive to UV light intensity than to relative humidity (RH) and external OH reactivity (OHRext), as both non-OH reactants and OH scale roughly proportional to UV intensity. We show that for field studies in forested regions and also the urban area of Los Angeles, reactants of atmospheric interest are predominantly consumed by OH. We find that O(1D), O(3P), and O3 have relative contributions to VOC consumption that are similar or lower than in the troposphere. The impact of O atoms can be neglected under most conditions in both OFR and troposphere. Under pathological OFR conditions of low RH and/or high OHRext, the importance of non-OH reactants is enhanced because OH is suppressed. Some biogenics can have substantial destructions by O3, and photolysis at non-tropospheric wavelengths (185 and 254 nm) may also play a significant role in the degradation of some aromatics under pathological conditions. Working under low O2 with the OFR185 mode allows OH to completely dominate over O3 reactions even for the biogenic species most reactive with O3. Non-tropospheric VOC photolysis may have been a problem in some laboratory and source studies, but can be avoided or lessened in future studies by diluting source emissions and working at lower precursor concentrations in lab studies, and by

  11. 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.

  12. 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).

  13. Forensic Chemistry

    Science.gov (United States)

    Bell, Suzanne

    2009-07-01

    Forensic chemistry is unique among chemical sciences in that its research, practice, and presentation must meet the needs of both the scientific and the legal communities. As such, forensic chemistry research is applied and derivative by nature and design, and it emphasizes metrology (the science of measurement) and validation. Forensic chemistry has moved away from its analytical roots and is incorporating a broader spectrum of chemical sciences. Existing forensic practices are being revisited as the purview of forensic chemistry extends outward from drug analysis and toxicology into such diverse areas as combustion chemistry, materials science, and pattern evidence.

  14. 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.

  15. Ion chemistry at elevated ion–molecule interaction energies in a selected ion flow-drift tube: reactions of H3O+, NO+ and O2+ with saturated aliphatic ketones

    Czech Academy of Sciences Publication Activity Database

    Spesyvyi, Anatolii; Smith, D.; Španěl, Patrik

    2017-01-01

    Roč. 19, č. 47 (2017), s. 31714-31723 ISSN 1463-9076 R&D Projects: GA ČR(CZ) GJ17-13157Y EU Projects: European Commission(XE) 674911 - IMPACT Institutional support: RVO:61388955 Keywords : reactions of H3O+, NO+ and O2+ * SIFT-MS Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.123, year: 2016

  16. 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.

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

    Science.gov (United States)

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

    2011-04-01

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

  18. A continuous flow microfluidic calorimeter: 3-D numerical modeling with aqueous reactants

    Energy Technology Data Exchange (ETDEWEB)

    Sen, Mehmet A., E-mail: mehmet.sen@mathworks.com [Northeastern University, Department of Mechanical and Industrial Engineering, 360 Hungtington Avenue, 334 Snell Engineering Center, Boston, MA 02115 (United States); Kowalski, Gregory J., E-mail: gkowal@coe.neu.edu [Northeastern University, Department of Mechanical and Industrial Engineering, 360 Hungtington Avenue, 334 Snell Engineering Center, Boston, MA 02115 (United States); Fiering, Jason, E-mail: jfiering@draper.com [Charles Stark Draper Laboratory, 555 Technology Square, Cambridge, MA 02139 (United States); Larson, Dale, E-mail: dlarson@draper.com [Charles Stark Draper Laboratory, 555 Technology Square, Cambridge, MA 02139 (United States)

    2015-03-10

    Highlights: • A co-flow microreactor is modeled in flow, reaction/diffusion, and thermal domains. • Analysis shows how arrayed temperature sensors can provide enthalpy of reaction. • Optical plasmonic temperature sensors could be arrayed suitably for calorimetry. • The reactor studied has a volume of 25 nL. - Abstract: A computational analysis of the reacting flow field, species diffusion and heat transfer processes with thermal boundary layer effects in a microchannel reactor with a coflow configuration was performed. Two parallel adjacent streams of aqueous reactants flow along a wide, shallow, enclosed channel in contact with a substrate, which is affixed to a temperature controlled plate. The Fluent computational fluid dynamics package solved the Navier–Stokes, mass transport and energy equations. The energy model, including the enthalpy of reaction as a nonuniform heat source, was validated by calculating the energy balance at several control volumes in the microchannel. Analysis reveals that the temperature is nearly uniform across the channel thickness, in the direction normal to the substrate surface; hence, measurements made by sensors at or near the surface are representative of the average temperature. Additionally, modeling the channel with a glass substrate and a silicone cover shows that heat transfer is predominantly due to the glass substrate. Finally, using the numerical results, we suggest that a microcalorimeter could be based on this configuration, and that temperature sensors such as optical nanohole array sensors could have sufficient spatial resolution to determine enthalpy of reaction.

  19. 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.

  20. THE INFLUENCE OF BENZENE AS A TRACE REACTANT IN TITAN AEROSOL ANALOGS

    Energy Technology Data Exchange (ETDEWEB)

    Trainer, Melissa G. [Planetary Environments Laboratory, Code 699, NASA Goddard Space Flight Center, Greenbelt, MD 20771 (United States); Sebree, Joshua A. [NASA Postdoctoral Program Fellow, Code 699, Goddard Space Flight Center, Greenbelt, MD 20771 (United States); Heidi Yoon, Y.; Tolbert, Margaret A., E-mail: melissa.trainer@nasa.gov [Cooperative Institute for Research in Environmental Sciences, University of Colorado at Boulder, Box 216 UCB, Boulder, CO 80309 (United States)

    2013-03-20

    Benzene has been detected in Titan's atmosphere by Cassini instruments, with concentrations ranging from sub-ppb in the stratosphere to ppm in the ionosphere. Sustained levels of benzene in the haze formation region could signify that it is an important reactant in the formation of Titan's organic aerosol. To date, there have not been laboratory investigations to assess the influence of benzene on aerosol properties. We report a laboratory study on the chemical composition of organic aerosol formed from C{sub 6}H{sub 6}/CH{sub 4}/N{sub 2} via far ultraviolet irradiation (120-200 nm). The compositional results are compared to those from aerosol generated by a more ''traditional Titan'' mixture of CH{sub 4}/N{sub 2}. Our results show that even a trace amount of C{sub 6}H{sub 6} (10 ppm) has significant impact on the chemical composition and production rates of organic aerosol. There are several pathways by which photolyzed benzene may react to form larger molecules, both with and without the presence of CH{sub 4}, but many of these reaction mechanisms are only beginning to be explored for the conditions at Titan. Continued work investigating the influence of benzene in aerosol growth will advance understanding of this previously unstudied reaction system.

  1. Modification of the liquid cooling channel of PEMFCs for their operation with dry reactant gases

    International Nuclear Information System (INIS)

    Shyu, Jin-Cherng; Hsueh, Kan-Lin; Tsau, Fanghei; Chen, Fa-Lin

    2011-01-01

    In order to tackle both water and thermal problems, a modified PEMFC is proposed in the present study for its operation with dry reactant gases via the modification of liquid cooling channel with circulating liquid electrolyte. Fuel cell with both circulating liquid electrolyte and solid polymer membrane operated with either dry or humidified H 2 /O 2 is compared in the present study at temperatures of 40, 50, 65, and 80 o C, respectively. The measured E-I data show that such single cell can be operated at 80 o C without humidification. Besides, a semi-empirical equation to predict the current/voltage relationship, and the electrochemical impedance method are also employed in the present study for cell resistance analysis. The analysis results show that the high interfacial resistance should be one of the major reasons for the inferior performance of the present cell. Based on the discovery, an improvement of the present fuel cell is further proposed by Nafion ionomer spreading on the electrode before the assembly of membrane and electrode. The maximum power density of the cell after electrode treatment reaches 75 mW/cm 2 for dry H 2 /O 2 operation at 0.4 V, which is almost threefold improvement compared with that without electrode treatment.

  2. A continuous flow microfluidic calorimeter: 3-D numerical modeling with aqueous reactants

    International Nuclear Information System (INIS)

    Sen, Mehmet A.; Kowalski, Gregory J.; Fiering, Jason; Larson, Dale

    2015-01-01

    Highlights: • A co-flow microreactor is modeled in flow, reaction/diffusion, and thermal domains. • Analysis shows how arrayed temperature sensors can provide enthalpy of reaction. • Optical plasmonic temperature sensors could be arrayed suitably for calorimetry. • The reactor studied has a volume of 25 nL. - Abstract: A computational analysis of the reacting flow field, species diffusion and heat transfer processes with thermal boundary layer effects in a microchannel reactor with a coflow configuration was performed. Two parallel adjacent streams of aqueous reactants flow along a wide, shallow, enclosed channel in contact with a substrate, which is affixed to a temperature controlled plate. The Fluent computational fluid dynamics package solved the Navier–Stokes, mass transport and energy equations. The energy model, including the enthalpy of reaction as a nonuniform heat source, was validated by calculating the energy balance at several control volumes in the microchannel. Analysis reveals that the temperature is nearly uniform across the channel thickness, in the direction normal to the substrate surface; hence, measurements made by sensors at or near the surface are representative of the average temperature. Additionally, modeling the channel with a glass substrate and a silicone cover shows that heat transfer is predominantly due to the glass substrate. Finally, using the numerical results, we suggest that a microcalorimeter could be based on this configuration, and that temperature sensors such as optical nanohole array sensors could have sufficient spatial resolution to determine enthalpy of reaction

  3. Glycerol transesterification with ethyl acetate to synthesize acetins using ethyl acetate as reactant and entrainer

    Directory of Open Access Journals (Sweden)

    Amin Shafiei

    2017-03-01

    Full Text Available Transesterification of glycerol with ethyl acetate was performed over acidic catalysts in the batch and semi-batch systems. Ethyl acetate was used as reactant and entrainer to remove the produced ethanol during the reaction, through azeotrope formation. Since the azeotrope of ethyl acetate and ethanol forms at 70 oC, all the experiments were performed at this temperature. Para-toluene sulfonic acid, sulfuric acid, and Amberlyst 36 were used as catalyst. The effect of process parameters including ethyl acetate to glycerol molar ratio (6-12, reaction time (3-9 h, and the catalyst to glycerol weight (2.5-9.0%, on the conversion and products selectivities were investigated. Under reflux conditions, 100% glycerol conversion was obtained with 45%, 44%, and 11% selectivity to monoacetin, diacetin, and triacetin, respectively. Azeotropic reactive distillation led to 100% conversion of glycerol with selectivities of 3%, 48% and 49% for monoacetin, diacetin, and triacetin. During the azeotropic reactive distillation, it was possible to remove ethanol to shift the equilibrium towards diacetin and triacetin. Therefore, the total selectivity to diacetin and triacetin was increased from 55% to 97% through azeotropic distillation.

  4. Use of Gas Transported Reactants for Uranium Remediation in Vadose Zone Sediments

    International Nuclear Information System (INIS)

    Szecsody, James E.; Zhong, Lirong; Truex, Michael J.; Resch, Charles T.; Williams, Mark D.

    2010-01-01

    This laboratory-scale investigation is focused on decreasing mobility of uranium in subsurface contaminated sediments in the vadose zone by in situ geochemical manipulation at low water content. This geochemical manipulation of the sediment surface phases included reduction, pH change (acidic and alkaline), and additions of chemicals (phosphate, ferric iron) to form specific precipitates. Reactants were advected into 1-D columns packed with Hanford 200 area U-contaminated sediment as a reactive gas (for CO2, NH3, H2S, SO2), with a 0.1% water content mist (for NaOH, Fe(III), HCl, PO4) and with a 1% water content foam (for PO4). Because uranium is present in the sediment in multiple phases, changes in U surface phases were evaluated with a series of liquid extractions that dissolve progressively less soluble phases and electron microbe identification of mineral phases. In terms of the short-term decrease in U mobility (in decreasing order), NH3, NaOH mist, CO2, HCl mist, and Fe(III) mist showed 20% to 35% change in U surface phases. The two reductive gas treatments (H2S and SO2) showed little change. For long-term decrease in U transport, mineral phases created that had low solubility (phosphates, silicates) were desired, so NH3, phosphates (mist and foam delivered), and NaOH mist showed the greatest formation of these minerals.

  5. 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

  6. Charge distribution effects in polyatomic reactants involved in simple electron transfer reactions

    Czech Academy of Sciences Publication Activity Database

    Fawcett, W. R.; Chavis, G. J.; Hromadová, Magdaléna

    2008-01-01

    Roč. 53, č. 23 (2008), s. 6787-6792 ISSN 0013-4686 Institutional research plan: CEZ:AV0Z40400503 Keywords : electron transfer kinetics * charge distribution effects * double - layer effects in electrode kinetics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.078, year: 2008

  7. 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

  8. Organic chemistry

    International Nuclear Information System (INIS)

    2003-08-01

    This book with sixteen chapter explains organic chemistry on linkage isomerism such as alkane, cycloalkane, alkene, aromatic compounds, stereo selective isomerization, aromatic compounds, stereo selective isomerization, organic compounds, stereo selective isomerization, organic halogen compound, alcohol, ether, aldehyde and ketone, carboxylic acid, dicarboxylic acid, fat and detergent, amino, carbohydrate, amino acid and protein, nucleotide and nucleic acid and spectroscopy, a polymer and medical chemistry. Each chapter has introduction structure and characteristic and using of organic chemistry.

  9. Radiation chemistry

    Energy Technology Data Exchange (ETDEWEB)

    None

    1973-07-01

    Research progress is reported on radiation chemistry of heavy elements that includes the following topics: radiation chemistry of plutonium in nitric acid solutions (spectrophotometric analysis and gamma radiolysis of Pu(IV) and Pu(VI) in nitric acid solution); EPR studies of intermediates formed in radiolytic reactions with aqueous medium; two-phase radiolysis and its effect on the distribution coefficient of plutonium; and radiation chemistry of nitric acid. (DHM)

  10. Chemistry of cobalt bis(1,2-dicarbollide) ion; the synthesis of carbon substituted alkylamino derivatives from hydroxyalkyl derivatives via methylsulfonyl or p-toluenesulfonyl esters

    Czech Academy of Sciences Publication Activity Database

    Nekvinda, Jan; Švehla, Jaroslav; Císařová, I.; Grüner, Bohumír

    2015-01-01

    Roč. 798, č. 1 (2015), s. 112-120 ISSN 0022-328X R&D Projects: GA ČR GA15-05677S Institutional support: RVO:61388980 Keywords : Boranes * Carboranes * Metallacarboranes * Dicarbollide * Building blocks Subject RIV: CA - Inorganic Chemistry Impact factor: 2.336, year: 2015

  11. Technetium chemistry

    International Nuclear Information System (INIS)

    Burns, C.; Bryan, J.; Cotton, F.; Ott, K.; Kubas, G.; Haefner, S.; Barrera, J.; Hall, K.; Burrell, A.

    1996-01-01

    Technetium chemistry is a young and developing field. Despite the limited knowledge of its chemistry, technetium is the workhorse for nuclear medicine. Technetium is also a significant environmental concern because it is formed as a byproduct of nuclear weapons production and fission-power generators. Development of new technetium radio-pharmaceuticals and effective environmental control depends strongly upon knowledge of basic technetium chemistry. The authors performed research into the basic coordination and organometallic chemistry of technetium and used this knowledge to address nuclear medicine and environmental applications. This is the final report of a three-year Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL)

  12. Chemistry Technology

    Data.gov (United States)

    Federal Laboratory Consortium — Chemistry technology experts at NCATS engage in a variety of innovative translational research activities, including:Design of bioactive small molecules.Development...

  13. 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.

  14. Negative ions formed in N2/CH4/Ar discharge – a simulation of Titan's atmosphere chemistry

    OpenAIRE

    Horvath, G.; Aranda-Gonzalvo, Y.; Mason, N. J.; Zahoran, M.; Matejcik, S.

    2010-01-01

    The formation of negative ions produced in a negative point-to-plane corona discharge fed by a Ar/N2//CH4/ gas mixture has been studied using mass spectrometry. The measurements were carried out in flowing regime at ambient temperature and a reduced pressure of 460 mbar. The CN ? anion has been found to be the most dominant negative ion in the discharge and is believed to be the precursor of heavier negative ions such as C3/N ? and C5/N ? . The most likely pathway for the formation of such mo...

  15. 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

  16. 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.

  17. Effects of balneotherapy on the reactants of acute inflammation phase in Ankylosing spondylitis

    Directory of Open Access Journals (Sweden)

    Stamenković Bojana

    2009-01-01

    Full Text Available Introduction. Ankylosing spondylitis (AS is a chronic inflammatory disease that affects sacroiliac joints, spinal column and peripheral joints. Beside medication therapy, physical and balneotherapy play an important role in its complex treatment. Objective. The aim of the research was to establish serum concentrations of C-reactive protein (CRP, α 1-acid glycoprotein (α 1-AGP, ceruloplasmine (CP and erythrocyte sedimentation rate (SE before and after the balneotherapy in ankylosing spondylitis. Methods. The research included 50 AS patients according to the revised New York criteria, of mean age 43 years, who were treated for 14 days on the average at the Clinic for Rheumatology of the Institute 'Niška Banja'. All the patients received medications and balneotherapy (radioactive oligomineral baths, peloid, massage, kinesitherapy; the serum concentrations of CRP, α1-AGP, CP and SE were measured before and after balneotherapy. Serum proteins were determined using original Nor Partigen plates Boehringer. Erythrocyte sedimentation rate was measured by Westergreen method. Balneotherapy was applied individually, intensively or mildly, depending on the AS stage and activity phase. Results. After dosed balneotherapy, a significant decrease in the concentrations of CP (p<0.05, α1-AGP (p<0.01 and CRP (p<0.05 was registered in the serums of AS patients. ESR was not significantly reduced. Conclusion. The research proved that α 1-acid glycoprotein, ceruloplasmine and C-reactive protein represent more sensitive inflammation markers as compared to erythrocyte sedimentation rate. The identification of acute phase reactants is important in the evaluation of dosed balneotherapy efficiency in the treatment of ankylosing spondylitis.

  18. Cord Blood Acute Phase Reactants Predict Early Onset Neonatal Sepsis in Preterm Infants.

    Directory of Open Access Journals (Sweden)

    Leena B Mithal

    Full Text Available Early onset sepsis (EOS is a major cause of morbidity and mortality in preterm infants, yet diagnosis remains inadequate resulting in missed cases or prolonged empiric antibiotics with adverse consequences. Evaluation of acute phase reactant (APR biomarkers in umbilical cord blood at birth may improve EOS detection in preterm infants with intrauterine infection.In this nested case-control study, infants (29.7 weeks gestation, IQR: 27.7-32.2 were identified from a longitudinal cohort with archived cord blood and placental histopathology. Patients were categorized using culture, laboratory, clinical, and antibiotic treatment data into sepsis groups: confirmed sepsis (cEOS, n = 12; presumed sepsis (PS, n = 30; and no sepsis (controls, n = 30. Nine APRs were measured in duplicate from cord blood using commercially available multiplex immunoassays (Bio-Plex Pro™. In addition, placental histopathologic data were linked to biomarker results.cEOS organisms were Escherichia coli, Streptococcus agalactiae, Proteus mirabilis, Haemophilus influenzae and Listeria monocytogenes. C-reactive protein (CRP, serum amyloid A (SAA, haptoglobin (Hp, serum amyloid P and ferritin were significantly elevated in cEOS compared to controls (p<0.01. SAA, CRP, and Hp were elevated in cEOS but not in PS (p<0.01 and had AUCs of 99%, 96%, and 95% respectively in predicting cEOS. Regression analysis revealed robust associations of SAA, CRP, and Hp with EOS after adjustment for covariates. Procalcitonin, fibrinogen, α-2-macroglobulin and tissue plasminogen activator were not significantly different across groups. Placental acute inflammation was associated with APR elevation and was present in all cEOS, 9 PS, and 17 control infants.This study shows that certain APRs are elevated in cord blood of premature infants with EOS of intrauterine origin. SAA, CRP, and Hp at birth have potential diagnostic utility for risk stratification and identification of infants with EOS.

  19. Unravelling the secrets of Cs controlled secondary ion formation: Evidence of the dominance of site specific surface chemistry, alloying and ionic bonding

    Science.gov (United States)

    Wittmaack, Klaus

    2013-03-01

    Exposure of ion bombarded solids to Cs gives rise to a very strong enhancement of the yields of negatively charged secondary ions and, concurrently, to a lowering of positive ion yields. The phenomena have been explored in a large number of experimental and theoretical studies but attempts to clarify the mechanism of ion formation were not as successful as assumed. This review examines the state of the art in Cs controlled secondary ion mass spectrometry (SIMS) in great detail, with due consideration of low-energy alkali-ion scattering. In very basic studies on alkali induced secondary ion yield changes, sub-monolayer quantities of Cs or Li were deposited on the sample surface, followed by low-fluence ion bombardment, to avoid significant damage. If SIMS is applied to characterise the composition of solid materials, the simplest approach to achieving sample erosion as well as high negative-ion yields is bombardment with primary ions of Cs. Two other methods of sample loading with Cs provide more flexibility, (i) exposure to a collimated beam of Cs vapour and concurrent bombardment with high-energy non-Cs ions and (ii) the mixed-beam approach involving quasi-simultaneous bombardment with Cs and Xe ions. Both concepts have the advantage that undesirable sample overload with Cs can be avoided. High Cs concentrations reduce the formation probability of target specific molecular ions and lower the yields of all types of positive secondary ions, including Cs+, M+, X+, MCs+ and XCs+ (M and X denoting matrix and impurity elements). Quantitative SIMS analysis using MCs+ and XCs+ ions appears feasible, provided the Cs coverage is kept below about 5%. The semi-classical model of resonant charge transfer, also known as the tunnelling model, has long been considered a solid framework for the interpretation of Cs and Li based SIMS data. The model predicts ionisation probabilities for cases in which, at shallow distances from the surface, the affinity (ionisation) level of the

  20. Current organic chemistry

    National Research Council Canada - National Science Library

    1997-01-01

    Provides in depth reviews on current progress in the fields of asymmetric synthesis, organometallic chemistry, bioorganic chemistry, heterocyclic chemistry, natural product chemistry, and analytical...

  1. Nuclear chemistry

    International Nuclear Information System (INIS)

    Vertes, A.; Kiss, I.

    1987-01-01

    This book is an introduction to the application of nuclear science in modern chemistry. The first group of chapters discuss the basic phenomena and concepts of nuclear physics with emphasis on their relation to chemical problems, including the main properties and the composition of atomic nuclei, nuclear reactions, radioactive decay and interactions of radiation with matter. These chapters provide the basis for understanding the following chapters which encompass the wide scope of nuclear chemistry. The methods of the investigation of chemical structure based on the interaction of nuclear radiation with matter including positronium chemistry and other exotic atoms is elaborated in particular detail. Separate chapters are devoted to the use of radioactive tracers, the chemical consequences of nuclear processes (i.e. hot atom chemistry), radiation chemistry, isotope effects and their applications, and the operation of nuclear reactors

  2. Nuclear chemistry

    International Nuclear Information System (INIS)

    Vertes, A.; Kiss, I.

    1987-01-01

    This book is an introduction to the application of nuclear science in modern chemistry. The first group of chapters discuss the basic phenomena and concepts of nuclear physics with emphasis on their relation to chemical problems, including the main properties and the composition of atomic nuclei, nuclear reactions, radioactive decay and interactions of radiation with matter. These chapters provide the basis for understanding the following chapters which encompass the wide scope of nuclear chemistry. The methods of the investigation of chemical structure based on the interaction of nuclear radiation with matter including positronium chemistry and other exotic atoms is elaborated in particular detail. Separate chapters are devoted to the use of radioactive tracers, the chemical consequences of nuclear processes (i.e. hot atom chemistry), radiation chemistry, isotope effects and their applications, and the operation of nuclear reactors. (Auth.)

  3. Enhanced Reactant-Contaminant Contact through the Use of Persulfate In Situ Chemical Oxidation (ISCO)

    Science.gov (United States)

    2011-02-01

    248  Figure 7.4.1.5. Concentration versus depth profile for diffusion of 1 M persulfate in kaolin at...Figure 7.4.1.6. Concentration versus depth profile for diffusion of 0.1 M persulfate in kaolin at 82 days...acid. The complex chemistry of persulfate may change the permeability of soils and subsurface solids by inducing dispersion and flocculation, or by

  4. 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

  5. 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.

  6. Analysis of the current–voltage curves and saturation currents in burner-stabilised premixed flames with detailed ion chemistry and transport models

    KAUST Repository

    Belhi, Memdouh

    2018-05-22

    Current-voltage, or i–V, curves are used in combustion to characterise the ionic structure of flames. The objective of this paper is to develop a detailed modelling framework for the quantitative prediction of the i–V curves in methane/air flames. Ion and electron transport coefficients were described using methods appropriate for charged species interactions. An ionic reaction mechanism involving cations, anions and free electrons was used, together with up-to-date rate coefficients and thermodynamic data. Because of the important role of neutral species in the ion production process, its prediction by the detailed AramcoMech 1.4 mechanism was optimised by using available experimental measurements. Model predictions were evaluated by comparing to i–V curves measured in atmospheric-pressure, premixed, burner-stabilised flames. A detailed evaluation of the reliability of ion kinetic and transport parameters adopted was performed. The model provides good quantitative agreement with experimental data for various conditions.

  7. 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)

  8. 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

  9. 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

  10. Quantum chemistry

    CERN Document Server

    Lowe, John P

    1993-01-01

    Praised for its appealing writing style and clear pedagogy, Lowe's Quantum Chemistry is now available in its Second Edition as a text for senior undergraduate- and graduate-level chemistry students. The book assumes little mathematical or physical sophistication and emphasizes an understanding of the techniques and results of quantum chemistry, thus enabling students to comprehend much of the current chemical literature in which quantum chemical methods or concepts are used as tools. The book begins with a six-chapter introduction of standard one-dimensional systems, the hydrogen atom,

  11. 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.

  12. 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.

  13. The surface chemistry of divalent metal carbonate minerals; a critical assessment of surface charge and potential data using the charge distribution multi-site ion complexation model

    NARCIS (Netherlands)

    Wolthers, M.; Charlet, L.; Van Cappellen, P.

    2008-01-01

    The Charge Distribution MUltiSite Ion Complexation or CD–MUSIC modeling approach is used to describe the chemical structure of carbonate mineralaqueous solution interfaces. The new model extends existing surface complexation models of carbonate minerals, by including atomic scale information on

  14. Numerical simulation of the insert chemistry of the hollow cathode from the deep space 1 ion engine 30,000 Hrs life test

    OpenAIRE

    Coletti, Michele; Grubisic, Angelo; Gabriel, Stephen

    2007-01-01

    A model for the insert chemistry developed by the authors and based on the knowledge of the BaO – CaO – Al2O3 ternary system the ELT discharge cathode insert from the Deep Space 1 life test has been simulated. The computed data show a good agreement with the experimental one; the agreement increase with the imposition of boundary conditions closer to the experimental evidence. Tungsten deposition effect have been introduced into the model using experimental data and further improving the agre...

  15. Materials Chemistry

    CERN Document Server

    Fahlman, Bradley D

    2011-01-01

    The 2nd edition of Materials Chemistry builds on the strengths that were recognized by a 2008 Textbook Excellence Award from the Text and Academic Authors Association (TAA). Materials Chemistry addresses inorganic-, organic-, and nano-based materials from a structure vs. property treatment, providing a suitable breadth and depth coverage of the rapidly evolving materials field. The 2nd edition continues to offer innovative coverage and practical perspective throughout. After briefly defining materials chemistry and its history, seven chapters discuss solid-state chemistry, metals, semiconducting materials, organic "soft" materials, nanomaterials, and materials characterization. All chapters have been thoroughly updated and expanded with, for example, new sections on ‘soft lithographic’ patterning, ‘click chemistry’ polymerization, nanotoxicity, graphene, as well as many biomaterials applications. The polymer and ‘soft’ materials chapter represents the largest expansion for the 2nd edition. Each ch...

  16. 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.)

  17. Analytical chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jae Seong

    1993-02-15

    This book is comprised of nineteen chapters, which describes introduction of analytical chemistry, experimental error and statistics, chemistry equilibrium and solubility, gravimetric analysis with mechanism of precipitation, range and calculation of the result, volume analysis on general principle, sedimentation method on types and titration curve, acid base balance, acid base titration curve, complex and firing reaction, introduction of chemical electro analysis, acid-base titration curve, electrode and potentiometry, electrolysis and conductometry, voltammetry and polarographic spectrophotometry, atomic spectrometry, solvent extraction, chromatograph and experiments.

  18. Analytical chemistry

    International Nuclear Information System (INIS)

    Choi, Jae Seong

    1993-02-01

    This book is comprised of nineteen chapters, which describes introduction of analytical chemistry, experimental error and statistics, chemistry equilibrium and solubility, gravimetric analysis with mechanism of precipitation, range and calculation of the result, volume analysis on general principle, sedimentation method on types and titration curve, acid base balance, acid base titration curve, complex and firing reaction, introduction of chemical electro analysis, acid-base titration curve, electrode and potentiometry, electrolysis and conductometry, voltammetry and polarographic spectrophotometry, atomic spectrometry, solvent extraction, chromatograph and experiments.

  19. Analytical chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Chae, Myeong Hu; Lee, Hu Jun; Kim, Ha Seok

    1989-02-15

    This book give explanations on analytical chemistry with ten chapters, which deal with development of analytical chemistry, the theory of error with definition and classification, sample and treatment gravimetry on general process of gravimetry in aqueous solution and non-aqueous solution, precipitation titration about precipitation reaction and types, complexometry with summary and complex compound, oxidation-reduction equilibrium on electrode potential and potentiometric titration, solvent extraction and chromatograph and experiment with basic operation for chemical experiment.

  20. Analytical chemistry

    International Nuclear Information System (INIS)

    Chae, Myeong Hu; Lee, Hu Jun; Kim, Ha Seok

    1989-02-01

    This book give explanations on analytical chemistry with ten chapters, which deal with development of analytical chemistry, the theory of error with definition and classification, sample and treatment gravimetry on general process of gravimetry in aqueous solution and non-aqueous solution, precipitation titration about precipitation reaction and types, complexometry with summary and complex compound, oxidation-reduction equilibrium on electrode potential and potentiometric titration, solvent extraction and chromatograph and experiment with basic operation for chemical experiment.

  1. Green Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Collison, Melanie

    2011-05-15

    Green chemistry is the science of chemistry used in a way that will not use or create hazardous substances. Dr. Rui Resendes is working in this field at GreenCentre Canada, an offshoot of PARTEQ Innovations in Kingston, Ontario. GreenCentre's preliminary findings suggest their licensed product {sup S}witchable Solutions{sup ,} featuring 3 classes of solvents and a surfactant, may be useful in bitumen oil sands extraction.

  2. 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.

  3. 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.)

  4. 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

  5. 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

  6. A general solution-chemistry route to the synthesis LiMPO4 (M=Mn, Fe, and Co) nanocrystals with [010] orientation for lithium ion batteries

    International Nuclear Information System (INIS)

    Su Jing; Wei Bingqing; Rong Jiepeng; Yin Wenyan; Ye Zhixia; Tian Xianqing; Ren Ling; Cao Minhua; Hu Changwen

    2011-01-01

    A general and efficient solvothermal strategy has been developed for the preparation of lithium transition metal phosphate microstructures (LiMnPO 4 , LiFePO 4 , and LiCoPO 4 ), employing ethanol as the solvent, LiI as the Li source, metal salts as the M sources, H 3 PO 4 as the phosphorus source, and poly(vinyl pyrrolidone) (PVP) as the carbon source and template. This route features low cost, environmental benign, and one-step process for the cathode material production of Li-ion batteries without any complicated experimental setups and sophisticated operations. The as-synthesized LiMPO 4 microstructures exhibit unique, well-shaped and favorable structures, which are self-assembled from microplates or microrods. The b axis is the preferred crystal growth orientation of the products, resulting in a shorter lithium ion diffusion path. The LiFePO 4 microstructures show an excellent cycling stability without capacity fading up to 50 cycles when they are used as a cathode material in lithium-ion batteries. - Graphical abstract: A general and efficient solvothermal strategy has been developed for the preparation of lithium transition metal phosphate microstructures under solvothermal conditions in the presence of PVP. Highlights: → A general and efficient solvothermal strategy has been developed for the preparation of LiMPO 4 microstructures. → This route features low cost, environmental benign, and one-step process. → The LiMPO 4 microstructures exhibit unique, well-shaped, and favorable structures. → The LiFePO 4 microstructures show an excellent cycling stability up to 50 cycles as a cathode material of lithium-ion batteries.

  7. Exploring the atmospheric chemistry of O2SO3- and assessing the maximum turnover number of ion-catalysed H2SO4 formation

    DEFF Research Database (Denmark)

    Bork, Nicolai Christian; Kurtén, T.; Vehkamäki, H.

    2013-01-01

    molecule, but reaction (b) is in general much more probable. Although we are unable to assess the overall importance of this cycle in the real atmosphere due to the unknown influence of CO2 and NOx, we roughly estimate that ion-induced catalysis may contribute with several percent of H2SO4 levels......It has recently been demonstrated that the O2SO3- ion forms in the atmosphere as a natural consequence of ionizing radiation. Here, we present a density functional theory-based study of the reactions of O2SO3- with O-3. The most important reactions are (a) oxidation to O3SO3- and (b) cluster...... the two major sinks for O2SO3- is assessed, thereby providing a measure of the maximum turnover number of ion-catalysed SO2 oxidation, i.e. how many SO2 can be oxidized per free electron. The rate ratio between reactions (a) and (b) is significantly altered by the presence or absence of a single water...

  8. 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

  9. 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"…

  10. 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)

  11. 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)…

  12. 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.

  13. 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.

  14. Exploring the atmospheric chemistry of O2SO3− and assessing the maximum turnover number of ion-catalysed H2SO4 formation

    Directory of Open Access Journals (Sweden)

    N. Bork

    2013-04-01

    Full Text Available It has recently been demonstrated that the O2SO3− ion forms in the atmosphere as a natural consequence of ionizing radiation. Here, we present a density functional theory-based study of the reactions of O2SO3− with O3. The most important reactions are (a oxidation to O2SO3− and (b cluster decomposition into SO3, O2 and O3−. The former reaction is highly exothermic, and the nascent O2SO3− will rapidly decompose into SO4− and O2. If the origin of O2SO3− is SO2 oxidation by O3−, the latter reaction closes a catalytic cycle wherein SO2 is oxidized to SO3. The relative rate between the two major sinks for O2SO3− is assessed, thereby providing a measure of the maximum turnover number of ion-catalysed SO2 oxidation, i.e. how many SO2 can be oxidized per free electron. The rate ratio between reactions (a and (b is significantly altered by the presence or absence of a single water molecule, but reaction (b is in general much more probable. Although we are unable to assess the overall importance of this cycle in the real atmosphere due to the unknown influence of CO2 and NOx, we roughly estimate that ion-induced catalysis may contribute with several percent of H2SO4 levels in typical CO2-free and low NOx reaction chambers, e.g. the CLOUD chamber at CERN.

  15. 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

  16. 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…

  17. 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)

  18. Indoor Chemistry

    DEFF Research Database (Denmark)

    Weschler, Charles J.; Carslaw, Nicola

    2018-01-01

    This review aims to encapsulate the importance, ubiquity, and complexity of indoor chemistry. We discuss the many sources of indoor air pollutants and summarize their chemical reactions in the air and on surfaces. We also summarize some of the known impacts of human occupants, who act as sources...... and sinks of indoor chemicals, and whose activities (e.g., cooking, cleaning, smoking) can lead to extremely high pollutant concentrations. As we begin to use increasingly sensitive and selective instrumentation indoors, we are learning more about chemistry in this relatively understudied environment....

  19. 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.

  20. 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....

  1. Handbook of heterocyclic chemistry

    National Research Council Canada - National Science Library

    Katritzky, Alan R

    2010-01-01

    ... Heterocyclic Chemistry I (1984) Comprehensive Heterocyclic Chemistry II (1996) Comprehensive Heterocyclic Chemistry III (2008) Comprehensive Organic Functional Group Transformations I (1995) Compreh...

  2. Reinventing Chemistry

    OpenAIRE

    Whitesides, George McClelland

    2015-01-01

    Chemistry is in a period of change, from an era focused on molecules and reactions, to one in which manipulations of systems of molecules and reactions will be essential parts of controlling larger systems. This Essay traces paths from the past to possible futures.

  3. 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.

  4. 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.

  5. THE CHEMISTRY OF INTERSTELLAR OH{sup +}, H{sub 2}O{sup +}, AND H{sub 3}O{sup +}: INFERRING THE COSMIC-RAY IONIZATION RATES FROM OBSERVATIONS OF MOLECULAR IONS

    Energy Technology Data Exchange (ETDEWEB)

    Hollenbach, David [SETI Institute, Mountain View, CA 94043-5203 (United States); Kaufman, M. J. [Department of Physics and Astronomy, San Jose State University, San Jose, CA 95192-0106 (United States); Neufeld, D. [Department of Physics and Astronomy, The Johns Hopkins University, Baltimore, MD 21218 (United States); Wolfire, M. [Department of Astronomy, University of Maryland, College Park, MD 20742 (United States); Goicoechea, J. R. [Departamento de Astrofisica, Centro de Astrobiologia (CSIC-INTA), 28850 Madrid (Spain)

    2012-08-01

    We model the production of OH{sup +}, H{sub 2}O{sup +}, and H{sub 3}O{sup +} in interstellar clouds, using a steady-state photodissociation region code that treats the freezeout of gas species, grain surface chemistry, and desorption of ices from grains. The code includes polycyclic aromatic hydrocarbons (PAHs), which have important effects on the chemistry. All three ions generally have two peaks in abundance as a function of depth into the cloud, one at A{sub V} {approx}< 1 and one at A{sub V} {approx} 3-8, the exact values depending on the ratio of incident ultraviolet flux to gas density. For relatively low values of the incident far-ultraviolet flux on the cloud ({chi} {approx}< 1000; {chi} = 1 = local interstellar value), the columns of OH{sup +} and H{sub 2}O{sup +} scale roughly as the cosmic-ray primary ionization rate {zeta}{sub crp} divided by the hydrogen nucleus density n. The H{sub 3}O{sup +} column is dominated by the second peak, and we show that if PAHs are present, N(H{sub 3}O{sup +}) {approx}4 Multiplication-Sign 10{sup 13} cm{sup -2} independent of {zeta}{sub crp} or n. If there are no PAHs or very small grains at the second peak, N(H{sub 3}O{sup +}) can attain such columns only if low-ionization potential metals are heavily depleted. We also model diffuse and translucent clouds in the interstellar medium, and show how observations of N(OH{sup +})/N(H) and N(OH{sup +})/N(H{sub 2}O{sup +}) can be used to estimate {zeta}{sub crp}/n, {chi}/n and A{sub V} in them. We compare our models to Herschel observations of these two ions, and estimate {zeta}{sub crp} {approx}4-6 Multiplication-Sign 10{sup -16}(n/100 cm{sup -3}) s{sup -1} and {chi}/n = 0.03 cm{sup 3} for diffuse foreground clouds toward W49N.

  6. Methodological study of the diffusion of interacting cations through clays. Application: experimental tests and simulation of coupled chemistry-diffusion transport of alkaline ions through a synthetical bentonite

    International Nuclear Information System (INIS)

    Melkior, Th.

    2000-01-01

    The subject of this work deals with the project of underground disposal of radioactive wastes in deep geological formations. It concerns the study of the migration of radionuclides through clays. In these materials, the main transport mechanism is assumed to be diffusion under natural conditions. Therefore, some diffusion experiments are conducted. With interacting solutes which present a strong affinity for the material, the duration of these tests will be too long, for the range of concentrations of interest. An alternative is to determine on one hand the geochemical retention properties using batch tests and crushed rock samples and, on the other hand, to deduce the transport parameters from diffusion tests realised with a non-interacting tracer, tritiated water. These data are then used to simulate the migration of the reactive elements with a numerical code which can deal with coupled chemistry-diffusion equations. The validity of this approach is tested by comparing the numerical simulations with the results of diffusion experiments of cations through a clay. The subject is investigated in the case of the diffusion of cesium, lithium and sodium through a compacted sodium bentonite. The diffusion tests are realised with the through-diffusion method. The comparison between the experimental results and the simulations shows that the latter tends to under estimate the propagation of the considered species. The differences could be attributed to surface diffusion and to a decrease of the accessibility to the sites of fixation of the bentonite, from the conditions of clay suspensions in batch tests to the situation of compacted samples. The influence of the experimental apparatus used during the diffusion tests on the results of the measurement has also been tested. It showed that these apparatus have to be taken into consideration when the experimental data are interpreted. A specific model has been therefore developed with the numerical code CASTEM 2000. (author)

  7. 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

  8. 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

  9. Fine chemistry

    International Nuclear Information System (INIS)

    Laszlo, P.

    1988-01-01

    The 1988 progress report of the Fine Chemistry laboratory (Polytechnic School, France) is presented. The research programs are centered on the renewal of the organic chemistry most important reactions and on the invention of new, highly efficient and highly selective reactions, by applying low cost reagents and solvents. An important research domain concerns the study and fabrication of new catalysts. They are obtained by means of the reactive sputtering of the metals and metal oxydes thin films. The Monte Carlo simulations of the long-range electrostatic interaction in a clay and the obtention of acrylamides from anhydrous or acrylic ester are summarized. Moreover, the results obtained in the field of catalysis are also given. The published papers and the congress communications are included [fr

  10. 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.)

  11. 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.

  12. 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.)

  13. 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

  14. Radioanalytical chemistry

    International Nuclear Information System (INIS)

    1982-01-01

    The bibliography of Hungarian literature in the field of radioanalytical chemistry covers the four-year period 1976-1979. The list of papers contains 290 references in the alphabetical order of the first authors. The majority of the titles belongs to neutron activation analysis, labelling, separation and determination of radioactive isotopes. Other important fields like radioimmunoassay, environmental protection etc. are covered as well. (Sz.J.)

  15. Industrial chemistry engineering

    International Nuclear Information System (INIS)

    1993-01-01

    This book on industrial chemistry engineering is divided in two parts. The first part deals with industrial chemistry, inorganic industrial chemistry, organic industrial chemistry, analytical chemistry and practical questions. The last parts explain the chemical industry, a unit parts and thermodynamics in chemical industry and reference. It reveals the test subjects for the industrial chemistry engineering with a written examination and practical skill.

  16. Computational chemistry

    Science.gov (United States)

    Arnold, J. O.

    1987-01-01

    With the advent of supercomputers, modern computational chemistry algorithms and codes, a powerful tool was created to help fill NASA's continuing need for information on the properties of matter in hostile or unusual environments. Computational resources provided under the National Aerodynamics Simulator (NAS) program were a cornerstone for recent advancements in this field. Properties of gases, materials, and their interactions can be determined from solutions of the governing equations. In the case of gases, for example, radiative transition probabilites per particle, bond-dissociation energies, and rates of simple chemical reactions can be determined computationally as reliably as from experiment. The data are proving to be quite valuable in providing inputs to real-gas flow simulation codes used to compute aerothermodynamic loads on NASA's aeroassist orbital transfer vehicles and a host of problems related to the National Aerospace Plane Program. Although more approximate, similar solutions can be obtained for ensembles of atoms simulating small particles of materials with and without the presence of gases. Computational chemistry has application in studying catalysis, properties of polymers, all of interest to various NASA missions, including those previously mentioned. In addition to discussing these applications of computational chemistry within NASA, the governing equations and the need for supercomputers for their solution is outlined.

  17. Green chemistry

    International Nuclear Information System (INIS)

    Warner, John C.; Cannon, Amy S.; Dye, Kevin M.

    2004-01-01

    A grand challenge facing government, industry, and academia in the relationship of our technological society to the environment is reinventing the use of materials. To address this challenge, collaboration from an interdisciplinary group of stakeholders will be necessary. Traditionally, the approach to risk management of materials and chemicals has been through inerventions intended to reduce exposure to materials that are hazardous to health and the environment. In 1990, the Pollution Prevention Act encouraged a new tact-elimination of hazards at the source. An emerging approach to this grand challenge seeks to embed the diverse set of environmental perspectives and interests in the everyday practice of the people most responsible for using and creating new materials--chemists. The approach, which has come to be known as Green Chemistry, intends to eliminate intrinsic hazard itself, rather than focusing on reducing risk by minimizing exposure. This chapter addresses the representation of downstream environmental stakeholder interests in the upstream everyday practice that is reinventing chemistry and its material inputs, products, and waste as described in the '12 Principles of Green Chemistry'

  18. 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)

  19. Control of ion content and nitrogen species using a mixed chemistry plasma for GaN grown at extremely high growth rates >9 μm/h by plasma-assisted molecular beam epitaxy

    Science.gov (United States)

    Gunning, Brendan P.; Clinton, Evan A.; Merola, Joseph J.; Doolittle, W. Alan; Bresnahan, Rich C.

    2015-10-01

    Utilizing a modified nitrogen plasma source, plasma assisted molecular beam epitaxy (PAMBE) has been used to achieve higher growth rates in GaN. A higher conductance aperture plate, combined with higher nitrogen flow and added pumping capacity, resulted in dramatically increased growth rates up to 8.4 μm/h using 34 sccm of N2 while still maintaining acceptably low operating pressure. It was further discovered that argon could be added to the plasma gas to enhance growth rates up to 9.8 μm/h, which was achieved using 20 sccm of N2 and 7.7 sccm Ar flows at 600 W radio frequency power, for which the standard deviation of thickness was just 2% over a full 2 in. diameter wafer. A remote Langmuir style probe employing the flux gauge was used to indirectly measure the relative ion content in the plasma. The use of argon dilution at low plasma pressures resulted in a dramatic reduction of the plasma ion current by more than half, while high plasma pressures suppressed ion content regardless of plasma gas chemistry. Moreover, different trends are apparent for the molecular and atomic nitrogen species generated by varying pressure and nitrogen composition in the plasma. Argon dilution resulted in nearly an order of magnitude achievable growth rate range from 1 μm/h to nearly 10 μm/h. Even for films grown at more than 6 μm/h, the surface morphology remained smooth showing clear atomic steps with root mean square roughness less than 1 nm. Due to the low vapor pressure of Si, Ge was explored as an alternative n-type dopant for high growth rate applications. Electron concentrations from 2.2 × 1016 to 3.8 × 1019 cm-3 were achieved in GaN using Ge doping, and unintentionally doped GaN films exhibited low background electron concentrations of just 1-2 × 1015 cm-3. The highest growth rates resulted in macroscopic surface features due to Ga cell spitting, which is an engineering challenge still to be addressed. Nonetheless, the dramatically enhanced growth rates demonstrate

  20. Control of ion content and nitrogen species using a mixed chemistry plasma for GaN grown at extremely high growth rates >9 μm/h by plasma-assisted molecular beam epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Gunning, Brendan P.; Clinton, Evan A.; Merola, Joseph J.; Doolittle, W. Alan, E-mail: alan.doolittle@ece.gatech.edu [Georgia Institute of Technology, Atlanta, Georgia 30332 (United States); Bresnahan, Rich C. [Veeco Instruments, St. Paul, Minnesota 55127 (United States)

    2015-10-21

    Utilizing a modified nitrogen plasma source, plasma assisted molecular beam epitaxy (PAMBE) has been used to achieve higher growth rates in GaN. A higher conductance aperture plate, combined with higher nitrogen flow and added pumping capacity, resulted in dramatically increased growth rates up to 8.4 μm/h using 34 sccm of N{sub 2} while still maintaining acceptably low operating pressure. It was further discovered that argon could be added to the plasma gas to enhance growth rates up to 9.8 μm/h, which was achieved using 20 sccm of N{sub 2} and 7.7 sccm Ar flows at 600 W radio frequency power, for which the standard deviation of thickness was just 2% over a full 2 in. diameter wafer. A remote Langmuir style probe employing the flux gauge was used to indirectly measure the relative ion content in the plasma. The use of argon dilution at low plasma pressures resulted in a dramatic reduction of the plasma ion current by more than half, while high plasma pressures suppressed ion content regardless of plasma gas chemistry. Moreover, different trends are apparent for the molecular and atomic nitrogen species generated by varying pressure and nitrogen composition in the plasma. Argon dilution resulted in nearly an order of magnitude achievable growth rate range from 1 μm/h to nearly 10 μm/h. Even for films grown at more than 6 μm/h, the surface morphology remained smooth showing clear atomic steps with root mean square roughness less than 1 nm. Due to the low vapor pressure of Si, Ge was explored as an alternative n-type dopant for high growth rate applications. Electron concentrations from 2.2 × 10{sup 16} to 3.8 × 10{sup 19} cm{sup −3} were achieved in GaN using Ge doping, and unintentionally doped GaN films exhibited low background electron concentrations of just 1–2 × 10{sup 15} cm{sup −3}. The highest growth rates resulted in macroscopic surface features due to Ga cell spitting, which is an engineering challenge still to be

  1. Control of ion content and nitrogen species using a mixed chemistry plasma for GaN grown at extremely high growth rates >9 μm/h by plasma-assisted molecular beam epitaxy

    International Nuclear Information System (INIS)

    Gunning, Brendan P.; Clinton, Evan A.; Merola, Joseph J.; Doolittle, W. Alan; Bresnahan, Rich C.

    2015-01-01

    Utilizing a modified nitrogen plasma source, plasma assisted molecular beam epitaxy (PAMBE) has been used to achieve higher growth rates in GaN. A higher conductance aperture plate, combined with higher nitrogen flow and added pumping capacity, resulted in dramatically increased growth rates up to 8.4 μm/h using 34 sccm of N 2 while still maintaining acceptably low operating pressure. It was further discovered that argon could be added to the plasma gas to enhance growth rates up to 9.8 μm/h, which was achieved using 20 sccm of N 2 and 7.7 sccm Ar flows at 600 W radio frequency power, for which the standard deviation of thickness was just 2% over a full 2 in. diameter wafer. A remote Langmuir style probe employing the flux gauge was used to indirectly measure the relative ion content in the plasma. The use of argon dilution at low plasma pressures resulted in a dramatic reduction of the plasma ion current by more than half, while high plasma pressures suppressed ion content regardless of plasma gas chemistry. Moreover, different trends are apparent for the molecular and atomic nitrogen species generated by varying pressure and nitrogen composition in the plasma. Argon dilution resulted in nearly an order of magnitude achievable growth rate range from 1 μm/h to nearly 10 μm/h. Even for films grown at more than 6 μm/h, the surface morphology remained smooth showing clear atomic steps with root mean square roughness less than 1 nm. Due to the low vapor pressure of Si, Ge was explored as an alternative n-type dopant for high growth rate applications. Electron concentrations from 2.2 × 10 16 to 3.8 × 10 19 cm −3 were achieved in GaN using Ge doping, and unintentionally doped GaN films exhibited low background electron concentrations of just 1–2 × 10 15 cm −3 . The highest growth rates resulted in macroscopic surface features due to Ga cell spitting, which is an engineering challenge still to be addressed. Nonetheless, the

  2. 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)

  3. The reactants equation of state for the tri-amino-tri-nitro-benzene (TATB) based explosive PBX 9502

    Science.gov (United States)

    Aslam, Tariq D.

    2017-07-01

    The response of high explosives (HEs), due to mechanical and/or thermal insults, is of great importance for both safety and performance. A major component of how an HE responds to these stimuli stems from its reactant equation of state (EOS). Here, the tri-amino-tri-nitro-benzene based explosive PBX 9502 is investigated by examining recent experiments. Furthermore, a complete thermal EOS is calibrated based on the functional form devised by Wescott, Stewart, and Davis [J. Appl. Phys. 98, 053514 (2005)]. It is found, by comparing to earlier calibrations, that a variety of thermodynamic data are needed to sufficiently constrain the EOS response over a wide range of thermodynamic state space. Included in the calibration presented here is the specific heat as a function of temperature, isobaric thermal expansion, and shock Hugoniot response. As validation of the resulting model, isothermal compression and isentropic compression are compared with recent experiments.

  4. 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.)

  5. 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

  6. 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

  7. Interstellar chemistry.

    Science.gov (United States)

    Klemperer, William

    2006-08-15

    In the past half century, radioastronomy has changed our perception and understanding of the universe. In this issue of PNAS, the molecular chemistry directly observed within the galaxy is discussed. For the most part, the description of the molecular transformations requires specific kinetic schemes rather than chemical thermodynamics. Ionization of the very abundant molecular hydrogen and atomic helium followed by their secondary reactions is discussed. The rich variety of organic species observed is a challenge for complete understanding. The role and nature of reactions involving grain surfaces as well as new spectroscopic observations of interstellar and circumstellar regions are topics presented in this special feature.

  8. 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

  9. 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)

  10. 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.

  11. 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.)

  12. 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.)

  13. 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.)

  14. 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.

  15. 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.)

  16. 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.)

  17. Radiation chemistry and bioradical chemistry

    International Nuclear Information System (INIS)

    Ferradini, C.

    1991-01-01

    Oxygen metabolism results, at the cellular level, in the formation of superoxyde radical O 2 - · and probably also of hydroxyl radical OH·. Other radical species can be produced from exogenous or endogenous molecules and nearly all of them have the possibility to react with oxygen giving peroxyradicals. Some of these transients play a role in various biological processes such as phagocytosis, inflammation or ischemy although the mechanisms invoked are poorly understood. Radiation chemistry is an invaluable tool for obtaining a quantitative view of these mechanisms. A description is given of this interaction [fr

  18. Fundamentals of nuclear chemistry

    International Nuclear Information System (INIS)

    Majer, K.

    1982-01-01

    The textbook is a Czech-to-German translation of the second revised edition and covers the subject under the headings: general nuclear chemistry, methods of nuclear chemistry, preparative nuclear chemistry, analytical nuclear chemistry, and applied chemistry. The book is especially directed to students

  19. 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.

  20. 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).

  1. A universal fluorogenic switch for Fe(ii) ion based on N-oxide chemistry permits the visualization of intracellular redox equilibrium shift towards labile iron in hypoxic tumor cells.

    Science.gov (United States)

    Hirayama, Tasuku; Tsuboi, Hitomi; Niwa, Masato; Miki, Ayaji; Kadota, Satoki; Ikeshita, Yukie; Okuda, Kensuke; Nagasawa, Hideko

    2017-07-01

    Iron (Fe) species play a number of biologically and pathologically important roles. In particular, iron is a key element in oxygen sensing in living tissue where its metabolism is intimately linked with oxygen metabolism. Regulation of redox balance of labile iron species to prevent the generation of iron-catalyzed reactive oxygen species (ROS) is critical to survival. However, studies on the redox homeostasis of iron species are challenging because of a lack of a redox-state-specific detection method for iron, in particular, labile Fe 2+ . In this study, a universal fluorogenic switching system is established, which is responsive to Fe 2+ ion based on a unique N-oxide chemistry in which dialkylarylamine N-oxide is selectively deoxygenized by Fe 2+ to generate various fluorescent probes of Fe 2+ -CoNox-1 (blue), FluNox-1 (green), and SiRhoNox-1 (red). All the probes exhibited fluorescence enhancement against Fe 2+ with high selectivity both in cuvette and in living cells. Among the probes, SiRhoNox-1 showed an excellent fluorescence response with respect to both reaction rate and off/on signal contrast. Imaging studies were performed showing the intracellular redox equilibrium shift towards labile iron in response to reduced oxygen tension in living cells and 3D tumor spheroids using SiRhoNox-1, and it was found that the hypoxia induction of labile Fe 2+ is independent of iron uptake, hypoxia-induced signaling, and hypoxia-activated enzymes. The present studies demonstrate the feasibility of developing sensitive and specific fluorescent probes for Fe 2+ with refined photophysical characteristics that enable their broad application in the study of iron in various physiological and pathological conditions.

  2. Changes in streamflow and summary of major-ion chemistry and loads in the North Fork Red River basin upstream from Lake Altus, northwestern Texas and western Oklahoma, 1945-1999

    Science.gov (United States)

    Smith, S. Jerrod; Wahl, Kenneth L.

    2003-01-01

    Upstream from Lake Altus, the North Fork Red River drains an area of 2,515 square miles. The quantity and quality of surface water are major concerns at Lake Altus, and water-resource managers and consumers need historical information to make informed decisions about future development. The Lugert-Altus Irrigation District relies on withdrawals from the lake to sustain nearly 46,000 acres of agricultural land. Kendall's tau tests of precipitation data indicated no statistically significant trend over the entire 100 years of available record. However, a significant increase in precipitation occurred in the last 51 years. Four streamflow-gaging stations with more than 10 years of record were maintained in the basin. These stations recorded no significant trends in annual streamflow volume. Two stations, however, had significant increasing trends in the base-flow index, and three had significant decreasing trends in annual peak flows. Major-ion chemistry in the North Fork Red River is closely related to the chemical composition of the underlying bedrock. Two main lithologies are represented in the basin upstream from Lake Altus. In the upper reaches, young and poorly consolidated sediments include a range of sizes from coarse gravel to silt and clay. Nearsurface horizons commonly are cemented as calcium carbonate caliche. Finer-grained gypsiferous sandstones and shales dominate the lower reaches of the basin. A distinct increase in dissolved solids, specifically sodium, chloride, calcium, and sulfate, occurs as the river flows over rocks that contain substantial quantities of gypsum, anhydrite, and dolomite. These natural salts are the major dissolved constituents in the North Fork Red River.

  3. Cyclodextrin chemistry

    International Nuclear Information System (INIS)

    Khan, M.Z.; Chuaqui, C.A.

    1990-05-01

    The chemistry of cyclodextrins was studied. This study included synthesising some cyclodextrin derivatives, preparing selected inclusion complexes with cyclodextrin and investigating the effects of gamma irradiation on cyclodextrins and certain linear oligosaccharides. This report presents a brief review of the structure and properties of cyclodextrins, the synthesis of cyclodextrin derivatives, their complexation and applications. This is followed by a description of the synthesis of some cyclodextrin derivatives and the preparation of inclusion complexes of cyclodextrin with some organic compounds. Finally, the effects of gamma irradiation on cyclodextrins, some of their derivatives and certain structurally related carbohydrates are discussed. The gamma irradiation studies were carried out for two reasons: to study the effects of gamma irradiation on cyclodextrins and their derivatives; and to investigate selectivity during the gamma irradiation of cyclodextrin derivatives

  4. Reburning chemistry

    International Nuclear Information System (INIS)

    Kilpin, P.; Hupa, M.; Glarborg, P.

    1992-01-01

    No reduction chemistry in natural gas (methane) reburning was studied using detailed kinetic modeling. A reaction set including 225 reversible elementary gas-phase reactions and 48 chemical species was applied to an ideal plug flow reactor, and the most important reactions leading to NO reduction were identified and quantified for a number of conditions relevant for natural gas reburning. In addition, the influence of different process parameters on the NO reduction was investigated in the reburn zone and burn-out zone, respectively. Further, comparison of the calculations to available laboratory-scale data on reburning is made. In this paper, the impact of various fluid dynamic, mixing, and chemical effects---not accounted for in the calculations---on the NO reduction and the optimum reburning conditions predicted is discussed

  5. Combustion chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Brown, N.J. [Lawrence Berkeley Laboratory, CA (United States)

    1993-12-01

    This research is concerned with the development and use of sensitivity analysis tools to probe the response of dependent variables to model input variables. Sensitivity analysis is important at all levels of combustion modeling. This group`s research continues to be focused on elucidating the interrelationship between features in the underlying potential energy surface (obtained from ab initio quantum chemistry calculations) and their responses in the quantum dynamics, e.g., reactive transition probabilities, cross sections, and thermal rate coefficients. The goals of this research are: (i) to provide feedback information to quantum chemists in their potential surface refinement efforts, and (ii) to gain a better understanding of how various regions in the potential influence the dynamics. These investigations are carried out with the methodology of quantum functional sensitivity analysis (QFSA).

  6. Nuclear chemistry progress report

    International Nuclear Information System (INIS)

    1984-09-01

    The activities of the nuclear chemistry group at Indiana University during the period September 1, 1983 to August 31, 1984, are summarized. The primary thrust of our research program has continued to be the investigation of damped collision mechanisms at near-barrier energies and of linear momentum and energy transfer in the low-to-intermediate energy regime. In addition, during the past year we have initiated studies of complex fragment emission from highly excited nuclei and have also completed measurements relevant to understanding the origin and propagation of galactic cosmic rays. Equipment development efforts have resulted in significantly improving the resolution and solid-angle acceptance of our detector systems. The experimental program has been carried out at several accelerators including the Indiana University Cyclotron Facility, the Lawrence Berkeley Laboratory SuperHILAC, the Holifield Heavy-Ion Research Facility and the National Superconducting Cyclotron Laboratory at Michigan State University. Publications and activities are listed

  7. 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.

  8. Atomic layer deposition of Ru thin film using N{sub 2}/H{sub 2} plasma as a reactant

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Tae Eun [Busan Center, Korea Basic Science Institute, 1275 Jisadong, Gangseogu, Busan, 618-230 (Korea, Republic of); Mun, Ki-Yeung; Choi, Sang-Kyung; Park, Ji-Yoon [School of Materials Science and Engineering Yeungnam University 214-1, Dae-dong, Gyeongsan-si, Gyeongsangbuk-do, 712-749 (Korea, Republic of); Kim, Soo-Hyun, E-mail: soohyun@ynu.ac.kr [School of Materials Science and Engineering Yeungnam University 214-1, Dae-dong, Gyeongsan-si, Gyeongsangbuk-do, 712-749 (Korea, Republic of); Cheon, Taehoon [Center for Core Research Facilities, Daegu Gyeongbuk Institute of Science and Technology, Sang-ri, Hyeonpung-myeon, Dalseong-gun, Daegu (Korea, Republic of); Kim, Woo Kyoung [School of Chemical Engineering, Yeungnam University, 214-1, Dae-dong, Gyeongsan-si, Gyeongsangbuk-do, 712-749 (Korea, Republic of); Lim, Byoung-Yong; Kim, Sunjung [School of Materials Science and Engineering, University of Ulsan, Mugeo-dong, Nam-go, Ulsan, 680-749 (Korea, Republic of)

    2012-07-31

    Ruthenium (Ru) thin films were grown by atomic layer deposition using IMBCHRu [({eta}6-1-Isopropyl-4-MethylBenzene)({eta}4-CycloHexa-1,3-diene)Ruthenium(0)] as a precursor and a nitrogen-hydrogen mixture (N{sub 2}/H{sub 2}) plasma as a reactant, at the substrate temperature of 270 Degree-Sign C. In the wide range of the ratios of N{sub 2} and total gas flow rates (fN{sub 2}/N{sub 2} + H{sub 2}) from 0.12 to 0.70, pure Ru films with negligible nitrogen incorporation of 0.5 at.% were obtained, with resistivities ranging from {approx} 20 to {approx} 30 {mu} Ohm-Sign cm. A growth rate of 0.057 nm/cycle and negligible incubation cycle for the growth on SiO{sub 2} was observed, indicating the fast nucleation of Ru. The Ru films formed polycrystalline and columnar grain structures with a hexagonal-close-packed phase. Its resistivity was dependent on the crystallinity, which could be controlled by varying the deposition parameters such as plasma power and pulsing time. Cu was electroplated on a 10-nm-thick Ru film. Interestingly, it was found that the nitrogen could be incorporated into Ru at a higher reactant gas ratio of 0.86. The N-incorporated Ru film ({approx} 20 at.% of N) formed a nanocrystalline and non-columnar grain structure with the resistivity of {approx} 340 {mu} Ohm-Sign cm. - Highlights: Black-Right-Pointing-Pointer Atomic layer deposition (ALD) of Ru and N-incorporated Ru film using N{sub 2}/H{sub 2} plasma. Black-Right-Pointing-Pointer The growth rate of 0.057 nm/cycle and negligible incubation cycle. Black-Right-Pointing-Pointer A low resistivity of Ru ({approx} 16.5 {mu} Ohm-Sign cm) at the deposition temperature of 270 Degree-Sign C. Black-Right-Pointing-Pointer Electroplating of Cu on a 10-nm-thick ALD-Ru film.

  9. Why Teach Environmental Chemistry?

    Science.gov (United States)

    Gardner, Marjorie H.

    1974-01-01

    Discusses the importance of teaching environmental chemistry in secondary school science classes, and outlines five examples of environmental chemistry problems that focus on major concepts of chemistry and have critical implications for human survival and well-being. (JR)

  10. 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

  11. General chemistry

    International Nuclear Information System (INIS)

    2009-01-01

    This book explains chemical equilibrium with nature and characteristic of chemical equilibrium, law of mass action and direction of chemical equilibrium, acid-base equilibrium with principle of acid and base and amino acid, solubility and precipitation equilibrium with equilibrium of solubility, complex ion and solubility, electrochemistry on oxidation-reduction reaction, battery and fuel cell, decay and electrolysis, chemical reaction speed and nuclear reaction with Michaelis-Menten mechanism safety of nuclear, transition elements and coordination compound with introduction, name, structure and ligand EDTA and solid structure with categorization of solid and unit cell.

  12. 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

  13. Two series of reactant's ratio-dependent lanthanide organic frameworks derived from nicotinic acid N-oxide and oxalate: synthesis, crystal structures and luminescence properties.

    Science.gov (United States)

    Yu, Yanyan; Zhang, Lijuan; Zhou, Yunshan; Zuhra, Zareen

    2015-03-14

    Two series of lanthanide(III)–organic frameworks with the molecular formula [Ln2(NNO)2(OX)2(H2O)4]n (Ln = Eu 1, Tb 2, Sm 3, Dy 4, Gd 5) and [Ln2(NNO)4(OX)(H2O)2]n (Ln = Eu 6, Tb 7, Sm 8, Dy 9, Gd 10) were synthesized successfully under the same hydrothermal conditions with nicotinic N-oxide (HNNO) and oxalic acid (H2OX) as the mixed ligands merely through varying the molar ratio of the reactants. The compounds were characterized by IR, elemental analysis, UV, TG-DTA and powder X-ray diffraction (XRD). X-ray single-crystal diffraction analyses of compounds 1 and 7 selected as representatives and powder XRD analysis of the compounds revealed that both the series of compounds feature three-dimensional (3-D) open frameworks, and crystallize in the triclinic P1 space group while with different unit cell parameters. In compound 1, pairs of Eu(3+) ions and pairs of NNO(−) ligands connect with each other alternately to form a 1-D infinite Eu-NNO double chain, the adjacent 1-D double-chains are then joined together through OX(2−) ligands leading to a 2D layer, the 2-D layers are further ‘pillared’ by OX(2−) ligands resulting in a 3-D framework. In compound 7, the 1-D Tb-NNO infinite chain and its 2-D layer are formed in an almost similar fashion to that in compound 1. The difference between the structures of the two compounds 1 and 7 is that the adjacent 2-D layers in compound 7 are further connected by NNO(−) ligands resulting in a 3-D framework. The photoluminescence properties and energy transfer mechanism of the compounds were studied systematically. The energy level of the lowest triplet states of the HNNO ligand (23148 cm(−1)) was determined based on the phosphorescence spectrum of compound 5 at 77 K. The (5)D0 (Eu(3+)) and (5)D4 (Tb(3+)) emission lifetimes are 0.46 ms, 0.83 ms, 0.69 ms and 0.89 ms and overall quantum yields are 1.03%, 3.29%, 2.58% and 3.78% for the compounds 1, 2, 6 and 7, respectively.

  14. Environmental chemistry. Seventh edition

    Energy Technology Data Exchange (ETDEWEB)

    Manahan, S.E. [Univ. of Missouri, Columbia, MO (United States)

    1999-11-01

    This book presents a basic understanding of environmental chemistry and its applications. In addition to providing updated materials in this field, the book emphasizes the major concepts essential to the practice of environmental chemistry. Topics of discussion include the following: toxicological chemistry; toxicological chemistry of chemical substances; chemical analysis of water and wastewater; chemical analysis of wastes and solids; air and gas analysis; chemical analysis of biological materials and xenobiotics; fundamentals of chemistry; and fundamentals of organic chemistry.

  15. USSR Report Chemistry

    National Research Council Canada - National Science Library

    1986-01-01

    Contents: Adsorption, Chemistry,Alkaloids, Analytical Chemistry, Catalysis,Chemical Industry,,Coal Gasification, Combustion, Electrochemistry,Explosives and Explosions, Fertilizers, Free Radicals, Inorganic...

  16. Nuclear chemistry

    International Nuclear Information System (INIS)

    Anon.

    1979-01-01

    Topics covered include: mass asymmetry and total kinetic energy release in the spontaneous fission of 262 105; calculation of spontaneous fission properties of very heavy nuclei - 98 less than or equal to Z less than or equal to 106 and 150 less than or equal to N less than or equal to 164; energy losses for 84 Kr ions in nickel, aluminium and titanium; differences in compound nuclei formed with 40 Ar and 84 Kr projectiles; measurement of the energy division vs. mass in highly damped reactions; ambiguities in the inference of precompound emission from excitation function analysis; selective laser one-atom detection of neutral prompt fission fragments; laser induced nuclear polarization - application to the study of spontaneous fission isomers; quadrupole and hexadecapole deformations in the actinide nuclei; high-spin states in 164 Yb; contrasting behavior of h/sub 9/2/ and i/sub 13/2/ bands in 185 Au; multiple band crossings in 164 Er; recoil-distance measurement of lifetimes of rotational states in 164 Dy, lifetimes of ground-band states in 192 Pt and 194 Pt and application of the rotation-alignment model; coulomb excitation of vibrational nuclei with heavy ions; surface structure of deformed nuclei; valency contribution to neutron capture in 32 S; neutron capture cross section of manganese; search for superheavy elements in natural samples by neutron multiplicity counting; and gamma-ray studies on the geochemistry of achondritic meteorites

  17. 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)

  18. Experimental advances and preliminary mathematical modeling of the Swiss-roll mixed-reactant direct borohydride fuel cell

    Science.gov (United States)

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

    2014-11-01

    The Swiss-roll single-cell mixed reactant (SR-MRFC) borohydride - oxygen fuel cell equipped with Pt/carbon cloth 3D anode and either MnO2 or Ag gas-diffusion cathodes is investigated by a combination of experimental studies and preliminary mathematical modeling of the polarization curve. We investigate the effects of four variables: cathode side metallic mesh fluid distributor, separator type (Nafion 112® vs. Viledon®), cathode catalyst (MnO2 vs. Ag), and the hydrophilic pore volume fraction of the gas-diffusion cathode. Using a two-phase feed of alkaline borohydride solution (1 M NaBH4 - 2 M NaOH) and O2 gas in an SR-MRFC equipped with Pt/C 3D anode, MnO2 gas diffusion cathode, Viledon® porous diaphragm, expanded mesh cathode-side fluid distributor, the maximum superficial power density is 2230 W m-2 at 323 K and 105 kPa(abs). The latter superficial power density is almost 3.5 times higher than our previously reported superficial power density for the same catalyst combinations. Furthermore, with a Pt anode and Ag cathode catalyst combination, a superficial power density of 2500 W m-2 is achieved with superior performance durability compared to the MnO2 cathode. The fuel cell results are substantiated by impedance spectroscopy analysis and preliminary mathematical model predictions based on mixed potential theory.

  19. Characterization of Cr-rich Cr-Sb multilayer films: Syntheses of a new metastable phase using modulated elemental reactants

    International Nuclear Information System (INIS)

    Regus, Matthias; Mankovsky, Sergiy; Polesya, Svitlana; Kuhn, Gerhard; Ditto, Jeffrey; Schürmann, Ulrich; Jacquot, Alexandre; Bartholomé, Kilian; Näther, Christian; Winkler, Markus; König, Jan D.; Böttner, Harald; Kienle, Lorenz; Johnson, David C.; Ebert, Hubert; Bensch, Wolfgang

    2015-01-01

    The new metastable compound Cr 1+x Sb with x up to 0.6 has been prepared via a thin film approach using modulated elemental reactants and investigated by in-situ X-ray reflectivity, X-ray diffraction, differential scanning calorimetry, energy dispersive X-ray analysis as well as transmission electron microscopy and atomic force microscopy. The new Cr-rich antimonide crystallizes in a structure related to the Ni 2 In-type structure, where the crystallographic position (1/3, 2/3, 3/4) is partially occupied by excess Cr. The elemental layers of the pristine material interdiffused significantly before Cr 1+x Sb crystallized. A change in the activation energy was observed for the diffusion process when crystal growth starts. First-principles electronic structure calculations provide insight into the structural stability, magnetic properties and resistivity of Cr 1+x Sb. - Graphical abstract: 1 amorphous multilayered film 2 interdiffused amorphous film 3 metastable crystalline phase 4 thermodynamic stable phase (and by-product). - Highlights: • Interdiffusion of amorphous Cr and Sb occurs before crystallization. • Crystallization of a new metastable phase Cr 1.6 Sb in Ni 2 In-type structure. • The new Cr-rich phase shows half-metallic behavior

  20. Independent Orbiter Assessment (IOA): Assessment of the electrical power generation/power reactant storage and distribution subsystem FMEA/CIL

    Science.gov (United States)

    Ames, B. E.

    1988-01-01

    The results of the Independent Orbiter Assessment (IOA) of the Failure Modes and Effects Analysis (FMEA) and Critical Items List (CIL) is presented. The IOA effort first completed an analysis of the Electrical Power Generation/Power Reactant Storage and Distribution (EPG/PRSD) subsystem hardware, generating draft failure modes and potential critical items. To preserve independence, this analysis was accomplished without reliance upon the results contained within the NASA FMEA/CIL documentation. The IOA results were then compared to the NASA FMEA/CIL baselines with proposed Post 51-L updates included. A resolution of each discrepancy from the comparison is provided through additional analysis as required. The results of that comparison are documented for the Orbiter EPG/PRSD hardware. The comparison produced agreement on all but 27 FMEAs and 9 CIL items. The discrepancy between the number of IOA findings and NASA FMEAs can be partially explained by the different approaches used by IOA and NASA to group failure modes together to form one FMEA. Also, several IOA items represented inner tank components and ground operations failure modes which were not in the NASA baseline.

  1. Entropy and chemical change. 1: Characterization of product (and reactant) energy distributions in reactive molecular collisions: Information and enthropy deficiency

    Science.gov (United States)

    Bernstein, R. B.; Levine, R. D.

    1972-01-01

    Optimal means of characterizing the distribution of product energy states resulting from reactive collisions of molecules with restricted distributions of initial states are considered, along with those for characterizing the particular reactant state distribution which yields a given set of product states at a specified total energy. It is suggested to represent the energy-dependence of global-type results in the form of square-faced bar plots, and of data for specific-type experiments as triangular-faced prismatic plots. The essential parameters defining the internal state distribution are isolated, and the information content of such a distribution is put on a quantitative basis. The relationship between the information content, the surprisal, and the entropy of the continuous distribution is established. The concept of an entropy deficiency, which characterizes the specificity of product state formation, is suggested as a useful measure of the deviance from statistical behavior. The degradation of information by experimental averaging is considered, leading to bounds on the entropy deficiency.

  2. In situ generation of steam and alkaline surfactant for enhanced oil recovery using an exothermic water reactant (EWR)

    Science.gov (United States)

    Robertson, Eric P

    2011-05-24

    A method for oil recovery whereby an exothermic water reactant (EWR) encapsulated in a water soluble coating is placed in water and pumped into one or more oil wells in contact with an oil bearing formation. After the water carries the EWR to the bottom of the injection well, the water soluble coating dissolves and the EWR reacts with the water to produce heat, an alkali solution, and hydrogen. The heat from the EWR reaction generates steam, which is forced into the oil bearing formation where it condenses and transfers heat to the oil, elevating its temperature and decreasing the viscosity of the oil. The aqueous alkali solution mixes with the oil in the oil bearing formation and forms a surfactant that reduces the interfacial tension between the oil and water. The hydrogen may be used to react with the oil at these elevated temperatures to form lighter molecules, thus upgrading to a certain extent the oil in situ. As a result, the oil can flow more efficiently and easily through the oil bearing formation towards and into one or more production wells.

  3. Solar fuel production in a novel polymeric electrolyte membrane photoelectrochemical (PEM-PEC) cell with a web of titania nanotube arrays as photoanode and gaseous reactants

    NARCIS (Netherlands)

    Stoll, T.; Zafeiropoulos, G.; Tsampas, M. N.

    2016-01-01

    A novel photoelectrochemical (PEC) cell design is proposed and investigated for H-2 production with gaseous reactants. The core of the cell is a membrane electrode assembly (MEA) that consists of a TiO2 nanotube arrays photoanode, a Pt/C cathode, a Pt/C reference electrode and a proton conducting

  4. 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...

  5. 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

  6. Dehalogenation of Polychlorinated Biphenyls (PCB) by Nucleofile Reactants at the Presence of Ionic Liquids and under Application of Microwaves

    Czech Academy of Sciences Publication Activity Database

    Kaštánek, P.; Kaštánek, František; Hájek, Milan; Sobek, Jiří; Šolcová, Olga

    2011-01-01

    Roč. 13, č. 1 (2011), s. 59-64 ISSN 1790-7632 R&D Projects: GA ČR GA104/09/0694 Institutional research plan: CEZ:AV0Z40720504 Keywords : nucleophilic substitution * ionic liqiud * microwaves Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.536, year: 2011

  7. 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

  8. 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

  9. 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

  10. Electron tunneling in chemistry

    International Nuclear Information System (INIS)

    Zamaraev, K.I.; Khajrutdinov, R.F.; Zhdanov, V.P.; Molin, Yu.N.

    1985-01-01

    Results of experimental and theoretical investigations are outlined systematically on electron tunnelling in chemical reactions. Mechanism of electron transport to great distances is shown to be characteristic to chemical compounds of a wide range. The function of tunnel reactions is discussed for various fields of chemistry, including radiation chemistry, electrochemistry, chemistry of solids, chemistry of surface and catalysis

  11. 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

  12. 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 ...

  13. 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 ...

  14. 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.

  15. 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

  16. 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)

  17. Modelling electric discharge chemistry

    International Nuclear Information System (INIS)

    McFarlane, J.; Wren, J.C.

    1991-07-01

    The chemistry occurring in a electric discharge was modelled to predict how it would be influenced by discharge conditions. The discharge was characterized by a calculated Boltzmann electron-energy distribution, from which rate constants for electron-molecule processes in air were determined. These rate constants were used in a chemical kinetics calculation that also included reactions between neutral molecules, ions, free radicals and electronically excited species. The model describes how the discharge chemistry was influenced by humidity, electric field, electron number density, and concentrations of key reagents identified in the study. The use of an electric discharge to destroy airborne contaminant molecules was appraised, the targeted contaminants being CF 2 Cl 2 , HCN, and SO 2 . The modelling results indicate that an electric discharge should be able to remove HCN and CF 2 Cl 2 effectively, especially if the discharge conditions have been optimized. Effective destruction is achieved with a moderate electric field (over 1 x 10 -15 V.cm 2 ), a substantial electron number density (over 1 x 10 12 cm -3 ), and the presence of H 2 0 in the process air. The residence time in the discharge was also shown to be important in contaminant destruction. An attempt was made to explain the results of the electric discharge abatement of SO 2 , a component of a simulated flue-gas mixture. Results from the model indicate that the discharge parameters that increase the concentration of hydroxyl radical also increase the rate of decomposition of SO 2 . An objective of the study was to explain the apparent enhancement of SO 2 destruction by the presence of a small amount of NO 2 . It was thought that a likely explanation would be the stabilization of HOSO 2 , an important intermediate in the oxidation of SO 2 by NO 2 . (49 figs., 14 tabs., 75 refs.)

  18. Green chemistry: A tool in Pharmaceutical Chemistry

    OpenAIRE

    Smita Talaviya; Falguni Majumdar

    2012-01-01

    Green chemistry expresses an area of research developing from scientific discoveries about pollution awareness and it utilizes a set of principles that reduces or eliminates the use or generation of hazardous substances in all steps of particular synthesis or process. Chemists and medicinal scientists can greatly reduce the risk to human health and the environment by following all the valuable principles of green chemistry. The most simple and direct way to apply green chemistry in pharmaceut...

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Characterization of Reactants Reaction Mechanisms and Reaction Products Leading to Extreme Acid Rain and Acid Aerosol Conditions in Southern California

    OpenAIRE

    Hoffmann, Michael R.; Morgan, J. J.; Jacob, D. J.; Munger, J. W.; Waldman, J. M.

    1983-01-01

    Analyses of fogwater collected by inertial impaction in the Los Angeles basin and the San Joaquin Valley indicated unusually high concentrations of major and minor ions. The dominant ions measured were NO_3^-, SO_4^(2-), NH_4^+ and H^+ Nitrate exceeded sulfate on an equivalent basis by a factor of 2.5 in the central and coastal regions of the Los Angeles basin, but was approximately equal in the eastern Los Angeles basin and the San Joaquin Valley. Maximum observed values for NH_4^+, NO_3^- a...

  5. 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

  6. 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

  7. 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

  8. The latest general chemistry

    International Nuclear Information System (INIS)

    Ryu, Geun Bae; Choi, Se Yeong; Kim, Chin Yeong; Yoon, Gil Jung; Lee, Eun Seok; Seo, Moon Gyu

    1995-02-01

    This book deals with the latest general chemistry, which is comprised of twenty-three chapters, the contents of this book are introduction, theory of atoms and molecule, chemical formula and a chemical reaction formula, structure of atoms, nature of atoms and the periodic table, structure of molecule and spectrum, gas, solution, solid, chemical combination, chemical reaction speed, chemical equilibrium, thermal chemistry, oxidation-reduction, electrochemistry, acid-base, complex, aquatic chemistry, air chemistry, nuclear chemistry, metal and nonmetal, organic chemistry and biochemistry. It has exercise in the end of each chapter.

  9. 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.

  10. 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.)

  11. 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.)

  12. 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.)

  13. Advanced Chemistry Laboratory

    Data.gov (United States)

    Federal Laboratory Consortium — Description/History: Chemistry laboratoryThe Advanced Chemistry Laboratory (ACL) is a unique facility designed for working with the most super toxic compounds known...

  14. Electrostatics in Chemistry

    Indian Academy of Sciences (India)

    fundamental concepts of electrostatics as applied to atoms and molecules. The electric ... chemistry, the chemistry of the covalent bond, deals with the structures ..... the position of an asteroid named Ceres ... World Scientific. Singapore, 1992.

  15. Mars aqueous chemistry experiment

    Science.gov (United States)

    Clark, Benton C.; Mason, Larry W.

    1994-06-01

    Mars Aqueous Chemistry Experiment (MACE) is designed to conduct a variety of measurements on regolith samples, encompassing mineral phase analyses, chemical interactions with H2O, and physical properties determinations. From these data, much can be learned or inferred regarding the past weathering environment, the contemporaneous soil micro-environments, and the general chemical and physical state of the Martian regolith. By analyzing both soil and duricrust samples, the nature of the latter may become more apparent. Sites may be characterized for comparative purposes and criteria could be set for selection of high priority materials on future sample return missions. The second year of the MACE project has shown significant progress in two major areas. MACE Instrument concept definition is a baseline design that has been generated for the complete MACE instrument, including definition of analysis modes, mass estimates and thermal model. The design includes multiple reagent reservoirs, 10 discrete analysis cells, sample manipulation capability, and thermal control. The MACE Measurement subsystems development progress is reported regarding measurement capabilities for aqueous ion sensing, evolved gas sensing, solution conductivity measurement, reagent addition (titration) capabilities, and optical sensing of suspended particles.

  16. Mars aqueous chemistry experiment

    Science.gov (United States)

    Clark, Benton C.; Mason, Larry W.

    1994-01-01

    Mars Aqueous Chemistry Experiment (MACE) is designed to conduct a variety of measurements on regolith samples, encompassing mineral phase analyses, chemical interactions with H2O, and physical properties determinations. From these data, much can be learned or inferred regarding the past weathering environment, the contemporaneous soil micro-environments, and the general chemical and physical state of the Martian regolith. By analyzing both soil and duricrust samples, the nature of the latter may become more apparent. Sites may be characterized for comparative purposes and criteria could be set for selection of high priority materials on future sample return missions. The second year of the MACE project has shown significant progress in two major areas. MACE Instrument concept definition is a baseline design that has been generated for the complete MACE instrument, including definition of analysis modes, mass estimates and thermal model. The design includes multiple reagent reservoirs, 10 discrete analysis cells, sample manipulation capability, and thermal control. The MACE Measurement subsystems development progress is reported regarding measurement capabilities for aqueous ion sensing, evolved gas sensing, solution conductivity measurement, reagent addition (titration) capabilities, and optical sensing of suspended particles.

  17. Computational chemistry research

    Science.gov (United States)

    Levin, Eugene

    1987-01-01

    Task 41 is composed of two parts: (1) analysis and design studies related to the Numerical Aerodynamic Simulation (NAS) Extended Operating Configuration (EOC) and (2) computational chemistry. During the first half of 1987, Dr. Levin served as a member of an advanced system planning team to establish the requirements, goals, and principal technical characteristics of the NAS EOC. A paper entitled 'Scaling of Data Communications for an Advanced Supercomputer Network' is included. The high temperature transport properties (such as viscosity, thermal conductivity, etc.) of the major constituents of air (oxygen and nitrogen) were correctly determined. The results of prior ab initio computer solutions of the Schroedinger equation were combined with the best available experimental data to obtain complete interaction potentials for both neutral and ion-atom collision partners. These potentials were then used in a computer program to evaluate the collision cross-sections from which the transport properties could be determined. A paper entitled 'High Temperature Transport Properties of Air' is included.

  18. Nuclear chemistry progress report

    International Nuclear Information System (INIS)

    1983-09-01

    The activities of the nuclear chemistry program at Indiana University during the period September 1, 1982 to August 31, 1983 are reviewed. As in the past, these investigations have focused on understanding the properties of nucleus-nucleus collisions at low-to-intermediate energies. During the past year new programs have been initiated at the National Superconducting Cyclotron Laboratory at Michigan State University and the Hollifield Heavy-Ion Research Facility at Oak Ridge. With the unique beams provided by these accelerators we have extended our previous studies of energy dissipation phenomena into new energy regimes. The MSU measurements, performed with E/A = 15 to 30 MeV 14 N beams, combined with recent results we have obtained at IUCF, have indicated the existence of a saturation in the average amount of linear momentum that can be transferred in nucleus-nucleus collisions. This saturation value is about 140 (MeV/C)/A and occurs at beam energies in the E/A approx. 30 to 50 MeV range for 3 He- to 20 Ne-projectiles. At HHIRF, studies of the 56 Fe + 56 Fe reaction at E/A = 14.6 MeV have provided additional evidence for structure in the energy spectra of projectile-like fragments formed in symmetric collisions. Studies of near-barrier 56 Fe-induced reactions have continued at the Lawrence Berkeley Laboratory SuperHILAC

  19. Preparative radiation chemistry

    International Nuclear Information System (INIS)

    Drawe, H.

    1978-01-01

    Preparative synthesis of compounds with the aid of radiation chemistry is increasingly used in laboratories as well as on a technical scale. A large number of new compounds has been produced with the methods of radiation chemistry. With the increasing number of available radiation sources, also the number of synthesis metods in radiation chemistry has increased. This paper can only briefly mention the many possible ways of synthesis in radiation chemistry. (orig./HK) [de

  20. USSR Report Chemistry

    National Research Council Canada - National Science Library

    1986-01-01

    THIS REPORT CONTAINS FOREIGN MEDIA INFORMATION FROM THE USSR CONCERNING Adsorption, Alkaloids, ANALYTICAL CHEMISTRY, CATALYSIS, ELECTROCHEMISTRY, Fertilizers, INORGANIC COMPOUNDS, ORGANOPHOSPHOROUS...

  1. Frontiers in Gold Chemistry

    OpenAIRE

    Ahmed A. Mohamed

    2015-01-01

    Basic chemistry of gold tells us that it can bond to sulfur, phosphorous, nitrogen, and oxygen donor ligands. The Frontiers in Gold Chemistry Special Issue covers gold complexes bonded to the different donors and their fascinating applications. This issue covers both basic chemistry studies of gold complexes and their contemporary applications in medicine, materials chemistry, and optical sensors. There is a strong belief that aurophilicity plays a major role in the unending applications of g...

  2. Organic chemistry experiment

    International Nuclear Information System (INIS)

    Mun, Seok Sik

    2005-02-01

    This book deals with organic chemistry experiments, it is divided five chapters, which have introduction, the way to write the experiment report and safety in the laboratory, basic experiment technic like recrystallization and extraction, a lot of organic chemistry experiments such as fischer esterification, ester hydrolysis, electrophilic aromatic substitution, aldol reaction, benzoin condensation, wittig reaction grignard reaction, epoxidation reaction and selective reduction. The last chapter introduces chemistry site on the internet and way to find out reference on chemistry.

  3. Analytical chemistry instrumentation

    International Nuclear Information System (INIS)

    Laing, W.R.

    1986-01-01

    In nine sections, 48 chapters cover 1) analytical chemistry and the environment 2) environmental radiochemistry 3) automated instrumentation 4) advances in analytical mass spectrometry 5) fourier transform spectroscopy 6) analytical chemistry of plutonium 7) nuclear analytical chemistry 8) chemometrics and 9) nuclear fuel technology

  4. Fundamentals of nuclear chemistry

    International Nuclear Information System (INIS)

    Majer, V.

    1982-01-01

    The author of the book has had 25 years of experience at the Nuclear Chemistry of Prague Technical University. In consequence, the book is intended as a basic textbook for students of this field. Its main objectives are an easily understandable presentation of the complex subject and in spite of the uncertainty which still characterizes the definition and subjects of nuclear chemistry - a systematic classification and logical structure. Contents: 1. Introduction (history and definition); 2. General nuclear chemistry (physical fundamentals, hot atom chemistry, interaction of nuclear radiation with matter, radioactive elements, isotope effects, isotope exchange, chemistry of radioactive trace elements); 3. Methods of nuclear chemistry of nuclear chemistry (radiochemical methods, activation, separation and enrichment chemistry); 4. Preparative nuclear chemistry (isotope production, labelled compounds); 5. Analytival nuclear chemistry; 6. Applied nuclear chemistry (isotope applications in general physical and analytical chemistry). The book is supplemented by an annex with tables, a name catalogue and a subject index which will facilitate access to important information. (RB) [de

  5. Scandium Terminal Imido Chemistry.

    Science.gov (United States)

    Lu, Erli; Chu, Jiaxiang; Chen, Yaofeng

    2018-02-20

    of two p-d π bonds between the scandium ion and the nitrogen atom of the imido ligand and showed that the dianionic [NR] 2- imido ligand acts as a 2σ,4π electron donor. Subsequent studies of the scandium terminal imides revealed highly versatile and intriguing reactivity of the Sc═N bond. This included cycloaddition toward various unsaturated bonds, C-H/Si-H/B-H bond activations and catalytic hydrosilylation, dehydrofluorination of fluoro-substituted benzenes/alkanes, CO 2 and H 2 activations, activation of elemental selenium, coordination with other transition metal halides, etc. Since our initial success in 2010, and with contributions from us and across the community, this young, vibrant research field has rapidly flourished into one of the most active frontiers of rare-earth metal chemistry. The prospect of extending Ln═N chemistry to other rare-earth metals and/or different metal oxidation states, as well as exploiting their stoichiometric and catalytic reactivities, continues to attract research effort. Herein we present an account of our investigations into scandium terminal imido chemistry as a timely summary, in the hope that our studies will be of interest to this readership.

  6. 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

  7. 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)

  8. American Association for Clinical Chemistry

    Science.gov (United States)

    ... Find the answer to your question IN CLINICAL CHEMISTRY Hs-cTnI as a Gatekeeper for Further Cardiac ... Online Harmonization.net Commission on Accreditation in Clinical Chemistry American Board of Clinical Chemistry Clinical Chemistry Trainee ...

  9. 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,.

  10. 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.

  11. Specific processes and scrambling in the dehydrogenation of ethane and the degenerate hydrogen exchange in the gas-phase ion chemistry of the Ni(C,H3,O)+/C2H6 couple

    Czech Academy of Sciences Publication Activity Database

    Schlangen, M.; Schwarz, H.; Schröder, Detlef

    2007-01-01

    Roč. 90, č. 5 (2007), s. 847-853 ISSN 0018-019X Institutional research plan: CEZ:AV0Z40550506 Keywords : alkoxides * C-H activation * gas-phase investigations * mass spectrometry * nicel Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.515, year: 2007

  12. The New Color of Chemistry: Green Chemistry

    Directory of Open Access Journals (Sweden)

    Zuhal GERÇEK

    2012-01-01

    Full Text Available Green chemistry which is the new application of chemistry rules provides solutions to problems that mankind is faced with climate changes, sustainable agriculture, energy, toxics, depletion of natural sources e.g. designing new chemicals and processes that production and utilization of hazardous matters. So, it is the indispensible tool for sustainable development. Current and future chemists should consider the human health and ecological issues in their professional life. In order to provide a solution for this requirement, green chemistry rules and under standings should be primarily taken in the university curriculum and at all educational levels.

  13. Surface chemistry essentials

    CERN Document Server

    Birdi, K S

    2013-01-01

    Surface chemistry plays an important role in everyday life, as the basis for many phenomena as well as technological applications. Common examples range from soap bubbles, foam, and raindrops to cosmetics, paint, adhesives, and pharmaceuticals. Additional areas that rely on surface chemistry include modern nanotechnology, medical diagnostics, and drug delivery. There is extensive literature on this subject, but most chemistry books only devote one or two chapters to it. Surface Chemistry Essentials fills a need for a reference that brings together the fundamental aspects of surface chemistry w

  14. Fundamentals of reactor chemistry

    International Nuclear Information System (INIS)

    Akatsu, Eiko

    1981-12-01

    In the Nuclear Engineering School of JAERI, many courses are presented for the people working in and around the nuclear reactors. The curricula of the courses contain also the subject material of chemistry. With reference to the foreign curricula, a plan of educational subject material of chemistry in the Nuclear Engineering School of JAERI was considered, and the fundamental part of reactor chemistry was reviewed in this report. Since the students of the Nuclear Engineering School are not chemists, the knowledge necessary in and around the nuclear reactors was emphasized in order to familiarize the students with the reactor chemistry. The teaching experience of the fundamentals of reactor chemistry is also given. (author)

  15. 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

  16. 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)

  17. 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.

  18. 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

  19. Ion-ion collisions

    International Nuclear Information System (INIS)

    Salzborn, Erhard; Melchert, Frank

    2000-01-01

    Collisions between ions belong to the elementary processes occurring in all types of plasmas. In this article we give a short overview about collisions involving one-electron systems. For collisions involving multiply-charged ions we limit the discussion to one specific quasi-one-electron system. (author)

  20. 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)

  1. 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.)

  2. 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.

  3. Annual report 1985 Chemistry Department

    International Nuclear Information System (INIS)

    Funck, J.; Larsen, E.; Nielsen, O.J.

    1986-03-01

    This report contains a brief survey of the main activities in the Chemistry Department. All particles and reports published and lectures given in 1985 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry, analytical- and organic chemistry, environmental chemistry, polymer chemistry, geochemistry and waste disposal, radical chemistry, positron annihilation, mineral processing, and general. (author)

  4. Annual report 1984 Chemistry Department

    International Nuclear Information System (INIS)

    Funck, J.; Larsen, E.; Nielsen, O.J.

    1985-03-01

    This report contains a brief survey of the main activities in the Chemistry Department. All articles and reports published and lectures given in 1984 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry, analytical- and organic chemistry , environmental chemistry, polymer chemistry, geochemistry and waste disposal, radical chemistry, positron annihilation, mineral processing, and general. (author)

  5. Fundamentals of nuclear chemistry

    International Nuclear Information System (INIS)

    Matel, L.; Dulanska, S.

    2013-01-01

    This text-book is an introductory text in nuclear chemistry and radiochemistry, aimed on university undergraduate students in chemistry and related disciplines (physics, nuclear engineering). It covers the key aspects of modern nuclear chemistry. The text begins with basic theories in contemporary physics. It relates nuclear phenomena to key divisions of chemistry such as atomic structure, spectroscopy, equilibria and kinetics. It also gives an introduction to sources of ionizing radiation, detection of ionizing radiation, nuclear power industry and accident on nuclear installations as well as basic knowledge's of radiobiology. This book is essential reading for those taking a first course in nuclear chemistry and is a useful companion to other volumes in physical and analytical chemistry. It will also be of use to those new to working in nuclear chemistry or radiochemistry.

  6. Nuclear chemistry in the traditional chemistry program

    International Nuclear Information System (INIS)

    Kleppinger, E.W.

    1993-01-01

    The traditional undergraduate program for chemistry majors, especially at institutions devoted solely to undergraduate education, has limited space for 'special topics' courses in areas such as nuclear and radiochemistry. A scheme is proposed whereby the basic topics covered in an introductury radiochemistry course are touched upon, and in some cases covered in detail, at some time during the four-year sequence of courses taken by a chemistry major. (author) 6 refs.; 7 tabs

  7. The New Color of Chemistry: Green Chemistry

    OpenAIRE

    Zuhal GERÇEK

    2012-01-01

    Green chemistry which is the new application of chemistry rules provides solutions to problems that mankind is faced with climate changes, sustainable agriculture, energy, toxics, depletion of natural sources e.g. designing new chemicals and processes that production and utilization of hazardous matters. So, it is the indispensible tool for sustainable development. Current and future chemists should consider the human health and ecological issues in their professional life. In order to provid...

  8. 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.

  9. 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).

  10. 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

  11. 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.

  12. Antiparallel Dynamic Covalent Chemistries.

    Science.gov (United States)

    Matysiak, Bartosz M; Nowak, Piotr; Cvrtila, Ivica; Pappas, Charalampos G; Liu, Bin; Komáromy, Dávid; Otto, Sijbren

    2017-05-17

    The ability to design reaction networks with high, but addressable complexity is a necessary prerequisite to make advanced functional chemical systems. Dynamic combinatorial chemistry has proven to be a useful tool in achieving complexity, however with some limitations in controlling it. Herein we introduce the concept of antiparallel chemistries, in which the same functional group can be channeled into one of two reversible chemistries depending on a controllable parameter. Such systems allow both for achieving complexity, by combinatorial chemistry, and addressing it, by switching from one chemistry to another by controlling an external parameter. In our design the two antiparallel chemistries are thiol-disulfide exchange and thio-Michael addition, sharing the thiol as the common building block. By means of oxidation and reduction the system can be reversibly switched from predominantly thio-Michael chemistry to predominantly disulfide chemistry, as well as to any intermediate state. Both chemistries operate in water, at room temperature, and at mildly basic pH, which makes them a suitable platform for further development of systems chemistry.

  13. 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

  14. 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...

  15. Ion implantation

    International Nuclear Information System (INIS)

    Dearnaley, Geoffrey

    1975-01-01

    First, ion implantation in semiconductors is discussed: ion penetration, annealing of damage, gettering, ion implanted semiconductor devices, equipement requirements for ion implantation. The importance of channeling for ion implantation is studied. Then, some applications of ion implantation in metals are presented: study of the corrosion of metals and alloys; influence or ion implantation on the surface-friction and wear properties of metals; hyperfine interactions in implanted metals

  16. Atmospheric chemistry and climate

    OpenAIRE

    Satheesh, SK

    2012-01-01

    Atmospheric chemistry is a branch of atmospheric science where major focus is the composition of the Earth's atmosphere. Knowledge of atmospheric composition is essential due to its interaction with (solar and terrestrial) radiation and interactions of atmospheric species (gaseous and particulate matter) with living organisms. Since atmospheric chemistry covers a vast range of topics, in this article the focus is on the chemistry of atmospheric aerosols with special emphasis on the Indian reg...

  17. Chemistry of the elements

    International Nuclear Information System (INIS)

    Greenwood, N.N.; Earnshaw, A.

    1984-01-01

    This textbook presents an account of the chemistry of the elements for both undergraduate and postgraduate students. It covers not only the 'inorganic' chemistry of the elements, but also analytical, theoretical, industrial, organometallic;, bio-inorganic and other areas of chemistry which apply. The following elements of special nuclear interest are included: Rb, Cs, Fr, Sr, Ba, Ra, Po, At, Rn, Sc, Y, Zr, Hf, V, Nb, Ta, Mo, Tc, Ru, the Lanthanide Elements, the Actinide Elements. (U.K.)

  18. From trace chemistry to single atom chemistry

    International Nuclear Information System (INIS)

    Adloff, J.P.

    1993-01-01

    Hot atom chemistry in the vast majority of experimental works deals with the trace amount of radioactive matters. Accordingly, the concept of trace chemistry is at the heart of hot atom chemistry. Some aspects of the chemistry at trace scale and at subtrace scale are presented together with the related problems of speciation and the complication which may arise due to the formation of radio colloids. The examples of 127 I(n,γ) 128 I and 132 Te (β - ) 132 I are shown, and the method based on radioactivity was used. The procedure of separating the elements in pitchblende is shown as the example of the chemistry of traces. 13 27 Al+ 2 4 He→ 0 1 n+ 15 30 P and 15 30 P→ 14 30 Si+e + +V are shown, and how to recognize the presence of radioactive colloids is explained. The formation of radiocolloids is by the sorption of a trace radioelement on pre-existing colloidal impurity or the self-condensation of monomeric species. The temporal parameters of the nature of reactions at trace concentration are listed. The examples of Class A and Class B reactions are shown. The kinetics of reactions at trace level, radon concentration, anthropogenic Pu and natural Pu in environment, the behavior of Pu atoms and so on are described. (K.I.)

  19. Canopy Chemistry (OTTER)

    Data.gov (United States)

    National Aeronautics and Space Administration — ABSTRACT: Canopy characteristics: leaf chemistry, specific leaf area, LAI, PAR, IPAR, NPP, standing biomass--see also: Meteorology (OTTER) for associated...

  20. USSR Report, Chemistry

    National Research Council Canada - National Science Library

    1986-01-01

    This USSR Report on Chemistry contains articles on Aerosols, Adsorption, Biochemistry, Catalysis, Chemical Industry, Coal Gasification, Electrochemistry, Explosives and Explosions, Fertilizers, Food...

  1. Elements of environmental chemistry

    National Research Council Canada - National Science Library

    Hites, R. A; Raff, Jonathan D

    2012-01-01

    ... more. Extensively revised, updated, and expanded, this second edition includes new chapters on atmospheric chemistry, climate change, and polychlorinated biphenyls and dioxins, and brominated flame retardants...

  2. Green Chemistry Pedagogy

    Science.gov (United States)

    Kolopajlo, Larry

    2017-02-01

    This chapter attempts to show how the practice of chemistry teaching and learning is enriched by the incorporation of green chemistry (GC) into lectures and labs. To support this viewpoint, evidence from a wide range of published papers serve as a cogent argument that GC attracts and engages both science and nonscience students, enhances chemistry content knowledge, and improves the image of the field, while preparing the world for a sustainable future. Published pedagogy associated with green and sustainable chemistry is critically reviewed and discussed.

  3. 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.

  4. 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

  5. A three-dimensional numerical investigation of trapezoid baffles effect on non-isothermal reactant transport and cell net power in a PEMFC

    International Nuclear Information System (INIS)

    Perng, Shiang-Wuu; Wu, Horng-Wen

    2015-01-01

    Highlights: • We study how angle and height of trapezoid baffle affect PEMFC net power. • The jet-type, trapping, and blockage effects augment non-isothermal transport in flow channel. • Greater angles and heights of trapezoid baffles provide more reactant to the catalyst layer. • Baffles of 1.5 mm and 90° fully block flow channel to show bad heat transfer and large pressure drop. • Maximum enhancement of cell net power is 90% with baffles of 60° angle and 1.125 mm height. - Abstract: The present study performed a three-dimensional numerical simulation to observe how trapezoid baffles affect non-isothermal reactant transports and cell net power in the proton exchange membrane fuel cell (PEMFC) by the SIMPLE-C method. The geometric parameters of trapezoid baffles installed in the gas channel employed in this study include the angle and height with the same gas diffusion and catalyst layers to realize the cell net power considering the effect of liquid water formation on the fluid flow field. The cell net power is adopted to evaluate the real enhancement of cell performance due to the additional pumping power induced by the pressure loss through the PEMFC. The results illustrated that compared with traditional gas channel without baffles, the novel gas channel with trapezoid baffles, whose angle is 60° and height is 1.125 mm, enhances the cell net power best by approximately 90% among all trapezoid baffle designs

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. Annual report 1989 Chemistry Department

    International Nuclear Information System (INIS)

    Funck, J.; Neve Larsen, Aa.; Larsen, E.; Nielsen, O.J.

    1990-03-01

    This report contains a brief survey of the main activities in the Chemistry Department. The names and abstracts of all articles and reports published and lectures given in 1989 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry, analytical- and organic chemistry, environmental chemistry, polymer chemistry, chemical reactivity, mineral processing, and general. (author)

  11. Annual report 1988 Chemistry Department

    International Nuclear Information System (INIS)

    Funck, J.; Neve Larsen, Aa.; Larsen, E.; Nielsen, O.J.

    1989-05-01

    This report contains a brief survey of the main activities in the Chemistry Department. The names and abstracts of all articles and reports published and lectures given in 1988 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry, analytical- and organic chemistry, environmental chemistry, polymer chemistry, chemical reactivity, mineral processing, and general. (author)

  12. Annual report 1986 chemistry department

    International Nuclear Information System (INIS)

    Funck, J.; Larsen, E.; Nielsen, O.J.

    1987-03-01

    This report contains a brief survey of the main activities in the Chemistry Department. All articles and reports published and lectures given in 1986 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry, analytical- and organic chemistry, environmental chemistry, polymer chemistry, radical chemistral, mineral processing, and general. (author)

  13. A Study of Moroccan Pupils' Difficulties at Second Baccalaureate Year in Solving Chemistry Problems Relating to the Reactivity of Ethanoate Ions and to Copper-Aluminium Cells

    Science.gov (United States)

    Ouasri, Ali

    2017-01-01

    This paper investigates the difficulties that Moroccan pupils (18-19) of the second Baccalaureate year encountered in solving chemical equilibrium problems relating to ethanoate ions' reactivity with water and methanoic acid, and to copper-aluminum cells. The pupils were asked to provide answers to questions derived from two problems. The…

  14. 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.

  15. 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)

  16. 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.)

  17. Titanocene sulfide chemistry

    Czech Academy of Sciences Publication Activity Database

    Horáček, Michal

    2016-01-01

    Roč. 314, MAY 2016 (2016), s. 83-102 ISSN 0010-8545 R&D Projects: GA ČR(CZ) GAP207/12/2368 Institutional support: RVO:61388955 Keywords : titanocene sulfide chemistry * photolysis * titanocene hydrosulfides Ti-(SH)n Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 13.324, year: 2016

  18. A green chemistry approach

    Indian Academy of Sciences (India)

    Administrator

    One-pot synthesis of quinaldine derivatives by using microwave irradiation without any solvent – A green chemistry approach. JAVAD SAFARI*, SAYED HOSSEIN BANITABA and SEPEHR SADEGH SAMIEI. Department of Chemistry, The Faculty of sciences, University of Kashan, Kashan,. P.O. Box 87317-51167, I.R. Iran.

  19. Chemistry in Microfluidic Channels

    Science.gov (United States)

    Chia, Matthew C.; Sweeney, Christina M.; Odom, Teri W.

    2011-01-01

    General chemistry introduces principles such as acid-base chemistry, mixing, and precipitation that are usually demonstrated in bulk solutions. In this laboratory experiment, we describe how chemical reactions can be performed in a microfluidic channel to show advanced concepts such as laminar fluid flow and controlled precipitation. Three sets of…

  20. Chemistry of americium

    Energy Technology Data Exchange (ETDEWEB)

    Schulz, W.W.

    1976-01-01

    Essential features of the descriptive chemistry of americium are reviewed. Chapter titles are: discovery, atomic and nuclear properties, collateral reading, production and uses, chemistry in aqueous solution, metal, alloys, and compounds, and, recovery, separation, purification. Author and subject indexes are included. (JCB)

  1. Movies in Chemistry Education

    Science.gov (United States)

    Pekdag, Bulent; Le Marechal, Jean-Francois

    2010-01-01

    This article reviews numerous studies on chemistry movies. Movies, or moving pictures, are important elements of multimedia and signify a privileged or motivating means of presenting knowledge. Studies on chemistry movies show that the first movie productions in this field were devoted to university lectures or documentaries. Shorter movies were…

  2. WATER CHEMISTRY ASSESSMENT METHODS

    Science.gov (United States)

    This section summarizes and evaluates the surfce water column chemistry assessment methods for USEPA/EMAP-SW, USGS-NAQA, USEPA-RBP, Oho EPA, and MDNR-MBSS. The basic objective of surface water column chemistry assessment is to characterize surface water quality by measuring a sui...

  3. The Breath of Chemistry

    DEFF Research Database (Denmark)

    Josephsen, Jens

    The present preliminary text is a short thematic presentation in biological inorganic chemistry meant to illustrate general and inorganic (especially coordination) chemistry in biochemistry. The emphasis is on molecular models to explain features of the complicated mechanisms essential to breathing...

  4. Exercises in Computational Chemistry

    DEFF Research Database (Denmark)

    Spanget-Larsen, Jens

    2016-01-01

    A selection of HyperChem© PC-exercises in computational chemistry. Answers to most questions are appended (Roskilde University 2014-16).......A selection of HyperChem© PC-exercises in computational chemistry. Answers to most questions are appended (Roskilde University 2014-16)....

  5. Chemistry and Biology

    Science.gov (United States)

    Wigston, David L.

    1970-01-01

    Discusses the relationship between chemisty and biology in the science curriculum. Points out the differences in perception of the disciplines, which the physical scientists favoring reductionism. Suggests that biology departments offer a special course for chemistry students, just as the chemistry departments have done for biology students.…

  6. Transuranic Computational Chemistry.

    Science.gov (United States)

    Kaltsoyannis, Nikolas

    2018-02-26

    Recent developments in the chemistry of the transuranic elements are surveyed, with particular emphasis on computational contributions. Examples are drawn from molecular coordination and organometallic chemistry, and from the study of extended solid systems. The role of the metal valence orbitals in covalent bonding is a particular focus, especially the consequences of the stabilization of the 5f orbitals as the actinide series is traversed. The fledgling chemistry of transuranic elements in the +II oxidation state is highlighted. Throughout, the symbiotic interplay of experimental and computational studies is emphasized; the extraordinary challenges of experimental transuranic chemistry afford computational chemistry a particularly valuable role at the frontier of the periodic table. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. 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

  8. 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.)

  9. Korean Kimchi Chemistry: A Multicultural Chemistry Connection

    Science.gov (United States)

    Murfin, Brian

    2009-01-01

    Connecting science with different cultures is one way to interest students in science, to relate science to their lives, and at the same time to broaden their horizons in a variety of ways. In the lesson described here, students make kimchi, a delicious and popular Korean dish that can be used to explore many important chemistry concepts,…

  10. Chemistry and Nanoscience Research | NREL

    Science.gov (United States)

    Chemistry and Nanoscience Center at NREL investigates materials and processes for converting renewable and new technologies. NREL's primary research in the chemistry and nanoscience center includes the Electrochemical Engineering and Materials Chemistry Providing a knowledge base in materials science covering

  11. System approach to chemistry course

    OpenAIRE

    Lorina E. Kruglova; Valentina G. Derendyaeva

    2010-01-01

    The article considers the raise of chemistry profile for engineers and constructors training, discloses the system approach to chemistry course and singles out the most important modules from the course of general chemistry for construction industry.

  12. 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)

  13. Annual report 1987 Chemistry Department

    International Nuclear Information System (INIS)

    Funck, J.; Larsen, E.; Nielsen, O.J.

    1988-04-01

    This report contains a brief survey of the main activities in the Chemistry Department. The names and abstracts of all articles and reports published and lectures given in 1987 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry, analytical- and organic chemistry, environmental chemistry, polymer chemistry, radical chemistry, mineral processing, and general. 13 ills., (author)

  14. Annual report 1982 chemistry department

    International Nuclear Information System (INIS)

    Larsen, E.; Nielsen, O.J.

    1983-04-01

    The work going on in the Risoe National Laboratory, Chemistry Department is briefly surveyed by a presentation of all articles and reports published in 1982. The facilities and equipment are barely mentioned. The papers are divided into eight activities: 1. neutron activation analysis 2. analytical- and organic chemistry 3. environmental chemistry 4. polymer chemistry 5. geochemistry 6. radical chemistry 7. poitron annihilation 8. uranium process chemistry. (author)

  15. Indolenine meso-substituted dibenzotetraaza[14]annulene and its coordination chemistry toward the transition metal ions Mn(III), Fe(III), Co(II), Ni(II), Cu(II), and Pd(II).

    Science.gov (United States)

    Khaledi, Hamid; Olmstead, Marilyn M; Ali, Hapipah Mohd; Thomas, Noel F

    2013-02-18

    A new dibenzotetraaza[14]annulene bearing two 3,3-dimethylindolenine fragments at the meso positions (LH(2)), has been synthesized through a nontemplate method. X-ray crystallography shows that the whole molecule is planar. The basicity of the indolenine ring permits the macrocycle to be protonated external to the core and form LH(4)(2+)·2Cl(-). Yet another structural modification having strong C-H···π interactions was found in the chloroform solvate of LH(2). The latter two modifications are accompanied by a degree of nonplanar distortion. The antiaromatic core of the macrocycle can accommodate a number of metal ions, Mn(III), Fe(III), Co(II), Ni(II) and Cu(II), to form complexes of [Mn(L)Br], [Mn(L)Cl], [Fe(LH(2))Cl(2)](+)·Cl(-), [Co(L)], [Ni(L)], and [Cu(L)]. In addition, the reaction of LH(2) with the larger Pd(II) ion leads to the formation of [Pd(2)(LH(2))(2)(OAc)(4)] wherein the macrocycle acts as a semiflexible ditopic ligand to coordinate pairs of metal ions via its indolenine N atoms into dinuclear metallocycles. The compounds LH(2), [Co(L)], and [Ni(L)] are isostructural and feature close π-stacking as well as linear chain arrangements in the case of the metal complexes. Variable temperature magnetic susceptibility measurements showed thermally induced paramagnetism in [Ni(L)].

  16. Annual Report 1984. Chemistry Department

    DEFF Research Database (Denmark)

    Funck, Jytte; Nielsen, Ole John

    This report contains a brief survey of the main activities in the Chemistry Department. All articles and reports published and lectures given in 1984 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry, an......, analytical- and organic chemistry, environmental chemistry, polymer chemistry, geochemistry and waste disposal, radical chemistry, positron annihilation, mineral processing, and general.......This report contains a brief survey of the main activities in the Chemistry Department. All articles and reports published and lectures given in 1984 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry...

  17. Moderator Chemistry Program

    International Nuclear Information System (INIS)

    Dewitt, L.V.; Gibbs, A.; Lambert, D.P.; Bohrer, S.R.; Fanning, R.L.; Houston, M.W.; Stinson, S.L.; Deible, R.W.; Abdel-Khalik, S.I.

    1990-11-01

    Over the past fifteen months, the Systems Chemistry Group of the Reactor Engineering Department has undertaken a comprehensive study of the Department's moderator chemistry program at Savannah River Site (SRS). An internal review was developed to formalize and document this program. Objectives were as outlined in a mission statement and action plan. In addition to the mission statement and action plan, nine separate task reports have been issued during the course of this study. Each of these task reports is included in this document as a chapter. This document is an organized compilation of the individual reports issued by the Systems Chemistry Group in assessment of SRS moderator chemistry to determine if there were significant gaps in the program as ft existed in October, 1989. While these reviews found no significant gaps in that mode of operation, or any items that adversely affected safety, items were identified that could be improved. Many of the items have already been dear with or are in the process of completion under this Moderator Chemistry Program and other Reactor Restart programs. A complete list of the items of improvement found under this assessment is found in Chapter 9, along with a proposed time table for correcting remaining items that can be improved for the chemistry program of SRS reactors. An additional external review of the moderator chemistry processes, recommendations, and responses to/from the Reactor Corrosion Mitigation Committee is included as Appendix to this compilation

  18. 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.)

  19. Organic Chemistry of Meteorites

    Science.gov (United States)

    Chang, S.; Morrison, David (Technical Monitor)

    1994-01-01

    Studies of the molecular structures and C,N,H-isotopic compositions of organic matter in meteorites reveal a complex history beginning in the parent interstellar cloud which spawned the solar system. Incorporation of interstellar dust and gas in the protosolar nebula followed by further thermal and aqueous processing on primordial parent bodies of carbonaceous, meteorites have produced an inventory of diverse organic compounds including classes now utilized in biochemistry. This inventory represents one possible set of reactants for chemical models for the origin of living systems on the early Earth. Evidence bearing on the history of meteoritic organic matter from astronomical observations and laboratory investigations will be reviewed and future research directions discussed.

  20. Chemistry in water reactors

    International Nuclear Information System (INIS)

    Hermansson, H.P.; Norring, K.

    1994-01-01

    The international conference Chemistry in Water Reactors was arranged in Nice 24-27/04/1994 by the French Nuclear Energy Society. Examples of technical program areas were primary chemistry, operational experience, fundamental studies and new technology. Furthermore there were sessions about radiation field build-up, hydrogen chemistry, electro-chemistry, condensate polishing, decontamination and chemical cleaning. The conference gave the impression that there are some areas that are going to be more important than others during the next few years to come. Cladding integrity: Professor Ishigure from Japan emphasized that cladding integrity is a subject of great concern, especially with respect to waterside corrosion, deposition and release of crud. Chemistry control: The control of the iron/nickel concentration quotient seems to be not as important as previously considered. The future operation of a nuclear power plant is going to require a better control of the water chemistry than achievable today. One example of this is solubility control via regulation in BWR. Trends in USA: means an increasing use of hydrogen, minimization of SCC/IASCC, minimization of radiation fields by thorough chemistry control, guarding fuel integrity by minimization of cladding corrosion and minimization of flow assisted corrosion. Stellite replacement: The search for replacement materials will continue. Secondary side crevice chemistry: Modeling and practical studies are required to increase knowledge about the crevice chemistry and how it develops under plant operation conditions. Inhibitors: Inhibitors for IGSCC and IGA as well for the primary- (zinc) as for the secondary side (Ti) should be studied. The effects and mode of operation of the inhibitors should be documented. Chemical cleaning: of heat transfer surfaces will be an important subject. Prophylactic cleaning at regular intervals could be one mode of operation

  1. Antiphase dual-color correlation in a reactant-product pair imparts ultrasensitivity in reaction-linked double-photoswitching fluorescence imaging.

    Science.gov (United States)

    Wan, Wei; Zhu, Ming-Qiang; Tian, Zhiyuan; Li, Alexander D Q

    2015-04-08

    A pair of reversible photochemical reactions correlates their reactant and product specifically, and such a correlation uniquely distinguishes their correlated signal from others that are not linked by this reversible reaction. Here a nanoparticle-shielded fluorophore is photodriven to undergo structural dynamics, alternating between a green-fluorescence state and a red-fluorescence state. As time elapses, the fluorophore can be in either state but not both at the same time. Thus, the red fluorescence is maximized while the green fluorescence is minimized and vice versa. Such an antiphase dual-color (AD) corelationship between the red and green fluorescence maxima as well as between their minima can be exploited to greatly improve the signal-to-noise ratio, thus enhancing the ultimate detection limit. Potential benefits of this correlation include elimination of all interferences originating from single-color dyes and signal amplification of AD photoswitching molecules by orders of magnitude.

  2. Mathematics for physical chemistry

    CERN Document Server

    Mortimer, Robert G

    2013-01-01

    Mathematics for Physical Chemistry is the ideal supplementary text for practicing chemists and students who want to sharpen their mathematics skills while enrolled in general through physical chemistry courses. This book specifically emphasizes the use of mathematics in the context of physical chemistry, as opposed to being simply a mathematics text. This 4e includes new exercises in each chapter that provide practice in a technique immediately after discussion or example and encourage self-study. The early chapters are constructed around a sequence of mathematical topics, wit

  3. Spatially Resolved Artificial Chemistry

    DEFF Research Database (Denmark)

    Fellermann, Harold

    2009-01-01

    Although spatial structures can play a crucial role in chemical systems and can drastically alter the outcome of reactions, the traditional framework of artificial chemistry is a well-stirred tank reactor with no spatial representation in mind. Advanced method development in physical chemistry has...... made a class of models accessible to the realms of artificial chemistry that represent reacting molecules in a coarse-grained fashion in continuous space. This chapter introduces the mathematical models of Brownian dynamics (BD) and dissipative particle dynamics (DPD) for molecular motion and reaction...

  4. Experiments in physical chemistry

    CERN Document Server

    Wilson, J M; Denaro, A R

    1968-01-01

    Experiments in Physical Chemistry, Second Edition provides a compilation of experiments concerning physical chemistry. This book illustrates the link between the theory and practice of physical chemistry. Organized into three parts, this edition begins with an overview of those experiments that generally have a simple theoretical background. Part II contains experiments that are associated with more advanced theory or more developed techniques, or which require a greater degree of experimental skill. Part III consists of experiments that are in the nature of investigations wherein these invest

  5. Computational quantum chemistry website

    International Nuclear Information System (INIS)

    1997-01-01

    This report contains the contents of a web page related to research on the development of quantum chemistry methods for computational thermochemistry and the application of quantum chemistry methods to problems in material chemistry and chemical sciences. Research programs highlighted include: Gaussian-2 theory; Density functional theory; Molecular sieve materials; Diamond thin-film growth from buckyball precursors; Electronic structure calculations on lithium polymer electrolytes; Long-distance electronic coupling in donor/acceptor molecules; and Computational studies of NOx reactions in radioactive waste storage

  6. Spatially Resolved Artificial Chemistry

    DEFF Research Database (Denmark)

    Fellermann, Harold

    2009-01-01

    made a class of models accessible to the realms of artificial chemistry that represent reacting molecules in a coarse-grained fashion in continuous space. This chapter introduces the mathematical models of Brownian dynamics (BD) and dissipative particle dynamics (DPD) for molecular motion and reaction......Although spatial structures can play a crucial role in chemical systems and can drastically alter the outcome of reactions, the traditional framework of artificial chemistry is a well-stirred tank reactor with no spatial representation in mind. Advanced method development in physical chemistry has...

  7. DOE fundamentals handbook: Chemistry

    International Nuclear Information System (INIS)

    1993-01-01

    The Chemistry 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. The handbook includes information on the atomic structure of matter; chemical bonding; chemical equations; chemical interactions involved with corrosion processes; water chemistry control, including the principles of water treatment; the hazards of chemicals and gases, and basic gaseous diffusion processes. This information will provide personnel with a foundation for understanding the chemical properties of materials and the way these properties can impose limitations on the operation of equipment and systems

  8. Agent-based simulation of reactions in the crowded and structured intracellular environment: Influence of mobility and location of the reactants

    Directory of Open Access Journals (Sweden)

    Lapin Alexei

    2011-05-01

    Full Text Available Abstract Background In this paper we apply a novel agent-based simulation method in order to model intracellular reactions in detail. The simulations are performed within a virtual cytoskeleton enriched with further crowding elements, which allows the analysis of molecular crowding effects on intracellular diffusion and reaction rates. The cytoskeleton network leads to a reduction in the mobility of molecules. Molecules can also unspecifically bind to membranes or the cytoskeleton affecting (i the fraction of unbound molecules in the cytosol and (ii furthermore reducing the mobility. Binding of molecules to intracellular structures or scaffolds can in turn lead to a microcompartmentalization of the cell. Especially the formation of enzyme complexes promoting metabolic channeling, e.g. in glycolysis, depends on the co-localization of the proteins. Results While the co-localization of enzymes leads to faster reaction rates, the reduced mobility decreases the collision rate of reactants, hence reducing the reaction rate, as expected. This effect is most prominent in diffusion limited reactions. Furthermore, anomalous diffusion can occur due to molecular crowding in the cell. In the context of diffusion controlled reactions, anomalous diffusion leads to fractal reaction kinetics. The simulation framework is used to quantify and separate the effects originating from molecular crowding or the reduced mobility of the reactants. We were able to define three factors which describe the effective reaction rate, namely f diff for the diffusion effect, f volume for the crowding, and f access for the reduced accessibility of the molecules. Conclusions Molecule distributions, reaction rate constants and structural parameters can be adjusted separately in the simulation allowing a comprehensive study of individual effects in the context of a realistic cell environment. As such, the present simulation can help to bridge the gap between in vivo and in vitro

  9. Non-thermally activated chemistry

    International Nuclear Information System (INIS)

    Stiller, W.

    1987-01-01

    The subject is covered under the following headings: state-of-the art of non-thermally activated chemical processes; basic phenomena in non-thermal chemistry including mechanochemistry, photochemistry, laser chemistry, electrochemistry, photo-electro chemistry, high-field chemistry, magneto chemistry, plasma chemistry, radiation chemistry, hot-atom chemistry, and positronium and muonium chemistry; elementary processes in non-thermal chemistry including nuclear chemistry, interactions of electromagnetic radiations, electrons and heavy particles with matter, ionic elementary processes, elementary processes with excited species, radicalic elementary processes, and energy-induced elementary processes on surfaces and interfaces; and comparative considerations. An appendix with historical data and a subject index is given. 44 figs., 41 tabs., and 544 refs

  10. Radiation chemistry of aqueous trichloroethene

    International Nuclear Information System (INIS)

    Cooper, R.

    1998-01-01

    Full text: Halogenated hydrocarbons have played a key role in Industrial processes for many years. The problems of disposal of used solvents and chloroderivatives is now a problem facing chemical companies, industrial and domestic users. A range of treatments have been suggested and tried from high efficiency incineration to photo-catalytic hydrolysis. Radiation chemistry offers a route to dissolution and dehalogenation of halocarbons in general by virtue of free radical reactions and in particular the dissociative electron capture process resulting from the generation of solvated electrons. RCl + e - aq → R + Cl - aq . The fate of the free radical, R, is crucial to the subsequent degradation of the halocarbon. It will probably contain more organic chlorine, or other halogens, which ideally should be degradable to inert inorganic halide. In this study pulse radiolysis studies have been conducted on aqueous solutions of trichloroethene (TCE) which is a commonly used industrial cleaning solvent. The production of free radicals has been monitored by fast time resolution absorption spectroscopy using a pulse radiolysis facility at the Australian Radiation Laboratory Yallambie Victoria. Fee radical species have been detected in pulse electron irradiated solutions of TCE at various pH's and in the presence of Oxygen and Nitrous oxide. The nature of these radical species will be discussed. The production of inorganic chlorine is being monitored by a spectrophotometric technique based upon a mercuric thiocyanate/ ferric ion complexation which can detect free chloride ion concentrations down to ppm levels

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Radionuclides in analytical chemistry

    International Nuclear Information System (INIS)

    Tousset, J.

    1984-01-01

    Applications of radionuclides in analytical chemistry are reviewed in this article: tracers, radioactive sources and activation analysis. Examples are given in all these fields and it is concluded that these methods should be used more widely [fr

  16. Electrostatics in Chemistry

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 4; Issue 7. Electrostatics in Chemistry - Molecular Electrostatic Potential: Visualization and Topography. Shridhar R Gadre Pravin K Bhadane. Series Article Volume 4 Issue 7 July 1999 pp 14-23 ...

  17. Organic Chemistry Masterclasses

    Indian Academy of Sciences (India)

    of Science Education that is published monthly by the Academy since January 1996. ...... Modern chemistry is also emerging from molecules derived from the .... photochemical reactions, the traditional correlation diagram approach is more ...

  18. Alcohol combustion chemistry

    KAUST Repository

    Sarathy, Mani; Oß wald, Patrick; Hansen, Nils; Kohse-Hö inghaus, Katharina

    2014-01-01

    . While biofuel production and its use (especially ethanol and biodiesel) in internal combustion engines have been the focus of several recent reviews, a dedicated overview and summary of research on alcohol combustion chemistry is still lacking. Besides

  19. General Chemistry for Engineers.

    Science.gov (United States)

    Kybett, B. D.

    1982-01-01

    Discusses the relationship between molecular structure, intermolecular forces, and tensile strengths of a polymer and suggests that this is a logical way to introduce polymers into a general chemistry course. (Author/JN)

  20. WHAT MAKES CHEMISTRY DIFFICULT?

    African Journals Online (AJOL)

    IICBA01

    School of Natural and Computational Science Dire Dawa University, Ethiopia,. 2 ... lack of teaching aids and the difficulty of the language of chemistry. ... lab every other week consisting of concept pretests on the web, hand-written homework, ...

  1. Indicators: Soil Chemistry

    Science.gov (United States)

    The chemical makeup of the soil can provide information on wetland condition, wetland water quality and services being provided by the wetland ecosystem. Analyzing soil chemistry reveals if the soil is contaminated with a toxic chemical or heavy metal.

  2. Applications of supramolecular chemistry

    CERN Document Server

    Schneider, Hans-Jörg

    2012-01-01

    ""The time is ripe for the present volume, which gathers thorough presentations of the numerous actually realized or potentially accessible applications of supramolecular chemistry by a number of the leading figures in the field. The variety of topics covered is witness to the diversity of the approaches and the areas of implementation…a broad and timely panorama of the field assembling an eminent roster of contributors.""-Jean-Marie Lehn, 1987 Noble Prize Winner in Chemistry

  3. Reference Sources in Chemistry

    OpenAIRE

    Sthapit, Dilip Man

    1995-01-01

    Information plays an important role in the development of every field. Therefore a brief knowledge regarding information sources is necessary to function in any field. There are many information sources about scientific and technical subjects. In this context there are many reference sources in Chemistry too. Chemistry is one important part of the science which deals with the study of the composition of substances and the chemical changes that they undergo. The purpose of this report is...

  4. Quantitative analysis chemistry

    International Nuclear Information System (INIS)

    Ko, Wansuk; Lee, Choongyoung; Jun, Kwangsik; Hwang, Taeksung

    1995-02-01

    This book is about quantitative analysis chemistry. It is divided into ten chapters, which deal with the basic conception of material with the meaning of analysis chemistry and SI units, chemical equilibrium, basic preparation for quantitative analysis, introduction of volumetric analysis, acid-base titration of outline and experiment examples, chelate titration, oxidation-reduction titration with introduction, titration curve, and diazotization titration, precipitation titration, electrometric titration and quantitative analysis.

  5. Chemistry and nuclear technology

    International Nuclear Information System (INIS)

    De Wet, W.J.

    1977-01-01

    The underlying principles of nuclear sciece and technology as based on the two basic phenomena, namely, radioactivity and nuclear reactions, with their relatively large associated energy changes, are outlined. The most important contributions by chemists in the overall historical development are mentioned and the strong position chemistry has attained in these fields is indicated. It is concluded that chemistry as well as many other scientific discplines (apart from general benefits) have largely benefitted from these nuclear developments [af

  6. EPA Environmental Chemistry Laboratory

    Science.gov (United States)

    1993-01-01

    The Environmental Protection Agency's (EPA) Chemistry Laboratory (ECL) is a national program laboratory specializing in residue chemistry analysis under the jurisdiction of the EPA's Office of Pesticide Programs in Washington, D.C. At Stennis Space Center, the laboratory's work supports many federal anti-pollution laws. The laboratory analyzes environmental and human samples to determine the presence and amount of agricultural chemicals and related substances. Pictured, ECL chemists analyze environmental and human samples for the presence of pesticides and other pollutants.

  7. Fundamentals of quantum chemistry

    CERN Document Server

    House, J E

    2004-01-01

    An introduction to the principles of quantum mechanics needed in physical chemistry. Mathematical tools are presented and developed as needed and only basic calculus, chemistry, and physics is assumed. Applications include atomic and molecular structure, spectroscopy, alpha decay, tunneling, and superconductivity. New edition includes sections on perturbation theory, orbital symmetry of diatomic molecules, the Huckel MO method and Woodward/Hoffman rules as well as a new chapter on SCF and Hartree-Fock methods. * This revised text clearly presents basic q

  8. Tropical Soil Chemistry

    DEFF Research Database (Denmark)

    Borggaard, Ole K.

    and environmental protection. Tropical Soil Chemistry by Ole K. Borggaard provides an overview of the composition, occurrence, properties, processes, formation, and environmental vulnerability of various tropical soil types (using American Soil Taxonomy for classification). The processes and the external factors...... soil chemical issues are also presented to assess when, why, and how tropical soils differ from soils in other regions. This knowledge can help agricultural specialists in the tropics establish sustainable crop production. Readers are assumed to be familiar with basic chemistry, physics...

  9. 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

  10. 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

  11. 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).

  12. Using MDECR-PECVD to study the impact of ion bombardment energy on microstructural properties of μc-Si:H thin film grown from an SiF{sub 4}/H{sub 2} chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Junkang; Florea, Ileana; Bulkin, Pavel V.; Maurice, Jean-Luc; Johnson, Erik V. [LPICM, CNRS, Ecole Polytechnique, Universite Paris Saclay, 91128 Palaiseau (France)

    2016-12-15

    The matrix-distributed electron cyclotron resonance plasma-enhanced chemical vapor deposition (MDECR-PECVD) technique has been shown to achieve high deposition rates for hydrogenated microcrystalline silicon (μc-Si:H) thin film. Due to the fact that plasma is sustained by a microwave discharge, by biasing the substrate holder with additional power supply, one can achieve independent control over the plasma density and the maximum ion bombardment energy (IBE). In this work, we present studies of the impact of IBE on the microstructural properties of the μc-Si:H film deposited by MDECR-PECVD. Insufficient ion bombardment is found to be responsible for the substantial presence of nano-porous regions within the material, resulting in significant post-deposition oxidation. Good agreement between transmission electron microscopy (TEM) Fresnel contrast analysis and the results of infrared absorption and hydrogen effusion measurements for the deposited films suggest that moderate IBE is of vital importance to achieve high quality μc-Si:H. In doing so, denser films with significantly decreased nano-porous regions and better stability are obtained, which is of great interest to optimize the process parameters for solar cell applications. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Henry Taube and Coordination Chemistry

    Science.gov (United States)

    dropdown arrow Site Map A-Z Index Menu Synopsis Henry Taube and Coordination Chemistry Resources with Professor of Chemistry, Emeritus, at Stanford University, received the 1983 Nobel Prize in Chemistry " there from 1940-41. "I became deeply interested in chemistry soon after I came to Berkeley,"

  14. Understanding of the structure activity relationship of PtPd bimetallic catalysts prepared by surface organometallic chemistry and ion exchange during the reaction of iso-butane with hydrogen

    KAUST Repository

    Al-Shareef, Reem A.; Harb, Moussab; Saih, Youssef; Ould-Chikh, Samy; Roldan, Manuel A.; Anjum, Dalaver H.; Guyonnet, Elodie Bile; Candy, Jean-Pierre; Jan, Deng-Yang; Abdo, Suheil F.; Aguilar-Tapia, Antonio; Proux, Olivier; Hazemann, Jean-Louis; Basset, Jean-Marie

    2018-01-01

    Well-defined silica supported bimetallic catalysts Pt100-x Pdx were prepared by Surface Organometallic Chemistry (SOMC) and Ionic-Exchange (IE) methods. For all investigated catalysts, iso-butane reaction with hydrogen under differential conditions led to the formation of methane and propane, n-butane, and traces of iso-butylene. The total reaction rate decreased with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the experimental results in combination with DFT calculations suggested a selective coverage of Pt (1 0 0) surface by agglomerated Pd atoms like “islands”, assuming that each metal roughly keeps its intrinsic catalytic properties with relatively small electron transfer from Pt to Pd in the case of Pt-rich sample and from Pd to Pt in the case of Pd-rich sample. For the PtPd catalysts prepared by IE, the catalytic behavior could be explained by the formation of a surface alloy between Pt and Pd in the case of Pd-rich sample and by the segregation of a small amount of Pd on the surface in the case of Pt-rich sample, as demonstrated by TEM, EXAFS and DFT. The catalytic results were explained by a structure activity relationship based on the proposed mechanism of CH bond and CC bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.

  15. Understanding of the structure activity relationship of PtPd bimetallic catalysts prepared by surface organometallic chemistry and ion exchange during the reaction of iso-butane with hydrogen

    KAUST Repository

    Alshareef, Reem Abdul aziz Hamed

    2018-04-25

    Well-defined silica supported bimetallic catalysts Pt100-x Pdx were prepared by Surface Organometallic Chemistry (SOMC) and Ionic-Exchange (IE) methods. For all investigated catalysts, iso-butane reaction with hydrogen under differential conditions led to the formation of methane and propane, n-butane, and traces of iso-butylene. The total reaction rate decreased with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the experimental results in combination with DFT calculations suggested a selective coverage of Pt (1 0 0) surface by agglomerated Pd atoms like “islands”, assuming that each metal roughly keeps its intrinsic catalytic properties with relatively small electron transfer from Pt to Pd in the case of Pt-rich sample and from Pd to Pt in the case of Pd-rich sample. For the PtPd catalysts prepared by IE, the catalytic behavior could be explained by the formation of a surface alloy between Pt and Pd in the case of Pd-rich sample and by the segregation of a small amount of Pd on the surface in the case of Pt-rich sample, as demonstrated by TEM, EXAFS and DFT. The catalytic results were explained by a structure activity relationship based on the proposed mechanism of CH bond and CC bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.

  16. 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

  17. 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...

  18. 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.)

  19. 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.)

  20. 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)