WorldWideScience

Sample records for chemistry phase relations

  1. 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

  2. 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

  3. Phase Relations and Defect Chemistry of Bismuth Strontium Calcium Copper Oxide Superconducting Oxides at Elevated Temperature

    Science.gov (United States)

    Hong, Byungsun

    1992-01-01

    Subsolidus phase relations in the system (Bi-Sr -Ca-Cu)-O at 800^circC were investigated via powder X-ray diffraction and electron probe microanalysis of solid-state reaction products. The only truly quaternary compound detected is the superconducting phase of n = 2 in Bi_2(Sr _{rm x}Ca_ {rm 1-x})_{ rm n+1}Cu_{rm n}O_{rm y} . The n = 2 phase is compatible with eight different binary or ternary phases. Tie lines, tie triangles, and compatibility tetrahedra involving superconducting phases were determined. The cation solubility limits of the n = 2 and n = 3 superconducting phases were established along tie lines with compatible phases via EPMA on bi- (or poly -) phasic samples prepared at 860^circ C. In each case football-shaped volumes in composition space were established as the solubility limits which bordered on the nominal compositions 2212 or 2223 with the long axis parallel to the Sr-Ca side of the quaternary but also extending toward Bi and Cu. T_{rm c} variations could be correlated with variations in Sr or (Bi+Sr) content and the length of the c-axis parameter. Via in-situ high temperature (550-650 ^circC) electrical conductivity and Seebeck coefficient measurements in Bi_ {2.1}Sr_{1.9} (Ca_{rm 1-x}Y _{rm x})Cu _2O_{rm y} , a point defect model/diagram is presented which explains the variation of thermopower with composition in the system. The reference, insulating composition should be between Bi_{2.1}Sr _{1.9}Ca_ {0.2}Y_{0.8} Cu_2O_{8.45 } and Bi_{2.1}Sr _{1.9}Ca_ {0.3}Y_{0.7} Cu_2O_{8.4 }. Y-contents higher than x = 0.8 result in a second phase. A structural phase transition from pseudo -tetragonal to orthorhombic takes place at x = 0.5, and plays a major role in determining the physical properties. Oxygen transfer from the Bi-O block to the Cu-O based perovskite block is suggested at the phase boundary of x = 0.5. Jonker analysis and oxygen pressure dependence of carrier concentration confirm p-type behavior despite the change in sign of the thermopower

  4. Six Phases of Cosmic Chemistry

    OpenAIRE

    Lukasz Lamza

    2014-01-01

    The article presents a conceptually unified, quantitative account of the development of chemical phenomena throughout the cosmic history, with a detailed discussion of the cosmological, astrophysical, geological, biological, and anthropological context. The totality of cosmic chemistry is represented by a list of 176 classes of phenomena, drawn from the Universal Decimal Classification (UDC) library cataloguing system, and divided into 6 phases: of no chemistry, of prestellar chemistry, of ga...

  5. The gas-phase thermal chemistry of tetralin and related model systems

    Energy Technology Data Exchange (ETDEWEB)

    Malandra, J.

    1993-05-01

    The thesis is divided into 5 papers: gas-phase thermal decomposition of tetralin; flash vacuum pyrolysis of 3-benzocycloheptenone and 1,3, 4,5-tetrahydro-2-benzothiepin-2,2-dioxide (model systems for gas-phase pyrolysis of tetralin); high-temperature gas-phase reactions of o-allylbenzyl radicals generated by flash vacuum pyrolysis of is(o-allylbenzyl) oxalate; flash vacuum pyrolysis of 1,4-diphenylbutane; and flash vacuum pyrolysis of o-allyltoluene, o-(3-butenyl)toluene and o-(pentenyl)toluene were also used.

  6. The chemistry of the Na-U-O system and related phases

    International Nuclear Information System (INIS)

    This thesis describes investigations into the following chemical systems; Na-U-O, Cs-U-O, Ba-U-O, Ba-Pr-O, Ba-Zr-O, Ba-Ce-O, Cs-Ce-O and Na-Pr-O. The sodium ternary oxides Na2U2O7, Na2UO4 and Na4UO5 were prepared by either solid state or liquid sodium reactions. The existence of a new phase in the sodium-rich portion of this system was also studied. The caesium uranates Cs2U2O7, Cs4U5O17 and Cs2UO4 were prepared similarly and characterised by X-ray powder diffraction. Several barium ternary oxides were synthesised and subsequently reacted with liquid sodium. An investigation into the Cs-Ce-O system, revealed a new phase, CsCeO2, which has a hexagonal structure. A galvanic electrochemical cell, which monitored the chemical potential of oxygen dissolved in either liquid sodium or caesium, was developed. The cell vessel was re-designed for the liquid caesium work, along with the development of computerised data collection. The use of various electrolyte materials for the cells was investigated, with the zirconia-based materials being found to be suitable electrolytes. The cells were used to study several of the systems above, and generated the following free energies of formation; (NaPrO2) = -1069 kJmol-1, (Cs2UO4) -1814 kJmol-1 and (CsCeO2) = - 1024 kJmol-1. (author)

  7. Introducing Relativity into Quantum Chemistry

    Science.gov (United States)

    Li, Wai-Kee; Blinder, S. M.

    2011-01-01

    It is not often realized by chemists that the special theory of relativity is behind several aspects of quantum chemistry. The Schrdinger equation itself is based on relations between space-time and energy-momentum four vectors. Electron spin is, of course, the most obvious manifestation of relativity. The chemistry of some heavy elements is…

  8. Modelling multi-phase halogen chemistry in the coastal marine boundary layer: investigation of the relative importance of local chemistry vs. long-range transport

    Directory of Open Access Journals (Sweden)

    D. Lowe

    2010-08-01

    Full Text Available Measurements of significant concentrations of IO, I2 and BrO in a semi-polluted coast environment at Roscoff, in North-West France, have been made as part of the Reactive Halogens in the Marine Boundary Layer (RHaMBLe campaign undertaken in September 2006. We use a one-dimensional column model, with idealised I2 emissions predicted using macroalgael maps and tidal data from the littoral area surrounding Roscoff, to investigate the probable causes for these observations. The coupled microphysical and chemical aerosol model simulates mixed-phase halogen chemistry using two separate particle modes, seasalt and non-seasalt, each comprising of eight size-sections. This work confirms the finding of a previous study that the BrO measurements are most likely caused by unknown, local sources. We find that the remote observations of IO and I2 are best replicated using the I2 recycling mechanism suggested by previous studies, but that such a mechanism is not wholly necessary. However we suggest that focussed observations of the changes in NOx and NOy concentrations, as well as changes in the nitrate fraction of the non-seasalt aerosol mode, in the presence of I2 bursts could be used to determine the atmospheric relevance of the predicted I2 recycling mechanism.

  9. Modelling multi-phase halogen chemistry in the coastal marine boundary layer: investigation of the relative importance of local chemistry vs. long-range transport

    Directory of Open Access Journals (Sweden)

    D. Lowe

    2011-02-01

    Full Text Available Measurements of significant concentrations of IO, I2 and BrO in a semi-polluted coast environment at Roscoff, in North-West France, have been made as part of the Reactive Halogens in the Marine Boundary Layer (RHaMBLe campaign undertaken in September 2006. We use a one-dimensional column model, with idealised I2 emissions predicted using macroalgael maps and tidal data from the littoral area surrounding Roscoff, to investigate the probable causes for these observations. The coupled microphysical and chemical aerosol model simulates mixed-phase halogen chemistry using two separate particle modes, seasalt and non-seasalt, each comprising of eight size-sections. This work confirms the finding of a previous study that the BrO measurements are most likely caused by unknown, local sources. We find that the remote observations of IO and I2 are best replicated using the I2 recycling mechanism suggested by previous studies, but that such a mechanism is not wholly necessary. However in-situ measurements of I2 can only be explained by invoking an I2 recycling mechanism. We suggest that focussed observations of the changes in NOx and NOy concentrations, as well as changes in the nitrate fraction of the non-seasalt aerosol mode, in the presence of I2 bursts could be used to determine the atmospheric relevance of the predicted I2 recycling mechanism.

  10. Gas phase chemistry of the transactinides

    Science.gov (United States)

    Türler, A.

    1999-01-01

    In the past few years the gas phase chemistry of the first three transactinide elements rutherfordium (element 104), dubnium (element 105) and seaborgium (element 106) has been studied experimentally using OLGA, the On-line Gas chemistry Apparatus, developed at Paul Scherrer Institute. In each experiment, the investigated transactinide element was identified by measuring the characteristic decay properties of its isotopes. In the chemistry of rutherfordium and dubnium evidence for relativistic effects were found, as predicted previously in theoretical calculations. For the first time, the volatility of Sg oxychlorides in comparison to its lighter homologues W and Mo was measured. Also, the half-lives and SF-branches of the nuclides 265Sg and 266Sg were determined. Finally, prospects for a chemical separation of bohrium (element 107) and hassium (element 108) using gas phase chemistry will be discussed.

  11. Gas phase chemistry of the transactinides

    International Nuclear Information System (INIS)

    In the past few years the gas phase chemistry of the first three transactinide elements Rutherfordium (element 104), Dubnium (element 105) and Seaborgium (element 106) has been studied experimentally using OLGA, the On-line Gas chemistry Apparatus, developed at Paul Scherrer Institute. In each experiment, the investigated transactinide element was identified by measuring the characteristic decay properties of its isotopes. In the chemistry of Rutherfordium and Dubnium evidence for relativistic effects were found, as predicted previously in theoretical calculations. For the first time, the volatility of Sg oxychlorides in comparison to its lighter homologues W and Mo was measured. Also, the half-lives and SF-branches of the nuclides 265Sg and 266Sg were determined. Finally, prospects for a chemical separation of Bohrium (element 107) and Hassium (108) using gas phase chemistry will be discussed. (author)

  12. Gas phase chemistry of the transactinides

    International Nuclear Information System (INIS)

    In the past few years the gas phase chemistry of the first three transactinide elements rutherfordium (element 104), dubnium (element 105) and seaborgium (element 106) has been studied experimentally using OLGA, the On-line Gas chemistry Apparatus, developed at Paul Scherrer Institute. In each experiment, the investigated transactinide element was identified by measuring the characteristic decay properties of its isotopes. In the chemistry of rutherfordium and dubnium evidence for relativistic effects were found, as predicted previously in theoretical calculations. For the first time, the volatility of Sg oxychlorides in comparison to its lighter homologues W and Mo was measured. Also, the half-lives and SF-branches of the nuclides 265Sg and 266Sg were determined. Finally, prospects for a chemical separation of bohrium (element 107) and hassium (element 108) using gas phase chemistry will be discussed. (author)

  13. Structural chemistry and phase relations in the ternary systems: rare earth (Nd)-Fe-(As,Sb,Bi)

    International Nuclear Information System (INIS)

    Phase equilibria in the system Nd-Fe-Sb have been determined in an isothermal section at 800 deg C. No compatibility was observed between Nd and the binary iron antimonides. There is virtually no solid solubility of Sb in binary Nd2Fe17. Seven ternary compounds were found to exist: Nd6Fe13Sb, NdFe3Sb2, NdFe2-xSb2, NdFe1-xSb2, 'Nd2Fe 3-xSb5', 'NdFeSb3'. The crystal structure of the latter two phases have not yet been characterized. Single crystal refinement of the Nd6Fe13Sb compound revealed isotypism with the Nd6Fe13Si structure type. A series of homologous compounds RE6(Fe, Co)13(As, Sb, Bi, Cu, Zn, Cd, Hg) have been prepared with RE= La, Pr, Nd, Sm. NdFe3Sb2 is the tetragonal high temperature modification of the orthorhombic NdFe2-xSb2 with significant Fe deficiency. Four-circle diffractometer data enabled refinement of the crystal structure of NdFe3Sb2 with the space group I4/mmm and Imm2 for the NdFe2-xSb2 structure. In contrast to the Pr, Sm compounds the isotypic La and Ce containing compounds show no orthorhombic distortion of the tetragonal diffraction pattern. Single crystal structure refinement revealed isotypism of NdFe1-xSb2 with the ZrCuSi2 structure type. Compounds RE(Fe, Co)1-xSb2 with RE= La, Ce, Pr, Sm, Gd showed isotypism with NdFe1-xSb2

  14. Radical Chemistry in the Gas Phase

    Czech Academy of Sciences Publication Activity Database

    Alcaraz, Ch.; Fischer, I.; Schröder, Detlef

    New York: John Wiley and Sons, 2012 - (Chatgilialoglu, C.; Studer, A.), s. 477-502 ISBN 978-0-470-97125-3 Grant ostatní: European Research Council(XE) AdG HORIZOMS Institutional research plan: CEZ:AV0Z40550506 Keywords : radicals * reactive intermediates * gas phase * photoionization * unimolecular reactions * bimolecular reactions Subject RIV: CF - Physical ; Theoretical Chemistry

  15. Mineral chemistry of radioactive and associated phases from neoproterozoic unconformity related uranium deposits from Koppunuru, Palnad sub-basin, Guntur District, Andhra Pradesh, India

    International Nuclear Information System (INIS)

    Unconformity proximal uranium mineralization at Koppunuru occurs in basement granitoids and the overlying Banganalapalle Formation of Kurnool Group in Palnad sub-basin. The U-mineralization transgresses the unconformity both above and below. Later remobilization of uranium is evident, as they are intermittently intercepted within the sediments overlying the unconformity. Subsurface exploration by drilling intercepted three mineralization bands, viz. Band A and B upto 80m above the unconformity in the overlying Banganapalle quartzite and Band C, mostly sub-parallel to the unconformity and confined to basal conglomerate/grit horizon except a few boreholes where it is transgressing to granitic horizon (2 (upto 2.00 %), ThO2 (0.03 to 1.51 %) and RE2O3 (0.12 to 3.56 %). Such activities signify the processes of epigenetic fluid/gel related to U-concentration. At increasing depths, possibility of AI- bearing radioactive phases is also envisaged. The radioactive phases present in the samples reveal negligible to low thorium indicating low temperature phenomena. They are likely to be emplaced by the epigenetic solution/gel rich in U, Ti, Si, AI, Ca, P and Pb, preferably along available spaces as vein, cavity and grain boundary. U-associated sulphides occurring as veins and fracture fills, essentially comprise pyrite, pyrrhotite, chalcopyrite, pentlandite and galena. They have normal chemistry but for subtle variations in minor elements. The pyrite and pyrrhotite are invariably arseniferous and they dominate the sulphides. Thus, it is concluded that the area has potential for multi-episodic epigenetic U-mineralization

  16. Relation between water chemistry and operational safety

    International Nuclear Information System (INIS)

    This report describes the relation between chemistry/radiochemistry and operational safety, the technics bases for chemical and radiochemical parameters and an analysis of the Annual Report of Angra I Operation and OSRAT Mission report to 1989 in this area too. Furthermore it contains the transcription of the technical Specifications related to the chemistry and radiochemistry for Angra I. (author)

  17. Gas phase chemistry studies of superheavy elements

    International Nuclear Information System (INIS)

    The present status of the chemical properties investigation for superheavy elements was described in this paper. The synthesis of superheavy elements and the experimental techniques used in studies on the gas phase chemistry of superheavy elements were briefly introduced. The current experimental studies about the gas-chromatography of Rf, Db, Sg, Bh, Hs and element 112 were discussed in detail. Finally, the development of synthesis of superheavy elements and the study on gas phase chemical properties of superheavy elements in China were prospected. (authors)

  18. Phase Chemistry of Tank Sludge Residual Components

    Energy Technology Data Exchange (ETDEWEB)

    KRUMHANSL,JAMES L.; LIU,JUN; NAGY,KATHRYN L.; BRADY,PATRICK V.

    1999-11-29

    We are attempting to understand the solid phase chemistry of the high level nuclear waste (HLW) stored in tanks at Hanford. Because this waste is compositionally complex, our approach is to study experimentally the aging dynamics of simplified systems whose bulk chemistry approximates that of the tank sludges. After a basic understanding of these dynamics has been attained we plan to increase the compositional complexities one component at a time, in order to assess the influence of each component. Results will allow for reliable prediction of sludge phase chemistry over a range of sludge compositions. Iron and aluminum comprise the bulk of most HLW sludges, so we chose to begin by studying the behavior of iron-aluminum systems. Fe/Al ratios were chosen to approximate those relevant to the solutions that produced the sludge. Aluminum and iron concentrations in the various process fluids are summarized and compared to our experimental starting solutions in Table 1 (process solution data from Krumhansl, personal communication, 1998). Our low aluminum experiments serve as direct analogues to both Bismuth Phosphate and low-Fe PUREX waste. Cornell and Giovanoli (1985) found that, in a pure iron system at 70 C, a 10-fold or even 50-fold increase in suspension concentration had only very slight effects on the final aged products. Since our experiments have similar Al/Fe ratios to some high Fe-PUREX process solutions our results are probably relevant to those wastes as well. However, our results may not apply to the high-Fe and high-Al PUREX wastes, as discussed below. The high Al experiments were designed specifically to simulate REDOX waste.

  19. In-situ ambient quantification of monoterpenes, sesquiterpenes, and related oxygenated compounds during BEARPEX 2007: implications for gas- and particle-phase chemistry

    Science.gov (United States)

    Bouvier-Brown, N. C.; Goldstein, A. H.; Gilman, J. B.; Kuster, W. C.; de Gouw, J. A.

    2009-08-01

    We quantified ambient mixing ratios of 9 monoterpenes, 6 sesquiterpenes, methyl chavicol, the oxygenated terpene linalool, and nopinone using an in-situ gas chromatograph with a quadrupole mass spectrometer (GC-MS). These measurements were a part of the 2007 Biosphere Effects on AeRosols and Photochemistry EXperiment (BEARPEX) at Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. To our knowledge, these observations represent the first direct in-situ ambient quantification of the sesquiterpenes α-bergamotene, longifolene, α-farnesene, and β-farnesene. From average diurnal mixing ratio profiles, we show that α-farnesene emissions are dependent mainly on temperature whereas α-bergamotene and β-farnesene emissions are temperature- and light-dependent. The amount of sesquiterpene mass quantified above the canopy was small (averaging a total of 3.3 ppt during the day), but nevertheless these compounds contributed 7.6% to the overall ozone-olefin loss rate above the canopy. Assuming that the monoterpene-to-sesquiterpene emission rate in the canopy is similar to that observed in branch enclosure studies at the site during comparable weather conditions, and the average yield of aerosol mass from these sesquiterpenes is 10-50%, the amount of sesquiterpene mass reacted within the Blodgett Forest canopy alone accounts for 6-32% of the total organic aerosol mass measured during BEARPEX. The oxygenated monoterpene linalool was also quantified for the first time at Blodgett Forest. The linalool mass contribution was small (9.9 ppt and 0.74 ppt within and above the canopy, respectively), but it contributed 1.1% to the total ozone-olefin loss rate above the canopy. Reactive and semi-volatile compounds, especially sesquiterpenes, significantly impact the gas- and particle-phase chemistry of the atmosphere at Blodgett Forest and should be included in both biogenic volatile organic carbon emission and atmospheric chemistry models.

  20. In-situ ambient quantification of monoterpenes, sesquiterpenes, and related oxygenated compounds during BEARPEX 2007 – implications for gas- and particle-phase chemistry

    Directory of Open Access Journals (Sweden)

    N. C. Bouvier-Brown

    2009-04-01

    Full Text Available We quantified ambient mixing ratios of 9 monoterpenes, 6 sesquiterpenes, methyl chavicol, the oxygenated terpene linalool, and nopinone using an in-situ gas chromatograph with a quadrupole mass spectrometer (GC-MS. These measurements were a part of the 2007 Biosphere Effects on AeRosols and Photochemistry EXperiment (BEARPEX at Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. To our knowledge, these observations represent the first direct in-situ ambient quantification of the sesquiterpenes α-bergamotene, longifolene, α-farnesene, and β-farnesene. From average diurnal mixing ratio profiles, we show that α-farnesene emissions are dependent mainly on temperature whereas α-bergamotene and β-farnesene emissions are temperature- and light-dependent. The amount of sesquiterpene mass quantified above the canopy was small (averaging a total of 3.3 ppt during the day, but nevertheless these compounds contributed 8.5% to the overall ozone reactivity above the canopy. Assuming that the monoterpene-to-sesquiterpene emission rate in the canopy is similar to that observed in branch enclosure studies at the site during comparable weather conditions, and the average yield of aerosol mass from these sesquiterpenes is 10–50%, the amount of sesquiterpene mass reacted within the Blodgett Forest canopy alone accounts for 8–38% of the total organic aerosol mass measured during BEARPEX. The oxygenated monoterpene linalool was also quantified for the first time at Blodgett Forest. The linalool mass contribution was small (9.9 ppt and 0.74 ppt within and above the canopy, respectively, but it contributed 1.2% to the total ozone reactivity above the canopy. Reactive and semi-volatile compounds, especially sesquiterpenes, significantly impact the gas- and particle-phase chemistry of the atmosphere at Blodgett Forest and should be included in both biogenic volatile organic carbon emission and atmospheric chemistry models.

  1. In-situ ambient quantification of monoterpenes, sesquiterpenes, and related oxygenated compounds during BEARPEX 2007: implications for gas- and particle-phase chemistry

    Directory of Open Access Journals (Sweden)

    N. C. Bouvier-Brown

    2009-08-01

    Full Text Available We quantified ambient mixing ratios of 9 monoterpenes, 6 sesquiterpenes, methyl chavicol, the oxygenated terpene linalool, and nopinone using an in-situ gas chromatograph with a quadrupole mass spectrometer (GC-MS. These measurements were a part of the 2007 Biosphere Effects on AeRosols and Photochemistry EXperiment (BEARPEX at Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. To our knowledge, these observations represent the first direct in-situ ambient quantification of the sesquiterpenes α-bergamotene, longifolene, α-farnesene, and β-farnesene. From average diurnal mixing ratio profiles, we show that α-farnesene emissions are dependent mainly on temperature whereas α-bergamotene and β-farnesene emissions are temperature- and light-dependent. The amount of sesquiterpene mass quantified above the canopy was small (averaging a total of 3.3 ppt during the day, but nevertheless these compounds contributed 7.6% to the overall ozone-olefin loss rate above the canopy. Assuming that the monoterpene-to-sesquiterpene emission rate in the canopy is similar to that observed in branch enclosure studies at the site during comparable weather conditions, and the average yield of aerosol mass from these sesquiterpenes is 10–50%, the amount of sesquiterpene mass reacted within the Blodgett Forest canopy alone accounts for 6–32% of the total organic aerosol mass measured during BEARPEX. The oxygenated monoterpene linalool was also quantified for the first time at Blodgett Forest. The linalool mass contribution was small (9.9 ppt and 0.74 ppt within and above the canopy, respectively, but it contributed 1.1% to the total ozone-olefin loss rate above the canopy. Reactive and semi-volatile compounds, especially sesquiterpenes, significantly impact the gas- and particle-phase chemistry of the atmosphere at Blodgett Forest and should be included in both biogenic volatile organic carbon emission and atmospheric chemistry

  2. Hydrocarbon radical thermochemistry: Gas-phase ion chemistry techniques

    Energy Technology Data Exchange (ETDEWEB)

    Ervin, Kent M. [Univ. of Nevada, Reno, NV (United States)

    2014-03-21

    Final Scientific/Technical Report for the project "Hydrocarbon Radical Thermochemistry: Gas-Phase Ion Chemistry Techniques." The objective of this project is to exploit gas-phase ion chemistry techniques for determination of thermochemical values for neutral hydrocarbon radicals of importance in combustion kinetics.

  3. Heterogenous phase as a mean in combinatorial chemistry

    International Nuclear Information System (INIS)

    Combinatorial chemistry is a rapid and inexpensive technique for the synthesis of hundreds of thousands of organic compounds of potential medicinal activity. In the past few decades a large number of combinatorial libraries have been constructed, and significantly supplement the chemical diversity of the traditional collections of the potentially active medicinal compounds. Solid phase synthesis was used to enrich the combinatorial chemistry libraries, through the use of solid supports (resins) and their modified forms. Most of the new libraries of compounds appeared recently, were synthesized by the use of solid-phase. Solid-phase combinatorial chemistry (SPCC) is now considered as an outstanding branch in pharmaceutical chemistry research and used extensively as a tool for drug discovery within the context of high-throughput chemical synthesis. The best pure libraries synthesized by the use of solid phase combinatorial chemistry (SPCC) may well be those of intermediate complexity that are free of artifact-causing nuisance compounds. (author)

  4. Structure, crystal chemistry and thermal evolution of the δ-Bi2O3-related phase Bi9ReO17

    International Nuclear Information System (INIS)

    The thermal evolution and structural properties of fluorite-related δ-Bi2O3-type Bi9ReO17 were studied with variable temperature neutron powder diffraction, synchrotron X-ray powder diffraction and electron diffraction. The thermodynamically stable room-temperature crystal structure is monoclinic P21/c, a=9.89917(5), b=19.70356(10), c=11.61597(6) A, β=125.302(2)o (Rp=3.51%, wRp=3.60%) and features clusters of ReO4 tetrahedra embedded in a distorted Bi-O fluorite-like network. This phase is stable up to 725 deg. C whereupon it transforms to a disordered δ-Bi2O3-like phase, which was modeled with δ-Bi2O3 in cubic Fm3-barm with a=5.7809(1) A (Rp=2.49%, wRp=2.44%) at 750 deg. C. Quenching from above 725 deg. C leads to a different phase, the structure of which has not been solved but appears on the basis of spectroscopic evidence to contain both ReO4 tetrahedra and ReO6 octahedra. - Abstract: The crystal structure of Bi9ReO17 viewed along the [101] direction. Bi atoms and bonds are light gray, O atoms and bonds are black and ReO4 are represented by gray tetrahedra. Display Omitted

  5. Gas Phase Sulfur, Chlorine and Potassium Chemistry in Biomass Combustion

    DEFF Research Database (Denmark)

    Løj, Lusi Hindiyarti

    2007-01-01

    Gas Phase Sulfur, Chlorine and Alkali Metal Chemistry in Biomass Combustion Concern about aerosols formation, deposits, corrosion, and gaseous emissions during biomass combustion, especially straw, continues to be a driving force for investigation on S, Cl, K-containing species under combustions...... uncertainties. In the present work, the detailed kinetic model for gas phase sulfur, chlorine, alkali metal, and their interaction has been updated. The K/O/H/Cl chemistry, S chemistry, and their interaction can reasonably predict a range of experimental data. In general, understanding of the interaction...... sulfur chemistry important for the SO2/SO3 ratio under combustion conditions has been updated. The uncertainties of the important rate constants have been minimized. Modeling predictions with a revised reaction mechanism for SO2/SO3 chemistry are in a good agreement with a range of experimental data from...

  6. The geometric phase controls ultracold chemistry

    International Nuclear Information System (INIS)

    In this study, the geometric phase is shown to control the outcome of an ultracold chemical reaction. The control is a direct consequence of the sign change on the interference term between two scattering pathways (direct and looping), which contribute to the reactive collision process in the presence of a conical intersection (point of degeneracy between two Born-Oppenheimer electronic potential energy surfaces). The unique properties of the ultracold energy regime lead to an effective quantization of the scattering phase shift enabling maximum constructive or destructive interference between the two pathways. By taking the O + OH → H + O2 reaction as an illustrative example, it is shown that inclusion of the geometric phase modifies ultracold reaction rates by nearly two orders of magnitude. Interesting experimental control possibilities include the application of external electric and magnetic fields that might be used to exploit the geometric phase effect reported here and experimentally switch on or off the reactivity

  7. An overview of peat related chemistry

    OpenAIRE

    Guan, Ting

    2015-01-01

    Peat is a type of renewable resource that has usually been ignored. Nowadays, people mainly apply peat as the heating energy resource instead of other purposes. This thesis elaborates many studies such as peat used in chemistry, which were utilized by researchers, and the product has been made according to special characteristics of peat. The aim of thesis is to give a summary of the achievement of research, which had been studied of peat that applied in chemistry. Eight studies of peat- r...

  8. Phase Chemistry of Tank Sludge Residual Components

    International Nuclear Information System (INIS)

    The US Department of Energy (DOE) has millions of gallons of high level nuclear waste stored in underground tanks at Hanford, Washington and Savannah River, South Carolina. These tanks will eventually be emptied and decommissioned. This will leave a residue of sludge adhering to the interior tank surfaces that may contaminate nearby groundwaters with radionuclides and RCRA metals. Performance assessment (PA) calculations must be carried out prior to closing the tanks. This requires developing radionuclide release models from the sludges so that the PA calculations can be based on credible source terms. These efforts continued to be hindered by uncertainties regarding the actual nature of the tank contents and the distribution of radionuclides among the various phases. In particular, it is of vital importance to know what radionuclides are associated with solid sludge components. Experimentation on actual tank sludges can be difficult, dangerous and prohibitively expensive. The research funded under this grant for the past three years was intended to provide a cost-effective method for developing the needed radionuclide release models using non-radioactive artificial sludges. Insights gained from this work will also have more immediate applications in understanding the processes responsible for heel development in the tanks and in developing effective technologies for removing wastes from the tanks

  9. A Closer Look at Phase Diagrams for the General Chemistry Course.

    Science.gov (United States)

    Gramsch, Stephen A.

    2000-01-01

    Information concerning structural chemistry and phase equilibria contained in the full phase diagrams of common substances is a great deal richer than the general chemistry students are given to believe. Discusses ways of enriching the traditional presentation of phase diagrams in general chemistry courses. (Contains over 20 references.) (WRM)

  10. Advances in solid-phase extraction disks for environmental chemistry

    Science.gov (United States)

    Thurman, E.M.; Snavely, K.

    2000-01-01

    The development of solid-phase extraction (SPE) for environmental chemistry has progressed significantly over the last decade to include a number of new sorbents and new approaches to SPE. One SPE approach in particular, the SPE disk, has greatly reduced or eliminated the use of chlorinated solvents for the analysis of trace organic compounds. This article discusses the use and applicability of various SPE disks, including micro-sized disks, prior to gas chromatography-mass spectrometry for the analysis of trace organic compounds in water. Copyright (C) 2000 Elsevier Science B.V.

  11. Exploring the Random Phase Approximately for materials chemistry and physics

    Energy Technology Data Exchange (ETDEWEB)

    Ruzsinsky, Adrienn [Temple University, Philadelphia, PA (United States)

    2015-03-23

    This proposal focuses on improved accuracy for the delicate energy differences of interest in materials chemistry with the fully nonlocal random phase approximation (RPA) in a density functional context. Could RPA or RPA-like approaches become standard methods of first-principles electronic-structure calculation for atoms, molecules, solids, surfaces, and nano-structures? Direct RPA includes the full exact exchange energy and a nonlocal correlation energy from the occupied and unoccupied Kohn-Sham orbitals and orbital energies, with an approximate but universal description of long-range van der Waals attraction. RPA also improves upon simple pair-wise interaction potentials or vdW density functional theory. This improvement is essential to capture accurate energy differences in metals and different phases of semiconductors. The applications in this proposal are challenges for the simpler approximations of Kohn-Sham density functional theory, which are part of the current “standard model” for quantum chemistry and condensed matter physics. Within this project we already applied RPA on different structural phase transitions on semiconductors, metals and molecules. Although RPA predicts accurate structural parameters, RPA has proven not equally accurate in all kinds of structural phase transitions. Therefore a correction to RPA can be necessary in many cases. We are currently implementing and testing a nonempirical, spatially nonlocal, frequency-dependent model for the exchange-correlation kernel in the adiabatic-connection fluctuation-dissipation context. This kernel predicts a nearly-exact correlation energy for the electron gas of uniform density. If RPA or RPA-like approaches prove to be reliably accurate, then expected increases in computer power may make them standard in the electronic-structure calculations of the future.

  12. REACTION CHEMISTRY RELATED TO FCC GASOLINE QUALITY

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    About 80% of the gasoline pool as a whole in China for supplying the domestic market at current stage directly originates from FCC units. Obviously, FCC gasoline quality is critical for refiners to meet the nations more and more stringent gasoline specifications. FCC process is expected to produce gasoline with reduced contents of olefins, aromatics, benzene, sulfur, and, contradictorily, still with high octane number.   Catalytic cracking process involves a series of acid catalyzed reactions. Bronsted acid sites dominate the surface of the catalyst used for FCC process. All the reactions of hydrocarbons in FCC process are based on carbonium ions of penta-coordinated, or carbenium ions of tri-coordinated. The monomolecular beta scission mechanism for alkane cracking explains that the cracking of carbon-carbon bonding occurs at the beta position to the carbon atom bearing positive charge, and hence forms two small hydrocarbon molecules: one alkane molecule and one olefin molecule. The molar ratio of alkane to olefin for the primary cracking product will be 1 and it will be less than 1 if the cracking reaction proceeds.   However, it is proved that bimolecular reaction pathways exist between surface carbenium ions and the feed molecules. The products of this bimolecular disproportionation reaction could be an alkane molecule and a newly formed carbenium ion. The better understanding of the reaction chemistry of FCC process based on monomolecular pathways and bimolecular pathways should be the basis for searching approaches to the improvement of FCC gasoline quality. In the complicated reaction scheme of the FCC process, the isomerization reaction leading to the formation of iso-alkanes is obviously a target reaction, which favors both olefin reduction and octane enhancement.   The cracking of small paraffin molecules, due to its limited number of reaction pathways and products, has been used to investigate cracking mechanism. In the present work the

  13. Verbal, Numerical and Perceptual Skills Related to Chemistry Achievement.

    Science.gov (United States)

    Bodner, George M.; And Others

    The relationship between students' relative ability in visual-spatial tasks as well as their verbal and numerical skills to their performance in an introductory college chemistry course was investigated. For 700 subjects, verbal and mathematics Scholastic Aptitude Test scores (SAT-V) and (SAT-M) and the following four perceptual tests were…

  14. Chemistry

    International Nuclear Information System (INIS)

    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 UF3 and dissolved UF4, and, in some cases, between the dissolved uranium fluorides and graphite, and the UC2. Several aspects of coolant-salt chemistry are under investigation. Hydroxy and oxy compounds that could be formed in molten NaBF4 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 U4+/U3+ ratios in fuel salt was tested in a forced-convection loop over a six-month period. (LK)

  15. Phase chemistry of tank sludge residual components. 1998 annual progress report

    International Nuclear Information System (INIS)

    'The proposed research will provide a scientific basis for predicting the long-term fate of radionuclides remaining with the sludge in decommissioned waste tanks. Nuclear activities in the United States and elsewhere produce substantial volumes of highly radioactive semi-liquid slurries that traditionally are stored in large underground tanks while final waste disposal strategies are established. Although most of this waste will eventually be reprocessed a contaminated structure will remain which must either be removed or decommissioned in place. To accrue the substantial savings associated with in-place disposal will require a performance assessment which, in turn, means predicting the leach behavior of the radionuclides associated with the residual sludges. The phase chemistry of these materials is poorly known so a credible source term cannot presently be formulated. Further, handling of actual radioactive sludges is exceedingly cumbersome and expensive. This proposal is directed at: (1) developing synthetic nonradioactive sludges that match wastes produced by the various fuel processing steps, (2) monitoring the changes in phase chemistry of these sludges as they age, and (3) relating the mobility of trace amounts of radionuclides (or surrogates) in the sludge to the phase changes in the aging wastes. This report summarizes work carried out during the first year of a three year project. A prerequisite to performing a meaningful study was to learn in considerable detail about the chemistry of waste streams produced by fuel reprocessing. At Hanford this is not a simple task since over the last five decades four different reprocessing schemes were used: the early BiPO4 separation for just Pu, the U recovery activity to further treat wastes left by the BiPO4 activities, the REDOX process and most recently, the PUREX processes. Savannah River fuel reprocessing started later and only PUREX wastes were generated. It is the working premise of this proposal that most of

  16. Postperovskite phase transition of ZnGeO3: comparative crystal chemistry of postperovskite phase transition from germanate perovskites.

    Science.gov (United States)

    Yusa, Hitoshi; Tsuchiya, Taku; Akaogi, Masaki; Kojitani, Hiroshi; Yamazaki, Daisuke; Hirao, Naohisa; Ohishi, Yasuo; Kikegawa, Takumi

    2014-11-01

    The postperovskite phase of ZnGeO3 was confirmed by laser heating experiments of the perovskite phase under 110-130 GPa at high temperature. Ab initio calculations indicated that the phase transition occurs at 133 GPa at 0 K. This postperovskite transition pressure is significantly higher than those reported for other germanates, such as MnGeO3 and MgGeO3. The comparative crystal chemistry of the perovskite-to-postperovskite transition suggests that a relatively elongated b-axis in the low-pressure range resulted in the delay in the transition to the postperovskite phase. Similar to most GdFeO3-type perovskites that transform to the CaIrO3-type postperovskite phase, ZnGeO3 perovskite eventually transformed to the CaIrO3-type postperovskite phase at a critical rotational angle of the GeO6 octahedron. The formation of the postperovskite structure at a very low critical rotational angle for MnGeO3 suggests that relatively large divalent cations likely break down the corner-sharing GeO6 frameworks without a large rotation of GeO6 to form the postperovskite phase. PMID:25310272

  17. Crystal chemistry of sartorite homologues and related sulfosalts

    DEFF Research Database (Denmark)

    Berlepsch, Peter; Makovicky, Emil; Balic-Zunic, Tonci

    2001-01-01

    sartorite homologues, sulfosalt, crystal chemistry, coordination polyhedra, bond-pairs, crankshaft chains......sartorite homologues, sulfosalt, crystal chemistry, coordination polyhedra, bond-pairs, crankshaft chains...

  18. Phase chemistry of the system Nb–Rh–O

    International Nuclear Information System (INIS)

    Phase relations in the system Nb–Rh–O at 1223 K were investigated by isothermal equilibration of eleven compositions and analysis of quenched samples using OM, XRD, SEM and EDS. The oxide phase in equilibrium with the alloy changes progressively from NbO to NbO2, NbO2.422 and Nb2O5−x with increasing Rh. Only one ternary oxide NbRhO4 with tetragonal structure (a=0.4708 nm and c=0.3017 nm) was detected. It coexists with Rh and Nb2O5. The standard Gibbs energy of formation of NbRhO4 from its component binary oxides measured using a solid-state electrochemical cell can be represented by the equation; ΔGf,oxo(J/mol)=−38,350+5.818×T(±96) Constructed on the basis of thermodynamic information of the various alloy and oxide phases are oxygen potential diagram for the system Nb–Rh–O at 1223 K and temperature–composition diagrams at constant partial pressures of oxygen. - Graphical abstract: Isothermal section of ternary phase diagram for the system Nb–Rh–O at 1223 K. - Highlights: • First complete isothermal section for the system Nb–Rh–O has been established. • An electrochemical cell is used to measure the thermodynamic properties of NbRhO4. • Oxygen potential diagram at 1223 K is computed from thermodynamic data. • Temperature–composition diagrams at constant oxygen partial pressures. • A complete thermodynamic characterization of the system Nb–Rh–O is presented

  19. Fast, copper-free click chemistry: a convenient solid-phase approach to oligonucleotide conjugation

    OpenAIRE

    Singh, Ishwar; Vyle, Joseph S.; Heaney, Frances

    2009-01-01

    Solid-phase oligonucleotide conjugation by nitrile oxide–alkyne click cycloaddition chemistry has been successfully demonstrated; the reaction, compatible with all nucleobases, requires no metal catalyst and proceeds under physiological conditions.

  20. Insight into solution chemistry from gas-phase experiments

    Czech Academy of Sciences Publication Activity Database

    Agrawal, Divya; Schröder, Detlef

    2011-01-01

    Roč. 30, č. 1 (2011), s. 32-35. ISSN 0276-7333 Grant ostatní: European Research Council(XE) AdG HORIZOMS Institutional research plan: CEZ:AV0Z40550506 Keywords : catalysis * electrospray ionization * mass spectrometry * organometallics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.963, year: 2011

  1. Relative effect of solder flux chemistry on the humidity related failures in electronics

    DEFF Research Database (Denmark)

    Verdingovas, Vadimas; Jellesen, Morten Stendahl; Ambat, Rajan

    2015-01-01

    Purpose - This paper aims to investigate the effect of no-clean flux chemistry with various weak organic acids (WOAs) as activators on the corrosion reliability of electronics with emphasis on the hygroscopic nature of the residue. Design/methodology/approach - The hygroscopicity of flux residue...... in the impedance measurements were observed. Practical implications - The findings are attributed to the deliquescence RH of the WOA(s) in the flux and chemistry of water-layer formation. The results show the importance of WOA type in relation to its solubility and deliquescence RH on the corrosion reliability...... selecting no-clean flux systems for electronics with applications in humid conditions....

  2. Host-Guest Chemistry of Dendrimers in the Gas Phase

    OpenAIRE

    Qi, Zhenhui; Schalley, Christoph A

    2010-01-01

    Abstract Since the early days of dendrimer chemistry, mass spectrometry has been an important analytical method for determining the purity and the detection of defects in dendrimers. Meanwhile, growing evidence demonstrates the great potential of mass spectrometry for the investigation of non-covalent dendritic host-guest complexes. Mass spectrometry provides an efficient means to isolate them in the high vacuum inside a mass spectrometer under environment-free conditions. Gas-phas...

  3. Preserving scientific heritage. Prague monuments related to history of chemistry

    Czech Academy of Sciences Publication Activity Database

    Štrbáňová, Soňa

    2011. Roč. 106, S /Special Issue/ (2012), s. 621. ISSN 1803-2389. [EuCheMS Chemistry Congress /4./. 26.08.2012-30.08.2012, Prague] Institutional support: RVO:68378114 Keywords : history of science * history of chemistry * science and culture Subject RIV: AB - History

  4. Plasma induced liquid phase chemistry and diagnostic challenges

    Czech Academy of Sciences Publication Activity Database

    Lukeš, Petr

    Leiden : Lorentz Center, 2014 - (Bruggeman, P.; Kushner, M.; Locke, B.) ISBN N. [Workshop on Gas/Plasma-Liquid Interface: Transport, Chemistry and Fundamental Data. Leiden (NL), 04.08.2014-08.08.2014] R&D Projects: GA MŠk(CZ) LD14080 Grant ostatní: European Cooperation in Science and Technology(XE) COST TD1208 Source of funding: R - rámcový projekt EK Keywords : plasma–liquid interactions * plasmachemistry * chemical diagnostics in water Subject RIV: BL - Plasma and Gas Discharge Physics http://lorentzcenter.nl/lc/web/2014/637/info.php3?wsid=637&venue=Oort

  5. Development and evaluation of the aerosol dynamic and gas phase chemistry model ADCHEM

    Directory of Open Access Journals (Sweden)

    P. Roldin

    2010-08-01

    Full Text Available The aim of this work was to develop a model ideally suited for detailed studies on aerosol dynamics, gas and particle phase chemistry within urban plumes, from local scale (1×1 km2 to regional or global scale. This article describes and evaluates the trajectory model for Aerosol Dynamics, gas and particle phase CHEMistry and radiative transfer (ADCHEM, which has been developed and used at Lund University since 2007. The model treats both vertical and horizontal dispersion perpendicular to an air mass trajectory (2-space dimensions, which is not treated in Lagrangian box-models (0-space dimensions. The Lagrangian approach enables a more detailed representation of the aerosol dynamics, gas and particle phase chemistry and a finer spatial and temporal resolution compared to that of available regional 3D-CTMs. These features make it among others ideally suited for urban plume studies. The aerosol dynamics model includes Brownian coagulation, dry deposition, wet deposition, in-cloud processing, condensation, evaporation, primary particle emissions and homogeneous nucleation. The gas phase chemistry model calculates the gas phase concentrations of 63 different species, using 119 different chemical reactions. Daily isoprene and monoterpene emissions from European forests were simulated separately with the vegetation model LPJ-GUESS, and included as input to ADCHEM. ADCHEM was used to simulate the ageing of the urban plumes from the city of Malmö in Southern Sweden (280 000 inhabitants. Several sensitivity tests were performed concerning the number of size bins, size structure method, coupled or uncoupled condensation, the volatility basis set (VBS or traditional 2-product model for secondary organic aerosol formation, different aerosol dynamic processes and vertical and horizontal mixing. The simulations show that the full-stationary size structure gives accurate results with little numerical diffusion when more than 50 size bins are used

  6. Simultaneous assessment of phase chemistry, phase abundance and bulk chemistry with statistical electron probe micro-analyses: Application to cement clinkers

    International Nuclear Information System (INIS)

    According to recent developments in cement clinker engineering, the optimization of chemical substitutions in the main clinker phases offers a promising approach to improve both reactivity and grindability of clinkers. Thus, monitoring the chemistry of the phases may become part of the quality control at the cement plants, along with the usual measurements of the abundance of the mineralogical phases (quantitative X-ray diffraction) and the bulk chemistry (X-ray fluorescence). This paper presents a new method to assess these three complementary quantities with a single experiment. The method is based on electron microprobe spot analyses, performed over a grid located on a representative surface of the sample and interpreted with advanced statistical tools. This paper describes the method and the experimental program performed on industrial clinkers to establish the accuracy in comparison to conventional methods. -- Highlights: •A new method of clinker characterization •Combination of electron probe technique with cluster analysis •Simultaneous assessment of phase abundance, composition and bulk chemistry •Experimental validation performed on industrial clinkers

  7. Magnetization of exsolution intergrowths of hematite and ilmenite: Mineral chemistry, phase relations, and magnetic properties of hemo-ilmenite ores with micron- to nanometer-scale lamellae from Allard Lake, Quebec

    DEFF Research Database (Denmark)

    McEnroe, S.A.; Robinson, P.; Langenhorst, F.;

    2007-01-01

    shows thermal unblocking similar to 595 -620 degrees C, was acquired during final exsolution in the two-phase region canted antiferromagnetic R(3) over bar c hematite + R (3) over bar ilmenite. Hysteresis measurements show a very strong anisotropy, with a stronger coercivity normal to, than parallel to...

  8. Partitioning of metals in different binding phases of tropical estuarine sediments: importance of metal chemistry

    Digital Repository Service at National Institute of Oceanography (India)

    Chakraborty, P.; Chakraborty, S.; Vudamala, K.; Sarkar, Arindam; Nath, B.N.

    1    Aurhor Version: Environ. Sci. Pollut. Res., vol.23(4); 2016; 3450-3462 Partitioning of metals in different binding phases of tropical estuarine sediments: Importance of metal chemistry P. Chakraborty1*, Sucharita Chakraborty1, Krushna... to predict the source rock of the sediments by looking at the residual metal percentages in the sediments (Forstner and Stoffers, 1981). However, there are only few studies that have attempted to understand the influences of metal chemistry on metal...

  9. Chemistry

    International Nuclear Information System (INIS)

    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 Te2 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 NaBF4 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, Na3CrF6 and Na5Cr3F14, 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 Li2BeF4 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 Fe2+ and Cr3+ and the determination of the U3+/U4+ ratio in MSBR fuel salt. Similar studies were conducted with the NaBF4--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 NaBF4--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)

  10. Application of acute phase protein measurements in veterinary clinical chemistry

    DEFF Research Database (Denmark)

    Petersen, Henning; Nielsen, J. P.; Heegaard, Peter M. H.

    2004-01-01

    The body's early defence in response to trauma, inflammation or infection, the acute phase response, is a complex set of systemic reactions seen shortly after exposure to a triggering event. One of the many components is an acute phase protein response in which increased hepatic synthesis leads to...... possible use as non-specific indicators of health in large animal veterinary medicine such as in the health status surveillance of pigs at the herd level, for the detection of mastitis in dairy cattle and for the prognosis of respiratory diseases in horses....

  11. Application of acute phase protein measurements in veterinary clinical chemistry

    DEFF Research Database (Denmark)

    Petersen, Henning; Nielsen, J. P.; Heegaard, Peter M. H.

    2004-01-01

    The body's early defence in response to trauma, inflammation or infection, the acute phase response, is a complex set of systemic reactions seen shortly after exposure to a triggering event. One of the many components is an acute phase protein response in which increased hepatic synthesis leads t...... possible use as non-specific indicators of health in large animal veterinary medicine such as in the health status surveillance of pigs at the herd level, for the detection of mastitis in dairy cattle and for the prognosis of respiratory diseases in horses....

  12. Phase Chemistry of the Complexes of RE Amino Acids

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Forty-three phase diagrams of ternary system concerning rare earth salts, α-amino acids and water, which were constructed by phase equilibrium methods, were expounded. The influences of the factors such as cations, anions, the structure of amino acids, temperature on the phase diagrams were discussed. Under the guidance of phase equilibrium results, over 150 new solid complexes were prepared. IR, reflecting, UV, FS, and Raman spectra for these complexes were investigated and the regularity of “tripartite effect”, “tetrad effect”, “Nephelanxetic effect”, “Oddo-Harkins” was observed. Thermal decomposition processes of the complexes were confirmed. Based on the comparison with the known crystal structures of rare earth-amino acid-complexes, an estimation method for predicting the crystal structure data of series complexes was founded. The constant volume combustion energies of the complexes were determined by RBC-1 type rotating bomb calorimeter. The standard enthalpies of combustion and standard enthalpies of formation were calculated for these complexes.

  13. Importance of Geometric Phase Effects in Ultracold Chemistry.

    Science.gov (United States)

    Hazra, Jisha; Kendrick, Brian K; Balakrishnan, Naduvalath

    2015-12-17

    It is demonstrated that the inclusion of the geometric phase has an important effect on ultracold chemical reaction rates. The effect appears in rotationally and vibrationally resolved integral cross sections as well as cross sections summed over all product quantum states. The effect arises from interference between scattering amplitudes of two reaction pathways: a direct path and a looping path that encircle the conical intersection between the two lowest adiabatic electronic potential energy surfaces. It is magnified when the two scattering amplitudes have comparable magnitude and they scatter into the same angular region which occurs in the isotropic scattering characteristic of the ultracold regime (s-wave scattering). Results are presented for the O + OH → H + O2 reaction for total angular momentum quantum number J = 0-5. Large geometric phase effects occur for collision energies below 0.1 K, but the effect vanishes at higher energies when contributions from different partial waves are included. It is also qualitatively demonstrated that the geometric phase effect can be modulated by applying an external electric field allowing the possibility of quantum control of chemical reactions in the ultracold regime. In this case, the geometric phase plays the role of a "quantum switch" which can turn the reaction "on" or "off". PMID:26317912

  14. Gender Differences in Cognitive and Noncognitive Factors Related to Achievement in Organic Chemistry

    Science.gov (United States)

    Turner, Ronna C.; Lindsay, Harriet A.

    2003-05-01

    For many college students in the sciences, organic chemistry poses a difficult challenge. Indeed, success in organic chemistry has proven pivotal in the careers of a vast number of students in a variety of science disciplines. A better understanding of the factors that contribute to achievement in this course should contribute to efforts to increase the number of students in the science disciplines. Further, an awareness of gender differences in factors associated with achievement should aid efforts to bolster the participation of women in chemistry and related disciplines. Using a correlation research design, the individual relationships between organic chemistry achievement and each of several cognitive variables and noncognitive variables were assessed. In addition, the relationships between organic chemistry achievement and combinations of these independent variables were explored. Finally, gender- and instructor-related differences in the relationships between organic chemistry achievement and the independent variables were investigated. Cognitive variables included the second-semester general chemistry grade, the ACT English, math, reading, and science-reasoning scores, and scores from a spatial visualization test. Noncognitive variables included anxiety, confidence, effectance motivation, and usefulness. The second-semester general chemistry grade was found to be the best indicator of performance in organic chemistry, while the effectiveness of other predictors varied between instructors. In addition, gender differences were found in the explanations of organic chemistry achievement variance provided by this study. In general, males exhibited stronger correlations between predictor variables and organic chemistry achievement than females.

  15. Towards a more detailed description of tropospheric aqueous phase organic chemistry: CAPRAM 3.0

    Science.gov (United States)

    Herrmann, H.; Tilgner, A.; Barzaghi, P.; Majdik, Z.; Gligorovski, S.; Poulain, L.; Monod, A.

    CAPRAM 3.0 is the latest development of the chemical aqueous phase radical mechanism (CAPRAM) series which is incorporating CAPRAM 2.4 (Ervens et al., 2003a, Journal of Geophysical Research—Atmospheres 108) and a new extended reaction mechanism for atmospherically relevant hydrocarbons containing more than two and up to six carbon atoms. The chemistry of organics containing three and four carbon atoms is now described in detail. Almost 400 new reactions are now implemented considering the chemistry of organic compounds containing different functional groups, i.e. alcohols, carbonyl compounds, mono- and dicarboxylic acids, polyfunctional compounds as well as some esters and one heterocyclic compound. The aqueous chemistry has been coupled to the gas phase mechanism RACM (regional atmospheric chemistry modeling) (Stockwell et al., 1997, Journal of Geophysical Research—Atmpspheres 102, 25847-25879), and phase exchange is treated using the resistance model of Schwartz (1986. In: Jaeschke, W. (Ed.), Chemistry of Multiphase Atmospheric Systems, NATO ASI Series, Springer, Berlin, pp. 415-471). The CAPRAM remote scenario which was chosen as the standard scenario showed that the introduction of the higher organic chemistry has a relevant influence on the standard subsystems. The diurnal peak concentration of OH radical in the droplets decreases with about 40% and the reactions of OH with hydrocarbons containing 3 or 4 carbon atoms account for about 10% out of the total sinks of OH in the droplets. A slightly stronger acidification of the aqueous phase in comparison to CAPRAM 2.4 is observed. The simulations for the standard scenario showed that there is an increase of organic mass within the droplets where the organic compounds containing 4 carbon atoms represent the 67.5% of the total mass, whereas in the urban and in the marine scenario the contribution of two carbon atom compounds is dominating. The formation and accumulation of substituted mono- and dicarboxylic

  16. General chemistry students' understanding of climate science principles relating to chemistry

    Science.gov (United States)

    Versprille, A. N.; Towns, M.; Mahaffy, P.; Martin, B.; McKenzie, L. C.; Kirchhoff, M.

    2012-12-01

    As part of the NSF funded Visualizing the Chemistry of Climate Science project, we are developing the chemistry of climate science inventory for use in general chemistry courses. The U.S. Climate Change Science Program (CCSP), which integrates federal research on climate and global change, has set out a climate literacy framework, Climate Literacy: the Essential Principles of Climate Science (US Climate Change Science Program, 2009). Developed by collaboration among NOAA, NASA, AAAS, and a distinguished group of scientists and educators, this Framework defines a set of essential principles and scientific thinking skills that a climate literate person should understand. We have based our interview protocol on misconceptions identified in the research literature and the essential principles of climate change outlined in the CCSP document that pertain to chemistry. We have interviewed 24 undergraduates to elicit their understanding of the Earth's energy system, global warming, climate change, greenhouse gases, climate, and weather. Our analysis and findings indicate that the fundamental science necessary to understand the Earth's energy system and climate change are not well understood by the undergraduates in this sample. Details of the interviews, analysis, and synthesis of findings will be shared.

  17. Gas phase chemistry of technetium and rhenium oxychlorides

    Energy Technology Data Exchange (ETDEWEB)

    Eichler, R. [Bern Univ. (Switzerland). Abt. fuer Chemie und Biochemie; Eichler, B.; Jost, D.T.; Piguet, D.; Tuerler, A. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Gaeggeler, H.W. [Bern Univ. (Switzerland). Abt. fuer Chemie und Biochemie; Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    2000-07-01

    The chloride and oxychloride chemistry of the group 7 elements TC and Re was investigated in order to develop an experimental approach to a gas chemical characterisation of bohrium (Bh, element 107). In thermochromatography experiments with trace amounts of {sup 101,104}Tc and {sup 183,184}Re the formation of one volatile compound was observed in O{sub 2}/HCl containing carrier gas, which was attributed to MO{sub 3}Cl (M=Tc, Re). From the measured deposition temperatures the adsorption enthalpies on quartz surfaces {delta}H{sub ads}(TcO{sub 3}Cl)=-51{+-}3 kJ/mol and {delta}H{sub ads}(ReO{sub 3}Cl)=-62{+-}3 kJ/mol were evaluated. The sublimation enthalpies were derived using an empirical correlation between {delta}H{sub ads} and {delta}H{sub subl}: {delta}H{sub subl}(TcO{sub 3}Cl)=49{+-}10 kJ/mol and {delta}H{sub subl}(ReO{sub 3}Cl)=67{+-}10 kJ/mol. A fast gas chemical separation technique for highly volatile compounds of short-lived isotopes based on isothermal gas solid adsorption chromatography (OLGA-principle) was developed. With a modified OLGA device, model studies with the short-lived nuclides {sup 106,107,108}Tc and {sup 169,170,174,176}Re were carried out in preparation of an experimental gas chemical investigation of bohrium (Bh, element 107). Separation times of less than 3 s were achieved. A good separation of the oxychlorides of group 7 elements from chloride and oxychloride compounds of {sup 152-155}Er, {sup 151-154}Ho (as models for actinide elements), {sup 98-101}Nb, {sup 99-102}Zr (as models for light transactinide elements), {sup 218}Po, and {sup 214}Bi was accomplished in this chemical system. (orig.)

  18. Gas phase chemistry of technetium and rhenium oxychlorides

    International Nuclear Information System (INIS)

    The chloride and oxychloride chemistry of the group 7 elements TC and Re was investigated in order to develop an experimental approach to a gas chemical characterisation of bohrium (Bh, element 107). In thermochromatography experiments with trace amounts of 101,104Tc and 183,184Re the formation of one volatile compound was observed in O2/HCl containing carrier gas, which was attributed to MO3Cl (M=Tc, Re). From the measured deposition temperatures the adsorption enthalpies on quartz surfaces ΔHads(TcO3Cl)=-51±3 kJ/mol and ΔHads(ReO3Cl)=-62±3 kJ/mol were evaluated. The sublimation enthalpies were derived using an empirical correlation between ΔHads and ΔHsubl: ΔHsubl(TcO3Cl)=49±10 kJ/mol and ΔHsubl(ReO3Cl)=67±10 kJ/mol. A fast gas chemical separation technique for highly volatile compounds of short-lived isotopes based on isothermal gas solid adsorption chromatography (OLGA-principle) was developed. With a modified OLGA device, model studies with the short-lived nuclides 106,107,108Tc and 169,170,174,176Re were carried out in preparation of an experimental gas chemical investigation of bohrium (Bh, element 107). Separation times of less than 3 s were achieved. A good separation of the oxychlorides of group 7 elements from chloride and oxychloride compounds of 152-155Er, 151-154Ho (as models for actinide elements), 98-101Nb, 99-102Zr (as models for light transactinide elements), 218Po, and 214Bi was accomplished in this chemical system. (orig.)

  19. Study of the gas phase hot atom chemistry using THOR

    International Nuclear Information System (INIS)

    Reactions of recoil tritium and chlorine atoms in the gas phase have been studied using the facility at Tsing Hua Open-pool Reactor (THOR). The C2H3T yield, due to unimolecular reaction of the excited CH4THO* or C2H3T* molecules, is decreased with increasing pressure in the T + C2H5OH system. The yield of H38Cl is found in the range of 3 - 17 % based on CF3Cl/C2H4 ratio in the recoil 38Cl atom with ethylene system. (author)

  20. An advanced scheme for wet scavenging and liquid-phase chemistry in a regional online-coupled chemistry transport model

    Directory of Open Access Journals (Sweden)

    C. Knote

    2012-10-01

    Full Text Available Clouds are reaction chambers for atmospheric trace gases and aerosols, and the associated precipitation is a major sink for atmospheric constituents. The regional chemistry-climate model COSMO-ART has been lacking a description of wet scavenging of gases and aqueous-phase chemistry. In this work we present a coupling of COSMO-ART with a wet scavenging and aqueous-phase chemistry scheme. The coupling is made consistent with the cloud microphysics scheme of the underlying meteorological model COSMO. While the choice of the aqueous-chemistry mechanism is flexible, the effects of a simple sulfur oxidation scheme are shown in the application of the coupled system in this work. We give details explaining the coupling and extensions made, then present results from idealized flow-over-hill experiments in a 2-D model setup and finally results from a full 3-D simulation. Comparison against measurement data shows that the scheme efficiently reduces SO2 trace gas concentrations by 0.3 ppbv (−30% on average, while leaving O3 and NOx unchanged. PM10 aerosol mass, which has been overestimated previously, is now in much better agreement with measured values due to a stronger scavenging of coarse particles. While total PM2.5 changes only little, chemical composition is improved notably. Overestimations of nitrate aerosols are reduced by typically 0.5–1 μg m−3 (up to −2 μg m−3 in the Po Valley while sulfate mass is increased by 1–1.5 μg m−3 on average (up to 2.5 μg m−3 in Eastern Europe. The effect of cloud processing of aerosols on its size distribution, i. e. a shift towards larger diameters, is observed. Compared against wet deposition measurements the system underestimates the total wet deposited mass for the simulated case study. We find that while evaporation of cloud droplets dominates in higher altitudes, evaporation of precipitation can

  1. Some applications of radioisotopes in physical chemistry - two-phase equilibria and packed-column techniques

    International Nuclear Information System (INIS)

    One of the most effective applications of radioisotopes in physical chemistry is the study of two-phase equilibria; our own studies for a number of years have been concentrated on ion exchange reactions with commercial organic and with new types of non-siliceous inorganic exchangers. With the former, the studies were carried out in depth, covering at times most elements in the periodic table, the objective being comparison of functional relationships of many systems rather than the detailed study of a few. With the inorganic exchangers, the objective was also broad coverage of many systems, particularly comparison of large numbers of adsorbents. Since these studies required hundreds of thousands of analyses, they would have been almost impossible with conventional analytical techniques. The feasibility of such studies can therefore be considered a direct outgrowth of the ready availability of radioactive tracers, and the steady increase in precision and convenience of counting techniques. More recently, packed-column techniques have been developed which, with radioactive tracers and relatively simple equipment, permit ready extension of studies of two-phase equilibria and of the kinetics of interfaces to higher temperatures (at present up to 200o C). Sampling and continuous monitoring techniques were used. Through adsorption and solubility studies, information on enthalpy and entropy changes of adsorption and ion-exchange reactions is reported as well as information on heats of solution, activity coefficients in concentrated electrolyte mixtures, and on complexing reactions in high-temperature aqueous systems. (author)

  2. Remark on Relations Between Different Non-integrable Phases

    Institute of Scientific and Technical Information of China (English)

    GU Zhi-Yu; QIAN Shang-Wu

    2005-01-01

    There are three non-integrable phases in literatures: Berry phase, Aharonov-Anandan phase, and Yang phase. This article discusses the definitions and relations between these three non-integrable phases.

  3. Random Phase Approximation in Surface Chemistry: Water Splitting on Iron.

    Science.gov (United States)

    Karlický, František; Lazar, Petr; Dubecký, Matúš; Otyepka, Michal

    2013-08-13

    The reaction of water with zero-valent iron (anaerobic corrosion) is a complex chemical process involving physisorption and chemisorption events. We employ random phase approximation (RPA) along with gradient-corrected and hybrid density functional theory (DFT) functionals to study the reaction of water with the Fe atom and Fe(100) surface. We show that the involvement of the exact electron exchange and nonlocal correlation effects in RPA improves the description of all steps of the reaction on the Fe surface with respect to standard [meaning local density approximation (LDA) or generalized gradient approximation (GGA)] DFT methods. The reaction profile calculated by range-separated hybrid functional HSE06 agrees reasonably well with the RPA profile, which makes HSE06 a computationally less demanding alternative to RPA. We also investigate the reaction of the Fe atom with water using DFT, RPA, and coupled-cluster through the perturbative triples complete basis set [CCSD(T)-3s3p-DKH/CBS] method. Local DFT methods significantly underestimate reaction barriers, while the reaction kinetics and thermodynamics from RPA agree with the reference CCSD(T) data. Both systems, i.e., the Fe atom and Fe(100), provide the same reaction mechanism, indicating that anaerobic corrosion is a stepwise process involving one-electron steps, with the first reaction step (formation of the HFeOH intermediate) representing the rate-limiting step. PMID:26584120

  4. Combination of organotrifluoroborates with photoredox catalysis marking a new phase in organic radical chemistry.

    Science.gov (United States)

    Koike, Takashi; Akita, Munetaka

    2016-08-01

    Combination of organotrifluoroborates and visible-light-driven photoredox catalysis, both of which have attracted the attention of synthetic chemists, marks a new phase in the field of organic radical chemistry. We have developed photoredox-catalyzed radical reactions with organotrifluoroborates, which turn out to serve not only as a source of organic radicals but also as radical acceptors. The first part of this Perspective deals with the generation of organic radicals from organotrifluoroborates, and the latter part describes addition of the CF3 radical to alkenyltrifluoroborates. The good chemistry between organoborates and photoredox catalysis and its future will be discussed. PMID:27282517

  5. Phthalates: European regulation, chemistry, pharmacokinetic and related toxicity.

    Science.gov (United States)

    Ventrice, Pasquale; Ventrice, Domenica; Russo, Emilio; De Sarro, Giovambattista

    2013-07-01

    Phthalates are chemicals widely used in industry and the consequences for human health caused by exposure to these agents are of significant current interest. Phthalate toxicity targets the reproductive and respiratory systems primarily, but they also may be involved in the processes of carcinogenesis and even in autism spectrum disorders. This article discusses the molecular and cellular mechanisms involved in organ toxicity of phthalates; furthermore, pharmacokinetic, chemistry and the European regulation are summarized. PMID:23603460

  6. Chemistry

    International Nuclear Information System (INIS)

    Research progress is reported in programs on fuel-salt chemistry, properties of compounds in the Li--Te system, Te spectroscopy UF4--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--BeF2--ThF4 for Fe and analysis of LiF--BeF--ThF4 for Te

  7. Phase chemistry of Apollo 14 soil sample 14259

    Science.gov (United States)

    1974-01-01

    0.26 gm of Apollo 14 soil sample 14259 has been investigated by optical, X-ray diffraction and electron microprobe techniques. The mineral abundances in the soil are 45% plagioclase, 41% pyroxene, 7% olivine, 3% oxides, 2% K-feldspar, 1% nickel-iron and less than 1% troilite. Eleven percent of the glasses have compositions like those of mare basalts or mare soils and are believed to be mare-derived. Eighty-six percent of the glasses are equivalent in composition to basalts that have higher Al, and lower Ca/Al and Fe/Mg ratios than mare basalts. The most abundant compositional type is named Fra Mauro basaltic glass and is subdivided into three related types. The other major glass type in the soil corresponds in composition to anorthositic gabbro.

  8. Read-based phasing of related individuals

    Science.gov (United States)

    Garg, Shilpa; Martin, Marcel; Marschall, Tobias

    2016-01-01

    Motivation: Read-based phasing deduces the haplotypes of an individual from sequencing reads that cover multiple variants, while genetic phasing takes only genotypes as input and applies the rules of Mendelian inheritance to infer haplotypes within a pedigree of individuals. Combining both into an approach that uses these two independent sources of information—reads and pedigree—has the potential to deliver results better than each individually. Results: We provide a theoretical framework combining read-based phasing with genetic haplotyping, and describe a fixed-parameter algorithm and its implementation for finding an optimal solution. We show that leveraging reads of related individuals jointly in this way yields more phased variants and at a higher accuracy than when phased separately, both in simulated and real data. Coverages as low as 2× for each member of a trio yield haplotypes that are as accurate as when analyzed separately at 15× coverage per individual. Availability and Implementation: https://bitbucket.org/whatshap/whatshap Contact: t.marschall@mpi-inf.mpg.de PMID:27307622

  9. High-pressure crystal chemistry of zircon, monazite, scheelite and related minerals

    International Nuclear Information System (INIS)

    Full text: Many crystal structures of ABO4 compounds consists AO8 bisdisphenoids and BO4 tetrahedra. They include important mineral structures, e.g. zircon (ZrSiO4), anhydrite (CaSO4), silver perchlorate (AgClO4), and scheelite (CaWO4). These oxides, because of their compositional diversity and structural simplicity, played a key role in developing comparative crystal chemistry. In addition, zircon-type oxides exist in Nature being important minerals in the Earth mantle. Due to their incorporation of rare-earth (RE) elements they control the RE distribution in igneous rocks. Thus, the knowledge of their high-pressure (HP) structural behavior is relevant for mineral physics and chemistry (also for petrology). On the other hand, last decade RE phosphates and vanadates gained attention due to their optical and luminescent properties. Furthermore, given the crystal-chemical similarity between RE and actinides, phosphates were investigated for their use as solid-state repository for radioactive waste. The study of the HP mechanical and structural properties of ABO4 oxides is relevant for all these subjects. In this presentation different HP pressure studies performed in zircon-, monazite-, and scheelite-type oxides and related minerals (e.g. wolframite, barite, and anhydrite) are reviewed. The studies include XRD, EXAFS, and Raman experiments using a diamond-anvil cell up to 50 GPa as well as ab initio calculations. The combination of the experiments and calculations reveals the existence of complex HP phase-diagrams. In particular, the occurrence of pressure-induced phase transitions is discussed in detail. The differential bond compressibility of different polyhedra is also commented and related to the anisotropic compressibility of the structures. Results for tungstates, molybdates, vanadates, phosphates, chromates, arsenates, silicates, and germanates are shown. Finally, a systematic for the HP structural sequence of the studied oxides is present and discussed (e

  10. Factors related to achievement in sophomore organic chemistry at the University of Arkansas

    Science.gov (United States)

    Lindsay, Harriet Arlene

    The purpose of this study was to identify the significant cognitive and non-cognitive variables that related to achievement in the first semester of organic chemistry at the University of Arkansas. Cognitive variables included second semester general chemistry grade, ACT composite score, ACT English, mathematics, reading, and science reasoning subscores, and spatial ability. Non-cognitive variables included anxiety, confidence, effectance motivation, and usefulness. Using a correlation research design, the individual relationships between organic chemistry achievement and each of the cognitive variables and non-cognitive variables were assessed. In addition, the relationships between organic chemistry achievement and combinations of these independent variables were explored. Finally, gender- and instructor-related differences in the relationships between organic chemistry achievement and the independent variables were investigated. The samples consisted of volunteers from the Fall 1999 and Fall 2000 sections of Organic Chemistry I at the University of Arkansas. All students in each section were asked to participate. Data for spatial ability and non-cognitive independent variables were collected using the Purdue Visualization of Rotations test and the modified Fennema-Sherman Attitude Scales. Data for other independent variables, including ACT scores and second semester general chemistry grades, were obtained from the Office of Institutional Research. The dependent variable, organic chemistry achievement, was measured by each student's accumulated points in the course and consisted of scores on quizzes and exams in the lecture section only. These totals were obtained from the lecture instructor at the end of each semester. Pearson correlation and stepwise multiple regression analyses were used to measure the relationships between organic chemistry achievement and the independent variables. Prior performance in chemistry as measured by second semester general

  11. Models of Gas-phase and Surface Chemistry for Plasma Enhanced Chemical Vapor Deposition

    Science.gov (United States)

    Meeks, Ellen

    1996-10-01

    Plasma enhanced chemical vapor deposition for inter-metal-layer gap-fill processes are increasingly important in semiconductor device manufacture, as the devices include increasing numbers of metal layers with decreasing linewidth and spacing. Optimization of these processes requires knowledge of the microscopic consequences of variations in reactor operating conditions. Topographical simulation can address the gap-fill performance of a depositing film, but the predictive capabiliities are limited by the ability of the model user to accurately supply ion and radical fluxes at a gas/surface interface. Critical to determining this information are the chemical kinetics between gas-phase species and the deposition surfaces. Recent improvements and extensions to the CHEMKIN and Surface CHEMKIN software allow general inclusion of detailed chemical mechanisms in plasma simulations and in models of plasma-surface interactions. In the results presented here (This work represents a collaboration with R. Larson and P. Ho at Sandia, J. Rey and J. Li at TMA, S. M. Han and E. Aydil of UCSB, and S. Huang at Lam Research Corporation), we have used a CHEMKIN-based well mixed reactor model of a high-density SiH_4/O_2/Ar plasma to predict and characterize species fluxes, oxide-deposition rates, and ion-milling rates on a flat surface. These calculated rates can be used as direct input to a topographical simulator. The gas-phase chemistry in the plasma reactor model is comprised of electron impact reactions with silane, oxygen, hydrogen, and argon, as well as neutral radical recombination, abstraction, and oxidation reactions. The surface reaction mechanism contains four classes of reactions: silicon-containing radical deposition, radical abstraction, ion-induced desorption, and physical ion sputtering. We include relative thermochemistry of the surface and gas species to allow reversible reaction dynamics. The plasma model results show good agreement with measured ion densities, as

  12. Uncertainty relations for general phase spaces

    Science.gov (United States)

    Werner, Reinhard F.

    2016-04-01

    We describe a setup for obtaining uncertainty relations for arbitrary pairs of observables related by a Fourier transform. The physical examples discussed here are the standard position and momentum, number and angle, finite qudit systems, and strings of qubits for quantum information applications. The uncertainty relations allow for an arbitrary choice of metric for the outcome distance, and the choice of an exponent distinguishing, e.g., absolute and root mean square deviations. The emphasis of this article is on developing a unified treatment, in which one observable takes on values in an arbitrary locally compact Abelian group and the other in the dual group. In all cases, the phase space symmetry implies the equality of measurement and preparation uncertainty bounds. There is also a straightforward method for determining the optimal bounds.

  13. Discovering Factors that Influence the Decision to Pursue a Chemistry-Related Career: A Comparative Analysis of the Experiences of Non Scientist Adults and Chemistry Teachers in Greece

    Science.gov (United States)

    Salta, Katerina; Gekos, Michael; Petsimeri, Irene; Koulougliotis, Dionysios

    2012-01-01

    This study aims at identifying factors that influence students' choice not to pursue a chemistry-related career by analyzing the experiences of secondary education chemistry teachers in Greece and of Greek adults who have not pursued studies related to science. Data collection was done with the method of individual structured interviews. The…

  14. Nanoparticles-chemistry, new synthetic approaches, gas phase clustering and novel applications

    Indian Academy of Sciences (India)

    A Sreekumaran Nair; Chandramouli Subramaniam; M J Rosemary; Renjis T Tom; V R Rajeev Kumar; D M David Jeba Singh; Jobin Cyriac; Prashant Jain; K A Kalesh; Shreya Bhattacharya; T Pradeep

    2005-10-01

    In this paper, an overview of the synthesis, chemistry and applications of nanosystems carried out in our laboratory is presented. The discussion is divided into four sections, namely (a) chemistry of nanoparticles, (b) development of new synthetic approaches, (c) gas phase clusters and (d) device structures and applications. In `chemistry of nanoparticles' we describe a novel reaction between nanoparticles of Ag and Au with halocarbons. The reactions lead to the formation of various carbonaceous materials and metal halides. In `development of new synthetic approaches' our one-pot methodologies for the synthesis of core-shell nanosystems of Au, Ag and Cu protected with TiO2 and ZrO2 as well as various polymers are discussed. Some results on the interaction of nanoparticles with biomolecules are also detailed in this section. The third section covers the formation of gas phase aggregates/clusters of thiol-protected sub-nanoparticles. Laser desorption of H2MoO4, H2WO4, MoS2, and WS2 giving novel clusters is discussed. The fourth section deals with the development of simple devices and technologies using nanomaterials described above.

  15. Using Graphs of Gibbs Energy versus Temperature in General Chemistry Discussions of Phase Changes and Colligative Properties

    Science.gov (United States)

    Hanson, Robert M.; Riley, Patrick; Schwinefus, Jeff; Fischer, Paul J.

    2008-01-01

    The use of qualitative graphs of Gibbs energy versus temperature is described in the context of chemical demonstrations involving phase changes and colligative properties at the general chemistry level. (Contains 5 figures and 1 note.)

  16. Liquid-phase and evanescent-wave cavity ring-down spectroscopy in analytical chemistry.

    Science.gov (United States)

    van der Sneppen, L; Ariese, F; Gooijer, C; Ubachs, W

    2009-01-01

    Due to its simplicity, versatility, and straightforward interpretation into absolute concentrations, molecular absorbance detection is widely used in liquid-phase analytical chemistry. Because this method is inherently less sensitive than zero-background techniques such as fluorescence detection, alternative, more sensitive measurement principles are being explored. This review discusses one of these: cavity ring-down spectroscopy (CRDS). Advantages of this technique include its long measurement pathlength and its insensitivity to light-source-intensity fluctuations. CRDS is already a well-established technique in the gas phase, so we focus on two new modes: liquid-phase CRDS and evanescent-wave (EW)-CRDS. Applications of liquid-phase CRDS in analytical chemistry focus on improving the sensitivity of absorbance detection in liquid chromatography. Currently, EW-CRDS is still in early stages: It is used to study basic interactions between molecules and silica surfaces. However, in the future this method may be used to develop, for instance, biosensors with high specificity. PMID:20636052

  17. Binary Solid-Liquid Phase Diagram of Phenol and t-Butanol: An Undergraduate Physical Chemistry Experiment

    Science.gov (United States)

    Xu, Xinhua; Wang, Xiaogang; Wu, Meifen

    2014-01-01

    The determination of the solid-liquid phase diagram of a binary system is always used as an experiment in the undergraduate physical chemistry laboratory courses. However, most phase diagrams investigated in the lab are simple eutectic ones, despite the fact that complex binary solid-liquid phase diagrams are more common. In this article, the…

  18. New Target Methodology: Polymer-Assisted Deposition and Its Applications on Gas-Phase Nuclear Chemistry with Rutherfordium

    OpenAIRE

    Garcia, Mitch Andre

    2009-01-01

    This work focuses on three research topics that were distinctly different but broadly centered around developing new methods to perform transactinide gas-phase chemistry. First, the application of a new materials science methodology, Polymer-Assisted Deposition (PAD), to target manufacturing is described. Second, the construction of a new experimental apparatus to conduct gas-phase chemistry and the design of circuits and electronics for the measurement of alpha-decay energy is discussed. Thi...

  19. From Polymer to Small Organic Molecules: A Tight Relationship between Radical Chemistry and Solid-Phase Organic Synthesis

    OpenAIRE

    Danilo Mirizzi; Maurizio Pulici

    2011-01-01

    Since Gomberg’s discovery of radicals as chemical entities, the interest around them has increased through the years. Nowadays, radical chemistry is used in the synthesis of 75% of all polymers, inevitably establishing a close relationship with Solid-Phase Organic Synthesis. More recently, the interest of organic chemists has shifted towards the application of usual “in-solution” radical chemistry to the solid-phase, ranging from the use of supported reagents for radical reactions, to the dev...

  20. New Dioxaborolane Chemistry Enables [(18)F]-Positron-Emitting, Fluorescent [(18)F]-Multimodality Biomolecule Generation from the Solid Phase.

    Science.gov (United States)

    Rodriguez, Erik A; Wang, Ye; Crisp, Jessica L; Vera, David R; Tsien, Roger Y; Ting, Richard

    2016-05-18

    New protecting group chemistry is used to greatly simplify imaging probe production. Temperature and organic solvent-sensitive biomolecules are covalently attached to a biotin-bearing dioxaborolane, which facilitates antibody immobilization on a streptavidin-agarose solid-phase support. Treatment with aqueous fluoride triggers fluoride-labeled antibody release from the solid phase, separated from unlabeled antibody, and creates [(18)F]-trifluoroborate-antibody for positron emission tomography and near-infrared fluorescent (PET/NIRF) multimodality imaging. This dioxaborolane-fluoride reaction is bioorthogonal, does not inhibit antigen binding, and increases [(18)F]-specific activity relative to solution-based radiosyntheses. Two applications are investigated: an anti-epithelial cell adhesion molecule (EpCAM) monoclonal antibody (mAb) that labels prostate tumors and Cetuximab, an anti-epidermal growth factor receptor (EGFR) mAb (FDA approved) that labels lung adenocarcinoma tumors. Colocalized, tumor-specific NIRF and PET imaging confirm utility of the new technology. The described chemistry should allow labeling of many commercial systems, diabodies, nanoparticles, and small molecules for dual modality imaging of many diseases. PMID:27064381

  1. Surface and coordination chemistry related to GaAs

    Science.gov (United States)

    Keys, Andrea

    The vapor phase structures of Al(tBU)3 and Ga(tBU)3 have been investigated by gas phase electron diffraction and consist of planar three-coordinate monomers. Salient structural parameters (ra) include: Al-C = 2.005(3) A, Ga-C = 2.034(2) A. The geometries are controlled by inter-ligand interactions. The electron diffraction structures are compared to those determined by ab initio calculations for M(tBU)3 (M = Al, Ga, In). To understand the most suitable linkages for the surface of GaAs, model compounds were synthesized by reacting Ga(tBU)3 and [tBu2Ga(mu-Cl]2 with one molar equivalent of varying ligands. The synthesized compounds include chlorides, benzenethiolate, dithiocarbamates, carboxylates, amides, benzohydroxamate, and phenylphosphonate. The Ga ⋯ Ga and Ga-ligand interatomic distances for these compounds, as well as Group 15 and 16 donor bridging ligands, are compared to the values for the surface of GaAs and cubic-GaS in order to determine their suitability as linkage groups for self-assembled monolayers. The most suitable linkages were determined to be benzenethiol and phenylphophonic acid, and these were used to grow self-assembled monolayers on {100} GaAs. Carboxylic acid was also used, to determine the success of the organometallic model compounds in predicting the suitability of ligands for surface reaction. Self-assembled monolayers were also grown on Al2O3, using carboxylic acids and phenylphosphonic acids as the surface linkages. Metallo-organic chemical vapor deposition was performed using single-source precursors ( tBU)2Ga(S2CNR2). The tert -butyl gallium bis-dialkyl-dithiocarbamate compounds, (tBu)Ga(S2CNR2)2, are formed as minor products via ligand disproportionation reactions. Gallium sulfide (GaS) thin films have been grown at 375-425°C by atmospheric pressure metal-organic chemical vapor deposition using compounds (tBu) 2Ga(S2CNMe2) and (tBu)2Ga(S 2CNEt2) as single source precursors. Polycrystalline samples of the chalcogenides InSe, In2Se3

  2. A Convergent Solid-Phase Synthesis of Actinomycin Analogues - Towards Implementation of Double-Combinatorial Chemistry

    DEFF Research Database (Denmark)

    Tong, Glenn; Nielsen, John

    1996-01-01

    The actinomycin antibiotics bind to nucleic acids via both intercalation and hydrogen bonding. We found this 'double-action attack' mechanism very attractive in our search for a novel class of nucleic acid binders. A highly convergent, solid-phase synthetic strategy has been developed for a class...... with the requirements for combinatorial synthesis and furthermore, the final segment condensation allows, for the first time, double-combinatorial chemistry to be performed where two combinatorial libraries can be reacted with each other. Copyright (C) 1996 Elsevier Science Ltd....

  3. Relative Humidity Dependence of HONO Chemistry in Urban Areas

    Energy Technology Data Exchange (ETDEWEB)

    Stutz, Jochen P.; Alicke, B.; Ackerman, Ralph; Geyer, A.; Wang, S. H.; White, A. B.; Williams, E. J.; Spicer, Chet W.; Fast, Jerome D.

    2004-02-13

    The nocturnal DOAS measurements of HONO and NO2 from three field experiments are presented. The observations show that [HONO]/[NO2] ratios between 10-30% relative humidity (RH) do not exceed 0.05, while values of up to 0.09 were observed at higher RH. These results are analyzed by interpreting the observed maximum [HONO]/[NO2] ratio at a given relative humidity as the pseudo steady state between the heterogeneous NO2 to HONO conversion and the HONO loss on surfaces. Theoretical condiderations show that the [HONO]/[NO2] ratio at the PSS is equal to the ratio of the heterogeneous NO2 to HONO conversion coefficient reactive HONO uptake coefficient, thus showing these processes depend on RH. This result has implications for the parameterizations of HONO formation in air pollution models.

  4. Novel synthesis of para-hydroxy-phenylglycine and related chemistry

    OpenAIRE

    Titulaer, Gerardus Theodorus Maria

    2003-01-01

    para-Hydroxy-Phenylglycine (HPG) is an important sidechain in several b-lactam antibiotics. In industry HPG is produced from phenol as the starting material via an electrophilic substitution reaction. A serious problem in this approach is the formation of ortho/para regioisomers, which is caused by activation of both the ortho and para positions of phenol. In this thesis a novel two-step synthesis of HPG from the relatively cheap benzoquinone is described, in which the ortho/para problem is c...

  5. Influence of surface chemistry on the electronic properties of graphene related carbon materials

    OpenAIRE

    Chutia, Arunabhirm; Cimpoesu, Fanica; Tsuboi, Hideyuki; Miyamotob, Akira

    2010-01-01

    A theoretical study on the influence of organic functional groups on the electronic properties of graphene related carbon materials was carried out. Here we report, using density functional theory and tight-binding approach, that the best candidates for conducting supramolecular devices can be obtained by engineering the surface chemistry and stacking conformation of these materials.

  6. Lunar carbon chemistry - Relations to and implications for terrestrial organic geochemistry.

    Science.gov (United States)

    Eglinton, G.; Maxwell, J. R.; Pillinger, C. T.

    1972-01-01

    Survey of the various ways in which studies of lunar carbon chemistry have beneficially affected terrestrial organic geochemistry. A lunar organic gas-analysis operating system is cited as the most important instrumental development in relation to terrestrial organic geochemistry. Improved methods of analysis and handling of organic samples are cited as another benefit derived from studies of lunar carbon chemistry. The problem of controlling contamination and minimizing organic vapors is considered, as well as the possibility of analyzing terrestrial samples by the techniques developed for lunar samples. A need for new methods of analyzing carbonaceous material which is insoluble in organic solvents is indicated.

  7. Cold flame on Biofilm - Transport of Plasma Chemistry from Gas to Liquid Phase

    Science.gov (United States)

    Kong, Michael

    2014-10-01

    One of the most active and fastest growing fields in low-temperature plasma science today is biological effects of gas plasmas and their translation in many challenges of societal importance such as healthcare, environment, agriculture, and nanoscale fabrication and synthesis. Using medicine as an example, there are already three FDA-approved plasma-based surgical procedures for tissue ablation and blood coagulation and at least five phase-II clinical trials on plasma-assisted wound healing therapies. A key driver for realizing the immense application potential of near room-temperature ambient pressure gas plasmas, commonly known as cold atmospheric plasmas or CAP, is to build a sizeable interdisciplinary knowledge base with which to unravel, optimize, and indeed design how reactive plasma species interact with cells and their key components such as protein and DNA. Whilst a logical objective, it is a formidable challenge not least since existing knowledge of gas discharges is largely in the gas-phase and therefore not directly applicable to cell-containing matters that are covered by or embedded in liquid (e.g. biofluid). Here, we study plasma inactivation of biofilms, a jelly-like structure that bacteria use to protect themselves and a major source of antimicrobial resistance. As 60--90% of biofilm is made of water, we develop a holistic model incorporating physics and chemistry in the upstream CAP-generating region, a plasma-exit region as a buffer for as-phase transport, and a downstream liquid region bordering the gas buffer region. A special model is developed to account for rapid chemical reactions accompanied the transport of gas-phase plasma species through the gas-liquid interface and for liquid-phase chemical reactions. Numerical simulation is used to illustrate how key reactive oxygen species (ROS) are transported into the liquid, and this is supported with experimental data of both biofilm inactivation using plasmas and electron spin spectroscopy (ESR

  8. A New Phase Unwrapping Algorithm Based on Relative Distance Oriented

    Science.gov (United States)

    Zhang, Qican; Su, Xianyu; Xiang, Liqun; Yu, Liang

    2010-04-01

    A relative distance-oriented phase unwrapping algorithm is presented in this paper. Considered the wrapped phase value and modulation distribution of the neighboring pixel, a relative distance of two adjacent pixels is calculated and localized in a complex coordinates, in which the relative distance tree will be composed by all the relative distances and will be used to determine the optimized path of phase unwrapping. The smaller relative distance shows that the phase difference between the two corresponding pixels is very small and the phase data waiting for unwrapping is more reliable. The closer the relative distance is, the more success the phase unwrapping will achieve. Combining the minimum spanning tree algorithm, the phase unwrapping order of each pixel can be determined and the whole phase unwrapping path can also be given. The phase unwrapping path is always directed from the minimum distance value to the greater one. Consequently, this algorithm could avoid error propagating in the phase unwrapping. The errors could be limited in the minimum local region in worst case and the error probability of the phase unwrapping is as low as possible. The physical significance of the relative distance and the fully algorithm for phase unwrapping are proposed in this paper. The result of the experiment show that this new algorithm is feasible and effective, it could control the path avoid crossing the poles, branch-cut and the shadow in the phase unwrapping.

  9. The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

    KAUST Repository

    Hong, Jongsup

    2015-08-01

    © 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors, thermochemical reactions take place in the gas-phase and on the membrane surface, both of which interact with oxygen permeation. However, this coupling between gas-phase and surface chemistry has not been examined in detail. In this study, a parametric analysis using numerical simulations is conducted to investigate this coupling and its impact on fuel conversion and oxygen permeation rates. A thermochemical model that incorporates heterogeneous chemistry on the membrane surface and detailed chemical kinetics in the gas-phase is used. Results show that fuel conversion and oxygen permeation are strongly influenced by the simultaneous action of both chemistries. It is shown that the coupling somewhat suppresses the gas-phase kinetics and reduces fuel conversion, both attributed to extensive thermal energy transfer towards the membrane which conducts it to the air side and radiates to the reactor walls. The reaction pathway and products, in the form of syngas and C2 hydrocarbons, are also affected. In addition, the operating regimes of ITM reactors in which heterogeneous- or/and homogeneous-phase reactions predominantly contribute to fuel conversion and oxygen permeation are elucidated.

  10. Improved machine learning method for analysis of gas phase chemistry of peptides

    Directory of Open Access Journals (Sweden)

    Ahn Natalie

    2008-12-01

    Full Text Available Abstract Background Accurate peptide identification is important to high-throughput proteomics analyses that use mass spectrometry. Search programs compare fragmentation spectra (MS/MS of peptides from complex digests with theoretically derived spectra from a database of protein sequences. Improved discrimination is achieved with theoretical spectra that are based on simulating gas phase chemistry of the peptides, but the limited understanding of those processes affects the accuracy of predictions from theoretical spectra. Results We employed a robust data mining strategy using new feature annotation functions of MAE software, which revealed under-prediction of the frequency of occurrence in fragmentation of the second peptide bond. We applied methods of exploratory data analysis to pre-process the information in the MS/MS spectra, including data normalization and attribute selection, to reduce the attributes to a smaller, less correlated set for machine learning studies. We then compared our rule building machine learning program, DataSqueezer, with commonly used association rules and decision tree algorithms. All used machine learning algorithms produced similar results that were consistent with expected properties for a second gas phase mechanism at the second peptide bond. Conclusion The results provide compelling evidence that we have identified underlying chemical properties in the data that suggest the existence of an additional gas phase mechanism for the second peptide bond. Thus, the methods described in this study provide a valuable approach for analyses of this kind in the future.

  11. Chemistry of UO2 fuel dissolution in relation to the disposal of used nuclear fuel

    International Nuclear Information System (INIS)

    This report reviews the chemistry of UO2 dissolution under conditions relevant to the disposal of used nuclear fuel in a geological vault. It provides the chemical understanding necessary for selecting the most appropriate model for estimating UO2 fuel dissolution rates in a nuclear waste disposal vault. The report briefly describes the solid-state structures of various uranium oxides; discusses the nature and mechanism of UO2 oxidation and dissolution in groundwaters; summarizes the factors affecting UO2 dissolution under oxidizing conditions; discusses the impact of various oxidants and water radiolysis on UO2 oxidation and dissolution; briefly comments on the effects of vault chemistry and secondary phase formation on the dissolution process; discusses the physical properties of UO2 that may influence the kinetics of dissolution; and describes our approach for developing a kinetic model of UO2 dissolution under oxidizing conditions

  12. Transforming Trauma: The Relational Unconscious and "Chemistry" in the Treatment of a Paraplegic Patient.

    Science.gov (United States)

    Steinberger, Claire Beth

    2014-06-01

    Therapeutic action with a traumatized paraplegic patient highlights the evocative-and transformative-influence of the relational unconscious. The patient's triumphant resolution suggests that formative bipersonal dynamics (including transference, countertransference, and mutual projective identifications) create an ongoing intersubjective enactment and relational chemistry pivotal to psychic shift. A broad systems perspective highlights contextual communication and the interweaving of the analyst's etiological contributions and subjective experience of trauma. Ultimately, an unconscious, co-created dynamic challenges traumatic fixations, supporting a reintegration of narcissistic, gender, and erotic representations and ego capacities. An eclectic perspective that illuminates the analyst's role-receptivity encompasses classical, object relations, relational, systems, and self psychological paradigms. PMID:24913551

  13. Reduction of aliasing ambiguities through phase relations

    Science.gov (United States)

    Sanderson, Richard B.; Tsui, James B. Y.; Freese, Nancy A.

    1992-10-01

    A method for digital determination of a single frequency from a sine wave sampled at less than the Nyquist rate is discussed. The method makes use of phase shift information to eliminate the aliasing ambiguity. Multiple sampled data are required to eliminate ambiguity completely. Computer modeling using simulated data corrupted by uncorrelated Gaussian noise was used to verify the approach. The results demonstrate that the frequency of an input sine wave can be correctly identified. This approach can be applied to electronic warfare (EW) receivers to increase their input bandwidth.

  14. Chemistry of zirconium related to the behavior of nuclear fuel cladding. Final report

    International Nuclear Information System (INIS)

    Studies of the chemistry of the zirconium-iodine and zirconium-oxygen systems were undertaken to elucidate their thermodynamics and kinetics. It is anticipated that the results obtained will lead to an improved understanding of the chemical processes involved in chemically assisted fuel rod failures. This project not only has classified the thermodynamics of both the gas phase and the solids in the zirconium-iodine system, it has also provided valuable information on the chemisorption of iodine and of oxygen on zirconium surfaces at high temperatures. In addition, the kinetics of reactions on zirconium surfaces were studied. These results have already been helpful in understanding the stress corrosion cracking of Zircaloy

  15. Evaluation of phase chemistry and petrochemical aspects of Samchampi–Samteran differentiated alkaline complex of Mikir Hills, northeastern India

    Indian Academy of Sciences (India)

    Abhishek Saha; Sohini Ganguly; Jyotisankar Ray; Nilanjan Chaterjee

    2010-10-01

    The Samchampi –Samteran alkaline complex occurs as a plug-like pluton within the Precambrian granite gneisses of Mikir Hills,Assam,northeastern India and it is genetically related to Sylhet Traps.The intrusive complex is marked by dominant development of syenite within which ijolite – melteigite suite of rocks is emplaced with an arcuate outcrop pattern.Inliers of alkali pyroxenite and alkali gabbro occur within this ijolite –melteigite suite of rocks.The pluton is also traversed by younger intrusives of nepheline syenite and carbonatite.Development of sporadic,lumpy magnetite ore bodies is also recorded within the pluton.Petrographic details of the constituent lithomembers of the pluton have been presented following standard nomenclatorial rules.Overall pyroxene compositions range from diopside to aegirine augite while alkali feldspars are typically orthoclase and plagioclase in syenite corresponds to oligoclase species.Phase chemistry of nepheline is suggestive of Na-rich alkaline character of the complex.Biotite compositions are typically restricted to a uniform compositional range and they belong to ‘biotite ’field in the relevant classification scheme.Garnets (developed in syenite and melteigite)typically tend to be Ti-rich andradite,which on a closer scan can be further designated as melanites.Opaque minerals mostly correspond to magnetite.Use of Lindsley ’s pyroxene thermometric method suggests an equilibration temperature from ∼450°–600°C for melteigite/alkali gabbro and ∼400° C for syenite.Critical assessment of other thermometric methods reveals a temperature of equilibration of ∼700°–1350°C for ijolite –melteigite suite of rocks in contrast to a relatively lower equilibration temperature of ∼600° C for syenite. Geobarometric data based on pyroxene chemistry yield an equilibration pressure of 5.32 –7.72 kb for ijolite,melteigite,alkali pyroxenite,alkali gabbro and nepheline syenite.The dominant syenite member of the

  16. Senior Seminar Focusing on Societal Issues Related to Chemistry and Biochemistry

    Science.gov (United States)

    White, Harold B., III; Johnston, Murray V.; Panar, Manuel

    2000-12-01

    The lack of a clearly defined content or structure provided the opportunity to transform a one-credit, pass-fail senior seminar course into a meaningful capstone experience for chemistry and biochemistry majors. In addition to individual and class exercises associated with employment, graduate school, communication skills, and professional ethics, small groups of students worked together to create informative Web sites that took positions on important societal issues related to chemistry. Each group presented a seminar and responded to questions from their peers and two or more unannounced visitors, "wild cards" who often had expertise in the seminar topic. Throughout the course, the instructors placed particular emphasis on developing students' ability to work cooperatively, locate and evaluate information, make informed judgments based on available information, and logically develop and defend their positions. Input from a retired industrial chemist helped define these skill elements.

  17. Three-phase relative permeability of Berea sandstone

    Energy Technology Data Exchange (ETDEWEB)

    Oak, M.J.; Baker, L.E. (Amoco Production Co., Tulsa, OK (US)); Thomas, C.C. (Amoco Corp., Naperville Research Center, IL (US))

    1990-08-01

    Reservoir engineering calculations frequently require consideration of coexisting oil, water, and gas phases. Such three-phase flow occurs when oil is displaced by simultaneous gas/water flow as in CO{sub 2}, water-alternating-gas flooding, steam-flooding, or other enhanced recovery processes. For this reason, reservoir simulators generally include three-phase relative permeability prediction methods. This paper presents two- and three-phase relative permeabilities measured on a water-wet fired Berea sandstone core with a fully automated steady-state method to investigate prediction methods experimentally.

  18. Michaelis-Menten Kinetics and the Activation Energy Relate Soil Peroxidase Kinetics to the Lignin Chemistry

    Science.gov (United States)

    Triebwasser-Freese, D.; Tharayil, N.; Preston, C. M.; Gerard, P.

    2013-12-01

    Recently, it has been suggested that lignin exhibit a turnover rate of less than 6 years, suggesting that the enzymatic mechanisms mediating the decay of lignin are less understood. One factor that could be affecting the mean residence time of lignin in the soil is the catalytic efficiency of soil oxidoreductase enzymes. We characterized the spatial and seasonal transitions in the Michaelis-Menten kinetics and activation energy of the soil oxidoreductase enzyme, peroxidase, across three ecosystems of differing litter chemistries- pine, deciduous forest, and a cultivated field- and associate it to the soil lignin chemistries. To interpret the combined effect of Vmax and Km, the two parameters were integrated into one term which we defined as the catalytic efficiency. Generally, the peroxidases in pine soils exhibited the highest Vmax and Km, resulting in the lowest catalytic efficiency, followed by that in the deciduous soils. Meanwhile, the agricultural soils which exhibited the lowest Vmax and Km contained the highest catalytic efficiency of peroxidase. Through linear regression analysis of the kinetic parameters to the soil lignin chemistry, we discerned that the catalytic efficiency term best associated to the lignin monomer ratios (C/V, P/V, and SCV/V). The Activation Energy of peroxidase varied by depth, and seasons across the ecosystems. However, the Activation Energy of peroxidase did not relate to the lignin chemistry or quantity. Collectively, our results show that although the peroxidase Vmax and Km in the phenolic-poor soils are low, the degradation efficiency of peroxidases in this soils can be equivalent or exceed that of phenolic-rich soils. This study, through the characterization of Michaelis-Menten kinetics, provides a new insight into the mechanisms that could moderate the decomposition of lignin in soils.

  19. Effects of phase transformation of steam-water relative permeabilities

    Energy Technology Data Exchange (ETDEWEB)

    Verma, A.K.

    1986-03-01

    A combined theoretical and experimental study of steam-water relative permeabilities (RPs) was carried out. First, an experimental study of two-phase concurrent flow of steam and water was conducted and a set of RP curves was obtained. These curves were compared with semi-empirical and experimental results obtained by other investigators for two-phase, two-component flow (oil/gas; gas/water; gas/oil). It was found that while the wetting phase RPs were in good agreement, RPs for the steam phase were considerably higher than the non-wetting phase RPs in two-component systems. This enhancement of steam RP is attributed to phase transformation effects at the pore level in flow channels. The effects of phase transformation were studied theoretically. This study indicates that there are two separate mechanisms by which phase transformation affects RP curves: (1) Phase transformation is converging-diverging flow channels can cause an enhancement of steam phase RP. In a channel dominated by steam a fraction of the flowing steam condenses upstream from the constriction, depositing its latent heat of condensation. This heat is conducted through the solid grains around the pore throat, and evaporation takes place downstream from it. Therefore, for a given bulk flow quality; a smaller fraction of steam actually flows through the throat segments. This pore-level effect manifests itself as relative permeability enhancement on a macroscopic level; and (2) phase transformation along the interface of a stagnant phase and the phase flowing around it controls the irreducible phase saturation. Therefore, the irreducible phase saturation in steam-water flow will depend, among other factors, on the boundary conditions of the flow.

  20. The contribution of solid-state chemistry in the determination of multicomponent phase diagrams

    Institute of Scientific and Technical Information of China (English)

    Jean Claude Tedenac; Franck Gascoin; Didier Ravot

    2006-01-01

    For a long period of time, the determination of phase diagrams was only supported by experiments related to thermal effects or thermodynamic measurements: thermal analysis, calorimetric measurements, vapor pressures, and EMF measurements. As a matter of fact, solid-solid transformations were not so accurately determined and could not be taken into account in the system's analysis. First, X-ray diffraction methods were used as a support for the thermal analysis. Sec ond, the implementation of novel tools in structural analysis (for example, the Rietveld method) has permitted to increase the knowledge of phase stability. Finally, modeling the phases using a Calphad method needed increasingly more structural results to determine and better understand the phase diagrams. On the other hand, the Calphad method has been widely developed for metallic systems, for oxide systems, and in the past 10 years, for some semi-conductor systems, for example,gallium arsenide, cadmium telluride, and lead telluride systems. In such applications, it is very important to bring point defects in the modeling of the phases to map the defects as a function of the chemical composition. Owing to its complexity,this characteristic, the knowledge of which is crucial for the understanding and the control of potential physical applications, was ignored in the previous assessment of semi-conductor systems.

  1. Effect of multilayer ice chemistry on gas-phase deuteration in starless cores

    Science.gov (United States)

    Sipilä, O.; Caselli, P.; Taquet, V.

    2016-06-01

    Context. Astrochemical models commonly used to study the deuterium chemistry in starless cores consider a two-phase approach in which the ice on the dust grains is assumed to be entirely reactive. Recent experimental studies suggest that cold interstellar ices are mostly inert, and a multilayer model distinguishing the chemical processes at the surface and in the ice bulk would be more appropriate. Aims: We investigate whether the multilayer model can be as successful as the bulk model in reproducing the observed abundances of various deuterated gas-phase species toward starless cores. Methods: We calculated abundances for various deuterated species as functions of time using a pseudo-time-dependent chemical model adopting fixed physical conditions. We also estimated abundance gradients in starless cores by adopting a modified Bonnor-Ebert sphere as a core model. In the multilayer ice scenario, we consider desorption from one or several monolayers on the surface. Results: We find that the multilayer model predicts abundances of DCO+ and N2D+ that are about an order of magnitude lower than observed; the difference is caused by the trapping of CO and N2 within the grain mantle. As a result of the mantle trapping, deuteration efficiency in the gas phase increases and we find stronger deuterium fractionation in ammonia than has been observed. Another distinguishing feature of the multilayer model is that becomes the main deuterated ion at high density. The bulk ice model is generally easily reconciled with observations. Conclusions: Our results underline that more theoretical and experimental work is needed to understand the composition and morphology of interstellar ices, and the desorption processes that can act on them. With the current constraints, the bulk ice model appears to reproduce the observations more accurately than the multilayer ice model. According to our results, the abundance ratio of H2D+ to N2D+ is higher than 100 in the multilayer model, while only

  2. Mass Spectrometry for Ion Chemistry and Links from the Gas Phase to "Real" Processes

    Czech Academy of Sciences Publication Activity Database

    Schröder, Detlef

    Vol. 1. Weinheim : Wiley-VCH, 2012 - (Schäfer, R.; Schmidt, P.), s. 63-84 ISBN 978-3-527-32745-4 Institutional research plan: CEZ:AV0Z40550506 Keywords : ion chemistry * mass spectrometry * reaction mechanisms Subject RIV: CF - Physical ; Theoretical Chemistry

  3. Design of a new multi-phase experimental simulation chamber for atmospheric photosmog, aerosol and cloud chemistry research

    Directory of Open Access Journals (Sweden)

    J. Wang

    2011-11-01

    Full Text Available A new simulation chamber has been built at the Interuniversitary Laboratory of Atmospheric Systems (LISA. The CESAM chamber (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber is designed to allow research in multiphase atmospheric (photo- chemistry which involves both gas phase and condensed phase processes including aerosol and cloud chemistry. CESAM has the potential to carry out variable temperature and pressure experiments under a very realistic artificial solar irradiation. It consists of a 4.2 m3 stainless steel vessel equipped with three high pressure xenon arc lamps which provides a controlled and steady environment. Initial characterization results, all carried out at 290–297 K under dry conditions, concerning lighting homogeneity, mixing efficiency, ozone lifetime, radical sources, NOy wall reactivity, particle loss rates, background PM, aerosol formation and cloud generation are given. Photolysis frequencies of NO2 and O3 related to chamber radiation system were found equal to (4.2 × 10−3 s−1 for JNO2 and (1.4 × 10−5 s−1 for JO1D which is comparable to the solar radiation in the boundary layer. An auxiliary mechanism describing NOy wall reactions has been developed. Its inclusion in the Master Chemical Mechanism allowed us to adequately model the results of experiments on the photo-oxidation of propene-NOx-Air mixtures. Aerosol yields for the α-pinene + O3 system chosen as a reference were determined and found in good agreement with previous studies. Particle lifetime in the chamber ranges from 10 h to 4 days depending on particle size distribution which indicates that the chamber can provide high quality data on aerosol aging processes and their effects. Being evacuable, it is possible to generate in this new chamber

  4. Design of a new multi-phase experimental simulation chamber for atmospheric photosmog, aerosol and cloud chemistry research

    Directory of Open Access Journals (Sweden)

    J. Wang

    2011-01-01

    Full Text Available A new simulation chamber has been built at the Interuniversitary Laboratory of Atmospheric Systems (LISA. The CESAM chamber (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber is designed to allow research in multiphase atmospheric (photo-chemistry which involves both gas phase and condensed phase processes including aerosol and cloud chemistry. CESAM has the potential to carry out variable temperature and pressure experiments under a very realistic artificial solar irradiation. It consists of a 4.2 m3 stainless steel vessel equipped with three high pressure xenon arc lamps which provides a controlled and steady environment. Initial characterization results, all carried out at 290–297 K under dry conditions, concerning lighting homogeneity, mixing efficiency, ozone lifetime, radical sources, NOy wall reactivity, particle loss rates, background PM, aerosol formation and cloud generation are given. Photolysis frequencies of NO2 and O3 related to chamber radiation system were found equal to (4.2 × 10−3 s−1 for JNO2 and (1.4 × 10-5 s−1 for J O1D which is comparable to the solar radiation in the boundary layer. An auxiliary mechanism describing NOy wall reactions has been developed. Its inclusion in the Master Chemical Mechanism allowed us to adequately model the results of experiments on the photo-oxidation of propene-NOx-air mixtures. Aerosol yields for the α-pinene + O3 system chosen as a reference were determined and found in good agreement with previous studies. Particle lifetime in the chamber ranges from 10 h to 4 days depending on particle size distribution which indicates that the chamber can provide high quality data on aerosol aging processes and their effects. Being evacuable, it is possible to generate in this new chamber clouds by fast

  5. Investigating Differences in Isoprene Oxidation Chemistry Between Gas-Phase Mechanisms Using a Constrained Chemical Box Model

    Science.gov (United States)

    Marvin, M. R.; Wolfe, G. M.; Salawitch, R. J.; Canty, T. P.; Hanisco, T. F.; Kaiser, J.; Keutsch, F. N.; Graus, M.; Warneke, C.; De Gouw, J. A.; Gilman, J.; Lerner, B. M.; Peischl, J.; Veres, P. R.; Min, K. E.; Holloway, J. S.; Aikin, K. C.; Ryerson, T. B.; Roberts, J. M.; Brown, S. S.; Pollack, I. B.; Hatch, C. D.; Lee, B. H.; Lopez-Hilfiker, F.; Thornton, J. A.; Diskin, G. S.; Sachse, G. W.; Huey, L. G.; Liu, X.; Wisthaler, A.; Mikoviny, T.; Wennberg, P. O.; St Clair, J.; Crounse, J.; Teng, A.

    2015-12-01

    Oxidation of isoprene by OH can significantly influence concentrations of important atmospheric pollutants such as ozone and secondary organic aerosols, but the chemistry that describes the relationships between these species is complex and not fully understood. Debate on the topic has led to differences in the isoprene oxidation schemes of several gas-phase chemical mechanisms currently applied in air chemistry models. We use the University of Washington Chemical Model (UWCMv3) to evaluate these mechanisms with respect to isoprene chemistry based on observations from the SENEX and SEAC4RS aircraft campaigns. The campaigns provide constraints on compounds measured over the Southeast United States, where isoprene concentrations are high and other conditions (e.g., NOx levels) vary widely. The payloads for both missions include observations of a wide range of isoprene oxidation products, which can provide insight into specific oxidation pathways. Analysis will focus on the characterization and comparison of isoprene oxidation chemistry for established gas-phase mechanisms that are prevalent in atmospheric modeling today, including the Carbon Bond mechanism (CB05 and CB6r2) and the Master Chemical Mechanism (versions 3.2 and 3.3).

  6. Na + and HTO diffusion in compacted bentonite: Effect of surface chemistry and related texture

    Science.gov (United States)

    Melkior, T.; Gaucher, E. C.; Brouard, C.; Yahiaoui, S.; Thoby, D.; Clinard, Ch.; Ferrage, E.; Guyonnet, D.; Tournassat, C.; Coelho, D.

    2009-05-01

    SummaryIn underground repository concepts for radioactive waste, bentonite is studied as a reference swelling material to be used as an engineered barrier. Under the changing geochemical conditions prevailing within the barrier (saturation with the fluid coming from the host formation, diffusion of various chemical plumes caused by the degradation of some constituents of the barrier-system, etc.), the surface chemistry of the clay particles could evolve. This work aims to characterize the effects of these changes on (i) the microstructure of compacted bentonite samples and (ii) the diffusion properties of HTO and Na in these samples. For this purpose, bentonite sets were equilibrated with different solutions: NaCl, CaCl 2, CsCl solutions as well as an artificial clayey porewater solution. The microstructure of the different samples was characterized by HRTEM and XRD, in a water saturated state. In parallel, effective diffusion coefficients of both HTO and 22Na were measured for the different samples. The density of the bentonite in the diffusion tests and in the HRTEM observations was set at 1.6 Mg m -3. From the microstructural observations and the results of diffusion tests, it is deduced that one key parameter is the occurrence of a gel phase in the material, which is found to depend strongly on the bentonite set: the gel phase dominates in Na-bentonite, while it is lacking in Cs-bentonite. The HTO diffusion coefficients are found to be lower in the samples with high gel phase content. Sodium diffusion does not follow the same trend: when compared with HTO, Na diffuses faster when the gel phase content is high. The latter result could indicate that the "accelerated diffusion mechanism" of cations, already mentioned in the literature, is enhanced in clayey materials that contain a gel phase.

  7. Hydrogen-related phase transformations in austenitic stainless steels

    Science.gov (United States)

    Narita, N.; Altstetter, C. J.; Birnbaum, H. K.

    1982-08-01

    The effect of hydrogen and stress (strain) on the stability of the austenite phase in stainless steels was investigated. Hydrogen was introduced by severe cathodic charging and by elevated temperature equilibration with high pressure H2 gas. Using X-ray diffraction and magnetic techniques, the behavior of two “stable” type AISI310 steels and an “unstable” type AISI304 steel was studied during charging and during the outgassing period following charging. Transformation from the fcc γ phase to an expanded fcc phase, γ*, and to the hcp ɛ phase occurred during cathodic charging. Reversion of the γ* and e phases to the original γ structure and formation of the bcc α structure were examined, and the kinetics of these processes was studied. The γ* phase was shown to be ferromagnetic with a subambient Curie temperature. The γ⇆ɛ phase transition was studied after hydrogen charging in high pressure gas, as was the formation of a during outgassing. These results are interpreted as effects of hydrogen and stress (strain) on the stability of the various phases. A proposed psuedo-binary phase diagram for the metal-hydrogen system was proposed to account for the formation of the γ* phase. The relation of these phase changes to hydrogen embrittlement and stress corrosion cracking of stainless steel is discussed.

  8. Thiol click chemistry on gold-decorated MoS2: elastomer composites and structural phase transitions

    Science.gov (United States)

    Topolovsek, Peter; Cmok, Luka; Gadermaier, Christoph; Borovsak, Milos; Kovac, J.; Mrzel, Ales

    2016-05-01

    We show that gold decorated MoS2 flakes are amenable to thiol chemistry by blending them with a cross-linkable thiolated polysiloxane (PMMS). PMMS prevents restacking of dispersed MoS2 when transforming the metallic to the semiconducting phase. Cross-linking PMMS yields an elastomer of good optical quality, containing individual, mostly single-layer MoS2 flakes.We show that gold decorated MoS2 flakes are amenable to thiol chemistry by blending them with a cross-linkable thiolated polysiloxane (PMMS). PMMS prevents restacking of dispersed MoS2 when transforming the metallic to the semiconducting phase. Cross-linking PMMS yields an elastomer of good optical quality, containing individual, mostly single-layer MoS2 flakes. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01490a

  9. Improvement and further development in CESM/CAM5: gas-phase chemistry and inorganic aerosol treatments

    OpenAIRE

    He, J.; Zhang, Y.

    2013-01-01

    Gas-phase chemistry and subsequent gas-to-particle conversion processes such as new particle formation, condensation, and thermodynamic partitioning have large impacts on air quality, climate, and public health through influencing the amounts and distributions of gaseous precursors and secondary aerosols. Their roles in global air quality and climate are examined in this work using the Community Earth System Model version 1.0.5 (CESM1.0.5) with the Community Atmosphere Model version 5....

  10. Gas-phase chemistry in the online multiscale NMMB/BSC Chemical Transport Model: Description and evaluation at global scale

    OpenAIRE

    Badia, Alba; JORBA Oriol; Voulgarakis, Apostolos; Dabdub, Donald; Pérez, Carlos; Hilboll, Andreas; Gonçalves, María; Janjic, Zavisa

    2016-01-01

    This paper presents a comprehensive description and benchmark evaluation of the tropospheric gas-phase chemistry component of the NMMB/BSC Chemical Transport Model (NMMB/BSC-CTM), an online chemical weather prediction system conceived for both the regional and the global scale. We provide an extensive evaluation of a global annual cycle simulation using a variety of background surface stations (EMEP, WDCGG and CASTNET), ozonesondes (WOUDC, CMD and SHADOZ), aircraft data (MOZAIC and several ca...

  11. Solution-phase-peptide synthesis via the Group-Assisted Purification (GAP) chemistry without using chromatography and recrystallization†

    OpenAIRE

    Wu, Jianbin; An, Guanghui; Lin, Siqi; Xie, Jianbo; Zhou, Wei; Sun, Hao; Pan, Yi; Li, Guigen

    2014-01-01

    The solution phase synthesis of N-protected amino acids and peptides has been achieved through the Group-Assisted Purification (GAP) chemistry by avoiding disadvantages of other methods in regard to the difficult scale-up, expenses of solid and soluble polymers, etc. The GAP synthesis can reduce the use of solvents, silica gels, energy and manpower. In addition, the GAP auxiliary can be conveniently recovered for re-use and is of environmentally friendly benign by substantially reducing waste...

  12. Antireflection and SiO2 Surface Passivation by Liquid-Phase Chemistry for Efficient Black Silicon Solar Cells: Preprint

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, H. C.; Oh, J.; Zhang, Y.; Kuznetsov, O. A.; Flood, D. J.; Branz, H. M.

    2012-06-01

    We report solar cells with both black Si antireflection and SiO2 surface passivation provided by inexpensive liquid-phase chemistry, rather than by conventional vacuum-based techniques. Preliminary cell efficiency has reached 16.4%. Nanoporous black Si antireflection on crystalline Si by aqueous etching promises low surface reflection for high photon utilization, together with lower manufacturing cost compared to vacuum-based antireflection coating. Ag-nanoparticle-assisted black Si etching and post-etching chemical treatment recently developed at NREL enables excellent control over the pore diameter and pore separation. Performance of black Si solar cells, including open-circuit voltage, short-circuit current density, and blue response, has benefited from these improvements. Prior to this study, our black Si solar cells were all passivated by thermal SiO2 produced in tube furnaces. Although this passivation is effective, it is not yet ideal for ultra-low-cost manufacturing. In this study, we report, for the first time, the integration of black Si with a proprietary liquid-phase deposition (LPD) passivation from Natcore Technology. The Natcore LPD forms a layer of <10-nm SiO2 on top of the black Si surface in a relatively mild chemical bath at room temperature. We demonstrate black Si solar cells with LPD SiO2 with a spectrum-weighted average reflection lower than 5%, similar to the more costly thermally grown SiO2 approach. However, LPD SiO2 provides somewhat better surface-passivation quality according to the lifetime analysis by the photo-conductivity decay measurement. Moreover, black Si solar cells with LPD SiO2 passivation exhibit higher spectral response at short wavelength compared to those passivated by thermally grown SiO2. With further optimization, the combination of aqueous black Si etching and LPD could provide a pathway for low-cost, high-efficiency crystalline Si solar cells.

  13. Insights into aerosol formation chemistry from comprehensive gas-phase precursor measurement in the TRAPOZ chamber experiments; an overview

    Science.gov (United States)

    Carr, Timo; Wyche, Kevin; Monks, Paul S.; Camredon, Marie; Alam, Mohammed S.; Bloss, William J.; Rickard, Andrew R.

    2010-05-01

    Aerosols have a profound affect on the environment on local, regional and even global levels, with impacts including adverse health effects, (Alfarra, Paulsen et al. 2006) visibility reduction, cloud formation, direct radiative forcing (Charlson, Schwartz et al. 1992) and an important role in influencing the climate due to their contribution to important atmospheric processes (Baltensperger, Kalberer et al. 2005; Alfarra, Paulsen et al. 2006). The Total Radical Production from the OZonolysis of alkenes (TRAPOZ) project was used to study the gas phase and radical chemistry along with secondary organic aerosol (SOA) formation for a number of different alkenes and terpenes. In order to better the scientific knowledge regarding the oxidation mechanisms of terpene and alkene species along with radical and SOA formation, the experiments were conducted under varying conditions controlled and monitored by the EUropean PHOto REactor (EUPHORE) simulation chamber in Valencia, Spain. A vast number of instruments enabled a detailed examination of the chemistry within oxidation of each precursor. However the work here will focus on the results obtained from the University of Leicester Chemical Ionisation Reaction Time-of-Flight Mass Spectrometer (CIR-TOF-MS). With regard to the gas phase chemistry an analysis of the degradation of the precursor Volatile Organic Compounds (VOCs) and evolution of certain gas phase species in each experiment has been presented and discussed.

  14. Instrumental Analysis in Environmental Chemistry - Liquid and Solid Phase Detection Systems

    Science.gov (United States)

    Stedman, Donald H.; Meyers, Philip A.

    1974-01-01

    This is the second of two reviews dealing with analytical methods applicable to environmental chemistry. Methods are discussed under gas, liquid, or solid depending upon the state of the analyte during detection. (RH)

  15. A Simple Experiment in the Separation of a Solid-Phase Mixture and Infrared Spectroscopy for Introductory Chemistry

    Science.gov (United States)

    Szalay, Paul S.

    2008-01-01

    This experiment was developed as a means of incorporating instrumental analyses into an introductory chemistry laboratory. A two-component solid mixture of caffeine and ibuprofen is separated through a series of solution extractions and precipitation and their relative amounts measured. These compounds were chosen because the combination of…

  16. General relativity with a topological phase: an action principle

    OpenAIRE

    Smolin, Lee; Starodubtsev, Artem

    2003-01-01

    An action principle is described which unifies general relativity and topological field theory. An additional degree of freedom is introduced and depending on the value it takes the theory has solutions that reduce it to 1) general relativity in Palatini form, 2) general relativity in the Ashtekar form, 3) $F\\wedge F$ theory for SO(5) and 4) $BF$ theory for SO(5). This theory then makes it possible to describe explicitly the dynamics of phase transition between a topological phase and a gravi...

  17. Impact of relative phase shift on inward turbulent spreading

    Energy Technology Data Exchange (ETDEWEB)

    Ma, C. H.; Xi, P. W. [Fusion Simulation Center, School of Physics, Peking University, Beijing (China); Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Xu, X. Q. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Xia, T. Y. [Institute of Plasma Physics, Chinese Academy of Sciences, Hefei (China); Lawrence Livermore National Laboratory, Livermore, California 94550 (United States)

    2015-01-15

    The relative cross-phase between density, temperature, and potential perturbations plays a major role in turbulent spreading and transport. Nonlinear Landau-Fluid simulations show that the electron wave-particle resonances provide a relatively strong parallel damping effect on the electron temperature perturbation and can induce a relative cross-phase shift of smaller than π∕2 angle between E × B velocity and the electron temperature perturbation for large electron temperature gradient, which yields a large spreading for electron. The relative phase for ions is about π∕2 and has no turbulent spreading effect on it. The inward turbulent spreading stops at the position where the radial turbulent correlation length is shorter than the magnetic surface spacing. The temperature pedestal height determines the energy loss due to the turbulent spreading.

  18. Dietary intake and serum bone related chemistry and their correlations inpostmenopausal Iranian women

    International Nuclear Information System (INIS)

    Objective was to determine dietary intake and bone related chemistry ofosteoporosis and their correlations in postmenopausal Iranian women. Across-sectional study was carried out on 58 healthy Iranian, postmenopausalwomen from January 2005 until August 2006, at Sina Hospital, Tabriz, Iran.Serum calcium, phosphorous, magnesium and alkaline phosphatase were measuredusing autoanalyzer and parathyroid hormone (PTH) by immune radio metricassay. Dietary intake was assessed by 3-day dietary record. Bone mineraldensity (BMD) was assessed by dual-energy x-ray absorptiometry (DXA) at thelumbar spine and left femur. Comparison between means of the groups wascarried out using one-way analysis of variance test. To examine thecorrelation between dietary factors and bone related chemistry markers,multiple and linear regression was used. According to the results of lumbarspine BMD, women (n=58) were classified into 3 groups: normal (n=18),osteopenia (n=22) and osteoporosis (n=18). The mean serum calcium,phosphorous, magnesium and alkaline phosphates in 3 groups were in the normalrange. Serum PTH in the osteoporosis group was higher than other groups. Themean dietary calcium intake in the osteoporosis groups was significantlylower than the normal group (p=0.01). The results of analyzing by linearregression, showed a significant correlation between calcium intake and PTH(r=-0.61, p=0.0001, B=-0.032). These findings suggest that postmenopausalwomen need to be educated regarding osteoporosis and the related preventivemeasures such as the effect of nutrients on bone health and the adequateintake of dairy products and calcium rich foods. (author)

  19. Current-phase relation of graphene Josephson junctions

    OpenAIRE

    Chialvo, C.; Moraru, I. C.; Van Harlingen, D. J.; Mason, N.

    2010-01-01

    The current-phase relation (CPR) of a Josephson junction reveals valuable information about the microscopic processes and symmetries that influence the supercurrent. In this Letter, we present direct measurements of the CPR for Josephson junctions with a graphene barrier, obtained by a phase-sensitive SQUID interferometry technique. We find that the CPR is skewed with respect to the commonly observed sinusoidal behavior. The amount of skewness varies linearly with critical current (Ic) regard...

  20. Phase analysis of circadian-related genes in two tissues

    Directory of Open Access Journals (Sweden)

    Li Leping

    2006-02-01

    Full Text Available Abstract Background Recent circadian clock studies using gene expression microarray in two different tissues of mouse have revealed not all circadian-related genes are synchronized in phase or peak expression times across tissues in vivo. Instead, some circadian-related genes may be delayed by 4–8 hrs in peak expression in one tissue relative to the other. These interesting biological observations prompt a statistical question regarding how to distinguish the synchronized genes from genes that are systematically lagged in phase/peak expression time across two tissues. Results We propose a set of techniques from circular statistics to analyze phase angles of circadian-related genes in two tissues. We first estimate the phases of a cycling gene separately in each tissue, which are then used to estimate the paired angular difference of the phase angles of the gene in the two tissues. These differences are modeled as a mixture of two von Mises distributions which enables us to cluster genes into two groups; one group having synchronized transcripts with the same phase in the two tissues, the other containing transcripts with a discrepancy in phase between the two tissues. For each cluster of genes we assess the association of phases across the tissue types using circular-circular regression. We also develop a bootstrap methodology based on a circular-circular regression model to evaluate the improvement in fit provided by allowing two components versus a one-component von-Mises model. Conclusion We applied our proposed methodologies to the circadian-related genes common to heart and liver tissues in Storch et al. 2, and found that an estimated 80% of circadian-related transcripts common to heart and liver tissues were synchronized in phase, and the other 20% of transcripts were lagged about 8 hours in liver relative to heart. The bootstrap p-value for being one cluster is 0.063, which suggests the possibility of two clusters. Our methodologies can

  1. XVIII Mendeleev congress on general and applied chemistry. Summaries of reports in five volumes. Volume 5. IV Russian-French symposium Supramolecular systems in chemistry and biology. II Russian-Indian symposium on organic chemistry. International symposium on present-day radiochemistry Radiochemistry: progress and prospects. International symposium Green chemistry, stable evolution and social responsibility of chemists. Symposium Nucleophilic hydrogen substitution in aromatic systems and related reactions

    International Nuclear Information System (INIS)

    The 5 volume of the XVIII Mendeleev congress on general and applied chemistry includes summaries of reports on the subjects of sypramolecular systems in chemistry and biology, organic chemistry, modern radiochemistry, green chemistry - development and social responsibility of chemists, nucleophilic hydrogen substitution in aromatic systems and related chemical reactions

  2. The role of phase space geometry in Heisenberg's uncertainty relation

    International Nuclear Information System (INIS)

    Aiming towards a geometric description of quantum theory, we study the coherent states-induced metric on the phase space, which provides a geometric formulation of the Heisenberg uncertainty relations (both the position-momentum and the time-energy ones). The metric also distinguishes the original uncertainty relations of Heisenberg from the ones that are obtained from non-commutativity of operators. Conversely, the uncertainty relations can be written in terms of this metric only, hence they can be formulated for any physical system, including ones with non-trivial phase space. Moreover, the metric is a key ingredient of the probability structure of continuous-time histories on phase space. This fact allows a simple new proof the impossibility of the physical manifestation of the quantum Zeno and anti-Zeno paradoxes. Finally, we construct the coherent states for a spinless relativistic particle, as a non-trivial example by which we demonstrate our results

  3. Fission gas release and fuel rod chemistry related to extended burnup

    International Nuclear Information System (INIS)

    The purpose of the meeting was to review the state of the art in fission gas release and fuel rod chemistry related to extended burnup. The meeting was held in a time when national and international programmes on water reactor fuel irradiated in experimental reactors were still ongoing or had reached their conclusion, and when lead test assemblies had reached high burnup in power reactors and been examined. At the same time, several out-of-pile experiments on high burnup fuel or with simulated fuel were being carried out. As a result, significant progress has been registered since the last meeting, particularly in the evaluation of fuel temperature, the degradation of the global thermal conductivity with burnup and in the understanding of the impact on fission gas release. Fifty five participants from 16 countries and one international organization attended the meeting. 28 papers were presented. A separate abstract was prepared for each of the papers. Refs, figs, tabs and photos

  4. Literature survey of the aqueous chemistry of technetium related to photolysis

    International Nuclear Information System (INIS)

    A literature survey was made to accumulate information about the chemistry of technetium as it relates to photolysis. The electrochemical potentials and the reactions of the various technetium compounds and complexes are discussed, along with the various absorption spectra of the different species. The TcCl62- ion has been shown to be photochemically active in HCl solutions. Hexachlorotechnetate(IV) is oxidized when exposed to sunlight in concentrated HCl. A ligand change occurs when it is exposed to either 254- or 34-nm radiation in more dilute HCl. No other photolysis reactions were found in the literature. It is possible that, under appropriate conditions, other valence states of technetium would be photochemically active, resulting in either redox or ligand exchange reactions. Proposals for investigating the photochemical reduction of the pertechnetate in HNO3 and other media are discussed

  5. Two-phase relative permeability models in reservoir engineering calculations

    Energy Technology Data Exchange (ETDEWEB)

    Siddiqui, S.; Hicks, P.J.; Ertekin, T.

    1999-01-15

    A comparison of ten two-phase relative permeability models is conducted using experimental, semianalytical and numerical approaches. Model predicted relative permeabilities are compared with data from 12 steady-state experiments on Berea and Brown sandstones using combinations of three white mineral oils and 2% CaCl1 brine. The model results are compared against the experimental data using three different criteria. The models are found to predict the relative permeability to oil, relative permeability to water and fractional flow of water with varying degrees of success. Relative permeability data from four of the experimental runs are used to predict the displacement performance under Buckley-Leverett conditions and the results are compared against those predicted by the models. Finally, waterflooding performances predicted by the models are analyzed at three different viscosity ratios using a two-dimensional, two-phase numerical reservoir simulator. (author)

  6. Solid-Phase Synthesis of Small Molecule Libraries using Double Combinatorial Chemistry

    DEFF Research Database (Denmark)

    Nielsen, John; Jensen, Flemming R.

    1997-01-01

    The first synthesis of a combinatorial library using double combinatorial chemistry is presented. Coupling of unprotected Fmoc-tyrosine to the solid support was followed by Mitsunobu O-alkylation. Introduction of a diacid linker yields a system in which the double combinatorial step can be...

  7. Gas phase chemistry and removal of CH{sub 3}I during a severe accident

    Energy Technology Data Exchange (ETDEWEB)

    Karhu, A. [VTT. Energy, Esbo (Finland)

    2001-01-01

    The purpose of this literature review was to gather valuable information on the behavior of methyl iodide on the gas phase during a severe accident. The potential of transition metals, especially silver and copper, to remove organic iodides from the gas streams was also studied. Transition metals are one of the most interesting groups in the context of iodine mitigation. For example silver is known to react intensively with iodine compounds. Silver is also relatively inert material and it is thermally stable. Copper is known to react with some radioiodine species. However, it is not reactive toward methyl iodide. In addition, it is oxidized to copper oxide under atmospheric conditions. This may limit the industrial use of copper.(au)

  8. Gas phase chemistry and removal of CH3I during a severe accident

    International Nuclear Information System (INIS)

    The purpose of this literature review was to gather valuable information on the behavior of methyl iodide on the gas phase during a severe accident. The potential of transition metals, especially silver and copper, to remove organic iodides from the gas streams was also studied. Transition metals are one of the most interesting groups in the context of iodine mitigation. For example silver is known to react intensively with iodine compounds. Silver is also relatively inert material and it is thermally stable. Copper is known to react with some radioiodine species. However, it is not reactive toward methyl iodide. In addition, it is oxidized to copper oxide under atmospheric conditions. This may limit the industrial use of copper.(au)

  9. Design improvements related to chemistry for the Evolutionary Power reactor (EPR) unit at Flamanville 3

    International Nuclear Information System (INIS)

    A significant number of improvements, including for chemistry, have been made for the design of the EPR turbine hall as a result of the considerable wealth of experience and feedback drawn from the EDF fleet. To reduce issues associated with flow accelerated corrosion, as well as Steam Generator (SG) fouling or clogging, appropriate materials for the piping and the exchangers, and an adequate chemical conditioning, were chosen to ensure a 60 year lifespan of the main components of the circuit. The condenser technology was also improved to mitigate the risks of raw water ingress. A dedicated local sampling line was added at feedwater (FW) to monitor the iron concentration. EPR includes a polishing system at start-up to ensure the purification of feedwater in a short time (less than 16 hours) along with reduced discharged effluents. Comprehensive studies were carried out, taking into account costs (investment, operation, and maintenance), consumption and discharge of chemical reagents, or risks of pollutions during the process. This lead to the choice of system dedicated to start-up only, similar to the mobile system used in some French Nuclear Power Plants (NPPs), instead of a condensate polishing plant. Emphasis was also placed on providing a flexible and secure injection system for the chemical reagents (SIR). Indeed, it will be possible to inject two amines and hydrazine, and to perform tailored injection in many parts of the circuit. Furthermore, the room was design to facilitate future design changes, such as if dispersant injection is required as a preventative solution for SG fouling. In addition to that, close attention was applied to mitigate chemical hazards, especially regarding the hydrazine CMR effect or explosive atmosphere. This paper describes the technical and the economical choices that lead to these improvements related to chemistry in the turbine hall design, along with a comprehensive overview of the chosen designs. (authors)

  10. Behavioral and physiological correlates of stress related to examination performance in college chemistry students.

    Science.gov (United States)

    Bardi, M; Koone, T; Mewaldt, S; O'Connor, K

    2011-09-01

    This study was designed to assess physiological and behavioral correlates of academic stress during a college course in organic chemistry in the USA. Participants (45 females, 46 males, mean age 19.88 years) were screened for their basal hypothalamic-pituitary-adrenocortical activity using saliva samples collected at the beginning of the course and after each major test. Displacement activities (DAs) were observed during each test by videotaping students' behavior when they were taking the tests. These variables were then used as predictors of the students' achievement as measured by their grade point average (GPA) scores, American College Testing (ACT) scores, and their final grade in the class. Ninety-one students, enrolled in Organic Chemistry I at Marshall University during the summer of 2009, were recruited for this study. It was found that individual differences in the physiological stress responses are a factor in predicting the students' ability to pass a challenging class. A logistic model built on GPA, DAs during stress, and salivary hormone (cortisol and dehydroepiandrosterone) concentrations was able to correctly classify almost 90% of the students passing the class. The same model was not nearly as successful in determining the possible factors behind failing the class, because the classification success was just 52%, a figure close to chance. We conclude that a clear set of characteristics related to the students' ability and resilience to psychological stress are necessary to succeed in a challenging class. The reason behind dropping or failing a class could be less defined. These data indicated that investigating the physiological and behavioral propensities associated with psychological stress can help us better understand an individual's coping responses to a long-term challenging situation. PMID:21682652

  11. Solution-phase-peptide synthesis via the group-assisted purification (GAP) chemistry without using chromatography and recrystallization.

    Science.gov (United States)

    Wu, Jianbin; An, Guanghui; Lin, Siqi; Xie, Jianbo; Zhou, Wei; Sun, Hao; Pan, Yi; Li, Guigen

    2014-02-01

    The solution phase synthesis of N-protected amino acids and peptides has been achieved through the Group-Assisted Purification (GAP) chemistry by avoiding disadvantages of other methods in regard to the difficult scale-up, expenses of solid and soluble polymers, etc. The GAP synthesis can reduce the use of solvents, silica gels, energy and manpower. In addition, the GAP auxiliary can be conveniently recovered for re-use and is environmentally friendly and benign, and substantially reduces waste production in academic labs and industry. PMID:24336500

  12. Crystal Chemistry of Three-component White Dwarfs and Neutron Star Crusts: Phase Stability, Phase Stratification, and Physical Properties

    Science.gov (United States)

    Engstrom, T. A.; Yoder, N. C.; Crespi, V. H.

    2016-02-01

    A systematic search for multicomponent crystal structures is carried out for five different ternary systems of nuclei in a polarizable background of electrons, representative of accreted neutron star crusts and some white dwarfs. Candidate structures are “bred” by a genetic algorithm and optimized at constant pressure under the assumption of linear response (Thomas-Fermi) charge screening. Subsequent phase equilibria calculations reveal eight distinct crystal structures in the T = 0 bulk phase diagrams, five of which are complicated multinary structures not previously predicted in the context of compact object astrophysics. Frequent instances of geometrically similar but compositionally distinct phases give insight into structural preferences of systems with pairwise Yukawa interactions, including and extending to the regime of low-density colloidal suspensions made in a laboratory. As an application of these main results, we self-consistently couple the phase stability problem to the equations for a self-gravitating, hydrostatically stable white dwarf, with fixed overall composition. To our knowledge, this is the first attempt to incorporate complex multinary phases into the equilibrium phase-layering diagram and mass-radius-composition dependence, both of which are reported for He-C-O and C-O-Ne white dwarfs. Finite thickness interfacial phases (“interphases”) show up at the boundaries between single-component body-centered cubic (bcc) crystalline regions, some of which have lower lattice symmetry than cubic. A second application—quasi-static settling of heavy nuclei in white dwarfs—builds on our equilibrium phase-layering method. Tests of this nonequilibrium method reveal extra phases that play the role of transient host phases for the settling species.

  13. The Relative Phase Asynchronization between Sunspot Numbers and Polar Faculae

    Indian Academy of Sciences (India)

    L. H. Deng; J. Y. Song; Y. Y. Xiang; Y. K. Tang

    2011-09-01

    The monthly sunspot numbers compiled by Temmer et al. and the monthly polar faculae from observations of the National Astronomical Observatory of Japan, for the interval of March 1954 to March 1996, are used to investigate the phase relationship between polar faculae and sunspot activity for total solar disk and for both hemispheres in solar cycles 19, 20, 21 and 22. We found that (1) the polar faculae begin earlier than sunspot activity, and the phase difference exhibits a consistent behaviour for different hemispheres in each of the solar cycles, implying that this phenomenon should not be regarded as a stochastic fluctuation; (2) the inverse correlation between polar faculae and sunspot numbers is not only a long-term behaviour, but also exists in short time range; (3) the polar faculae show leads of about 50–71 months relative to sunspot numbers, and the phase difference between them varies with solar cycle; (4) the phase difference value in the northern hemisphere differs from that in the southern hemisphere in a solar cycle, which means that phase difference also existed between the two hemispheres. Moreover, the phase difference between the two hemispheres exhibits a periodical behaviour. Our results seem to support the finding of Hiremath (2010).

  14. Application of Radiation Chemistry to Some Selected Technological Issues Related to the Development of Nuclear Energy.

    Science.gov (United States)

    Bobrowski, Krzysztof; Skotnicki, Konrad; Szreder, Tomasz

    2016-10-01

    The most important contributions of radiation chemistry to some selected technological issues related to water-cooled reactors, reprocessing of spent nuclear fuel and high-level radioactive wastes, and fuel evolution during final radioactive waste disposal are highlighted. Chemical reactions occurring at the operating temperatures and pressures of reactors and involving primary transients and stable products from water radiolysis are presented and discussed in terms of the kinetic parameters and radiation chemical yields. The knowledge of these parameters is essential since they serve as input data to the models of water radiolysis in the primary loop of light water reactors and super critical water reactors. Selected features of water radiolysis in heterogeneous systems, such as aqueous nanoparticle suspensions and slurries, ceramic oxides surfaces, nanoporous, and cement-based materials, are discussed. They are of particular concern in the primary cooling loops in nuclear reactors and long-term storage of nuclear waste in geological repositories. This also includes radiation-induced processes related to corrosion of cladding materials and copper-coated iron canisters, dissolution of spent nuclear fuel, and changes of bentonite clays properties. Radiation-induced processes affecting stability of solvents and solvent extraction ligands as well oxidation states of actinide metal ions during recycling of the spent nuclear fuel are also briefly summarized. PMID:27573502

  15. Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multi-layer model ADCHAM

    Directory of Open Access Journals (Sweden)

    P. Roldin

    2014-01-01

    Full Text Available We have developed the novel Aerosol Dynamics, gas- and particle-phase chemistry model for laboratory CHAMber studies (ADCHAM. The model combines the detailed gas phase Master Chemical Mechanism version 3.2, an aerosol dynamics and particle phase chemistry module (which considers acid catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions and a kinetic multilayer module for diffusion limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study: (1 the mass transfer limited uptake of ammonia (NH3 and formation of organic salts between ammonium (NH4+ and carboxylic acids (RCOOH, (2 the slow and almost particle size independent evaporation of α-pinene secondary organic aerosol (SOA particles, and (3 the influence of chamber wall effects on the observed SOA formation in smog chambers. ADCHAM is able to capture the observed α-pinene SOA mass increase in the presence of NH3(g. Organic salts of ammonium and carboxylic acids predominantly form during the early stage of SOA formation. These salts contribute substantially to the initial growth of the homogeneously nucleated particles. The model simulations of evaporating α-pinene SOA particles support the recent experimental findings that these particles have a semi-solid tar like amorphous phase state. ADCHAM is able to reproduce the main features of the observed slow evaporation rates if low-volatility and viscous oligomerized SOA material accumulates in the particle surface layer upon evaporation. The evaporation rate is mainly governed by the reversible decomposition of oligomers back to monomers. Finally, we demonstrate that the mass transfer limited uptake of condensable organic compounds onto wall deposited particles or directly onto the Teflon chamber walls of smog chambers can have profound influence on

  16. Multiconfigurational quantum chemistry for actinide containing systems: from isolated molecules to condensed phase

    International Nuclear Information System (INIS)

    Complete text of publication follows: Ab initio quantum chemistry is a mature science that allows the study of molecular species containing any of the atoms in the periodic system. In this lecture I will describe our latest achievements in the prediction of novel chemical bonds and chemical species, including the multiple bond in the early-di-actinide series [1] and some novel inorganic compounds containing the di-uranium moiety [2]. In nature most of actinide chemistry occurs in solution. We try to combine ab initio quantum chemistry with classical molecular dynamics simulations in order to understand the behavior of highly charged ions in solution. Our recent studies of uranyl [3] and Cm(III) [4] in water will be presented. References: [1] B. O. Roos, P.-A. Malmqvist and L. Gagliardi, Exploring the actinide-actinide bond: Theoretical studies of the chemical bond in Ac2, Th2, Pa2, and U2 J. Am. Chem. Soc. 128, 17000-17006 (2006) [2] G. La Macchia, M. Brynda, and L. Gagliardi, Quantum chemical calculations predict the diphenyl di-uranium compound, PhUUPh, to have a stable 1Ag ground state Angew. Chem. Int. Ed. 45, 6210-6213 (2006); [3] D. Hagberg, G. Karlstrom, B .O. Roos and L. Gagliardi, The coordination of uranyl in water: a combined quantum chemical and molecular simulation study J. Am. Chem. Soc. 127, 14250-14256 (2005); [4] E. Bednarz, D. Hagberg, L. Gagliardi in preparation

  17. Gas-phase chemistry of the silaformyl anion, HSiO sup minus

    Energy Technology Data Exchange (ETDEWEB)

    Gronert, S.; Prodnuk, S.; DePuy, C.H. (Univ. of Colorado, Boulder (USA)); O' Hair, R.A.J. (Univ. of Adelaide (Australia)); Suelzle, D. (Institut fuer Organische Chemie der Technischen Universitaet Berlin (West Germany)); Damrauer, R. (Univ. of Colorado, Denver (USA))

    1990-01-31

    The silaformyl anion, HSiO{sup {minus}}, has been prepared by collisionally induced dissociation (CID) of H{sub 3}SiO{sup {minus}} in a tandem flowing afterglow selected ion flow tube (FA-SIFT). The chemistry of the silaformyl anion has been studied in detail. Reactions with CO{sub 2}, COS, CS{sub 2}, SO{sub 2}, O{sub 2}, acetic acid, nitromethane, and hexafluorobenzene reveal a rich chemistry. For example, the sailaformyl anion reacts with CO{sub 2} by both an oxidative pathway giving HSiO{sub 2}{sup {minus}} and CO and a reductive path giving SiO and HCO{sub 2}{sup {minus}}. Typically, the silaformyl anion, which could have several sites of reactivity, behaves both as an oxygen nucleophile and as a hydride donor. Detailed mechanistic studies have been carried out on many of these reactions with isotopically labeled H{sup 29}SiO{sup {minus}} and HSi{sup 18}O{sup {minus}}. In addition to its reaction chemistry, the heat of formation of the silaformyl anion, its basicity, and the heat of formation of its parent compound have been estimated. Ab initio computations on the silaformyl anion have been carried out and demonstrate that HSiO{sup {minus}} is more than 40 kcal/mol more stable than HOSi{sup {minus}}.

  18. Crystal chemistry of three-component white dwarfs and neutron star crusts: phase stability, phase stratification, and physical properties

    CERN Document Server

    Engstrom, T A; Crespi, V H

    2015-01-01

    A systematic search for multicomponent crystal structures is carried out for five different ternary systems of nuclei in a polarizable background of electrons, representative of accreted neutron star crusts and some white dwarfs. Candidate structures are "bred" by a genetic algorithm, and optimized at constant pressure under the assumption of linear response (Thomas-Fermi) charge screening. Subsequent phase equilibria calculations reveal eight distinct crystal structures in the $T=0$ bulk phase diagrams, five of which are complicated multinary structures not before predicted in the context of compact object astrophysics. Frequent instances of geometrically similar but compositionally distinct phases give insight into structural preferences of systems with pairwise Yukawa interactions, including and extending to the regime of low density colloidal suspensions made in a laboratory. As an application of these main results, we self-consistently couple the phase stability problem to the equations for a self-gravit...

  19. Assistance in chemistry and chemical processes related to primary, secondary and ancillary systems of nuclear power plants

    International Nuclear Information System (INIS)

    Argentina is currently running two nuclear power plants: Atucha I (CNA I) and Embalse (CNE) operated by Nucleoelectrica Argentina (NASA) whereas the National Atomic Energy Commission (CNEA), among other activities, is responsible for research and development in the nuclear field, operates research reactors and carries out projects related to them. In particular, the Reactor Chemistry Section personnel (currently part of the Chemistry Dept.) has been working on the field of reactor water chemistry for more than 25 years, on research and support to the NPPs chemistry department. Though the most relevant tasks have been connected to primary and secondary circuits chemistry, ancillary systems show along the time unexpected problems or feasible improvements originated in the undergoing operating time as well as in phenomena not foreseen by the constructors. In the present paper are presented the tasks performed in relation to the following systems of Embalse NPP: 1) Heavy water upgrade column preliminary water treatment; 2) Liquid waste system preliminary water treatment; and 3) Primary heat transport system coolant crud composition. (author)

  20. The role of European Federation of Clinical Chemistry and Laboratory Medicine Working Group for Preanalytical Phase in standardization and harmonization of the preanalytical phase in Europe

    DEFF Research Database (Denmark)

    Cornes, Michael P; Church, Stephen; van Dongen-Lases, Edmée;

    2016-01-01

    Patient safety is a leading challenge in healthcare and from the laboratory perspective it is now well established that preanalytical errors are the major contributor to the overall rate of diagnostic and therapeutic errors. To address this, the European Federation of Clinical Chemistry and...... Laboratory Medicine Working Group for Preanalytical Phase (EFLM WG-PRE) was established to lead in standardization and harmonization of preanalytical policies and practices at a European level. One of the key activities of the WG-PRE is the organization of the biennial EFLM-BD conference on the preanalytical...... summarises the work that has and will be done in these areas. The goal of this initiative is to ensure the EFLM WG-PRE produces work that meets the needs of the European laboratory medicine community. Progress made in the identified areas will be updated at the next preanalytical phase conference and show...

  1. Gas-phase chemistry of curium: Reactions of Cm+ and CmO+ with alkenes, acetonitrile, and hexafluoropropene

    International Nuclear Information System (INIS)

    The metal ions, Cm+, U+, and Tb+, and their oxides, MO+, were reacted in the gas phase with alkenes, acetonitrile, and hexafluoropropene, Product compositions and abundances provide a survey of essential aspects of the gas-phase chemistry of the curium cation, now the heaviest element for which such systematic studies have been carried out (U and Tb were included to provide comparisons). Of particular interest is the difference in behavior between the 4f lanthanide and 5f actinide series and variations in chemistry across the actinide series. The primary emphasis was on reactions with alkenes, particularly dehydrogenation, as indicative of the ability of a M+ to activate C-H bonds (the extent of C-C activation was generally in parallel with that of C-H activation). With acetonitrile and all of the alkenes (except ethene), the three M+ ions induced dehydrogenation. Variations were evident for the different reactant substrates, but the overall qualitative ordering of dehydrogenation efficiency was U+ > Tb+ > Cm+. With hexafluoropropene, the primary reaction channel was F abstraction and the discrepant reactivities reflected the propensity for U to oxidize to higher valence states compared to Cm or Tb. The terminal MFn+ were CmIIIF2+, TbIIIF2+, and UIVF4+, and among the MO+, only UO+ induced F abstraction, producing UOFn+ with n = 1--3

  2. The Lampedusa supersite of ChArMex: observing aerosol-radiation interactions and gas phase chemistry in the Mediterranean

    Science.gov (United States)

    Formenti, Paola; di Sarra, Alcide Giorgio

    2014-05-01

    Within the frame of the ADRIMED (Aerosol Direct Radiative Impact in the regional climate in the MEDiterranean region) project of the Chemistry-Aerosol Mediterranean experiment (ChArMex), the ENEA Laboratory for Climate Study "Roberto Sarao" (WMO/GAW/NDACC) on the Island of Lampedusa (35°31'N, 12°37°E) has been augmented to one of the supersites of the first phase of the Special Observing Period 1 by the measurements of the in situ properties of aerosols and trace gases by the of the PortablE Gas and Aerosol Sampling Units (PEGASUS) mobile station. The ground-based measurements have been completed by several coordinated overpasses of the ATR-42 and the F20 of SAFIRE. In this paper we present the first highlights of operations, which took place between June 6 and July 8 2013. Insights on the data provide with an unprecedented characterisation of the physico-chemical and properties aerosols and gas phase chemistry on air masses of various origins (pollution, marine, mineral dust, …..). The effect of aerosols on radiation fields is ascertained by coupling ground-based and aircraft measurements during dedicated overpasses providing with measurements of upwelling and downwelling shortwave and longwave radiation fluxes together with the properties of the aerosol load resolved on the column. Coordination with CALIPSO overpasses will also be explored.

  3. Structure-property relations in bismuth-based Aurivillius phases

    CERN Document Server

    Sandoval, D Y S

    2001-01-01

    ferroelectric phase transition in Aurivillius phases. Orientational and translational domains arising from a change in crystal class and a doubling of the unit cell were detected. At the (PE) tetragonal - (PE) orthorhombic phase transition 90 deg ferroelastic domains are formed. Finally, at the (PE) orthorhombic to the (FE) orthorhombic phase transition centro-symmetry is lost, the ferroelastic orientation domain boundaries (ODBs) become ferroelectric and anti phase boundaries (APBs) are coupled with inversion domain boundaries (IDBs). The aim of this work was to relate the onset temperature and amplitude (qualitatively) of rotations of the octahedra to the onset of ferroelectricity in a range of Aurivillius compounds. Several stoichiometries were tested, including MBi sub 2 Nb sub 2 O sub 9 , MBi sub 4 Ti sub 4 O sub 1 sub 5 , M sub 2 Bi sub 4 Ti sub 5 O sub 1 sub 8 and MBi sub 8 Ti sub 7 O sub 2 sub 7 with the substitution of divalent (Ca sup 2 sup + , Sr sup 2 sup + , Pb sup 2 sup + and Ba sup 2 sup +) and...

  4. A Study of Motivation and Other Factors as Relating to Course Achievement in Introductory College Biology, Chemistry, and Physics.

    Science.gov (United States)

    Pridmore, Brooke M.; Halyard, Rebecca A.

    Results of a preliminary study that examined various factors relating to achievement in introductory level biology, chemistry, and physics classes at a public junior college are presented. Background variables, including age, sex, college major, grade point average, SAT-Verbal and SAT-Quantitative, and the sixteen-part scores of Academic…

  5. Development and Assessment of a Diagnostic Tool to Identify Organic Chemistry Students' Alternative Conceptions Related to Acid Strength

    Science.gov (United States)

    McClary, LaKeisha M.; Bretz, Stacey Lowery

    2012-01-01

    The central goal of this study was to create a new diagnostic tool to identify organic chemistry students' alternative conceptions related to acid strength. Twenty years of research on secondary and college students' conceptions about acids and bases has shown that these important concepts are difficult for students to apply to qualitative problem…

  6. The relationship between teacher-related factors and students' attitudes towards secondary school chemistry subject in Bureti district, Kenya

    Directory of Open Access Journals (Sweden)

    Salome Chepkorir

    2014-12-01

    Full Text Available This paper examines the relationship between teacher-related factors and student’s attitudes towards Chemistry subject in secondary schools in Kenya. The paper is based on a study conducted in Bureti District in Kericho County, Kenya. This paper highlights issues on the teaching methods used by chemistry teachers, the teachers’ availability to attend to various needs of students on the subject, their use of teaching and learning resources in teaching, teachers’ personal levels of skills and knowledge of the subject matter in Chemistry and the impact of students’ negative attitudes towards Chemistry on teachers’ effectiveness. The research design used in the study was descriptive survey. The target population comprised Form Four students in ten selected secondary schools in Bureti District of Rift Valley Province Kenya. Stratified random sampling technique was used to select the study sample. Schools were selected from the following categories: Girls’ schools, Boys’ schools and Co-educational schools. Simple random sampling was used to select the respondents from Form Four classes as well as a teacher in each school. In all, one hundred and eighty-nine students and ten teachers filled the questionnaires. The data collection instruments were questionnaires based on the Likert scale and document analysis. Data was analyzed descriptively using frequency tables, means and percentages while hypotheses were tested using Analysis of Variance. From the study findings, a number of indicators revealed that there are some factors influencing students’ attitudes towards Chemistry, including lack of successful experiences in Chemistry, poor teaching. It was recommended that science teachers’ should encourage development of positive self-concept of ability among students. Among other recommendations, the study suggests that guidance and counselling of students in schools should be encouraged, to ensure positive attitudes towards and full

  7. Nonsinusoidal Current-Phase Relation in SFS Josephson Junctions

    Science.gov (United States)

    Golubov, A. A.; Kupriyanov, M. Yu.; Fominov, Ya. V.

    2002-06-01

    Various types of the current-phase relation I(phi) in superconductor-ferromagnet-superconductor (SFS) point contacts and planar double-barrier junctions are studied within the quasiclassical theory in the limit of thin diffusive ferromagnetic interlayers. The physical mechanisms leading to highly nontrivial I(phi) dependence are identified by studying the spectral supercurrent density. These mechanisms are also responsible for the 0-pi transition in SFS Josephson junctions.

  8. Nonsinusoidal current-phase relation in SFS Josephson junctions

    International Nuclear Information System (INIS)

    Various types of the current-phase relation I(ψ) in superconductor-ferromagnet-superconductor (SFS) point contacts and planar double-barrier junctions are studied within the quasiclassical theory in the limit of thin diffusive ferromagnetic interlayers. The physical mechanisms, leading to highly nontrivial I(ψ) dependence, are identified by studying the spectral supercurrent density. These mechanisms are also responsible for the 0-π transition in SFS Josephson junctions

  9. Evaluation of innovative stationary phase ligand chemistries and analytical conditions for the analysis of basic drugs by supercritical fluid chromatography.

    Science.gov (United States)

    Desfontaine, Vincent; Veuthey, Jean-Luc; Guillarme, Davy

    2016-03-18

    Similar to reversed phase liquid chromatography, basic compounds can be highly challenging to analyze by supercritical fluid chromatography (SFC), as they tend to exhibit poor peak shape, especially those with high pKa values. In this study, three new stationary phase ligand chemistries available in sub -2μm particle sizes, namely 2-picolylamine (2-PIC), 1-aminoanthracene (1-AA) and diethylamine (DEA), were tested in SFC conditions for the analysis of basic drugs. Due to the basic properties of these ligands, it is expected that the repulsive forces may improve peak shape of basic substances, similarly to the widely used 2-ethypyridine (2-EP) phase. However, among the 38 tested basic drugs, less of 10% displayed Gaussian peaks (asymmetry between 0.8 and 1.4) using pure CO2/methanol on these phases. The addition of 10mM ammonium formate as mobile phase additive, drastically improved peak shapes and increased this proportion to 67% on 2-PIC. Introducing the additive in the injection solvent rather than in the organic modifier, gave acceptable results for 2-PIC only, with 31% of Gaussian peaks with an average asymmetry of 1.89 for the 38 selected basic drugs. These columns were also compared to hybrid silica (BEH), DIOL and 2-EP stationary phases, commonly employed in SFC. These phases commonly exhibit alternative retention and selectivity. In the end, the two most interesting ligands used as complementary columns were 2-PIC and BEH, as they provided suitable peak shapes for the basic drugs and almost orthogonal selectivities. PMID:26895829

  10. Partitioning of metals in different binding phases of tropical estuarine sediments: importance of metal chemistry.

    Science.gov (United States)

    Chakraborty, Parthasarathi; Chakraborty, Sucharita; Vudamala, Krushna; Sarkar, Arindam; Nath, B Nagender

    2016-02-01

    Distribution of metals in different binding phases of estuarine sediments provides chemically significant description of metal-sediment interactions. This study describes the influences of ligand field stabilization energy (LFSE), Jahn-Teller effect, and water exchange rate (k-w) on metal distribution in different binding phases of estuarine sediments. It was found that Cu had highest affinity for organic binding phases in the studied sediments followed by Ni and Pb. However, Pb showed strong association with Fe/Mn oxide phases followed by Ni and Cu. Faster k-w of Cu (II) (1 × 10(9) s(-1)) increased the rate of complex formation of Cu(2+) ion with ligand in the organic phases. The Cu-ligand (from organic phase) complexes gained extra stability by the Jahn-Teller effect. The combined effects of these two phenomena and high ionic potential increased the association of Cu with the organic phases of the sediments than Ni and Pb. The smaller ionic radii of Ni(2+) (0.72 Å) than Pb(2+) (1.20 Å) increase the stability of Ni-ligand complexes in the organic phase of the sediments. High LFSE of Ni(II) (compared with Pb(2+) ions) also make Ni-organic complexes increasingly stable than Pb. High k-w (7 × 10(9) s(-1)) of Pb did not help it to associate with organic phases in the sediments. The high concentration of Pb in the Fe/Mn oxyhydroxide binding phase was probably due to co-precipitation of Pb(2+) and Fe(3+). High surface area or site availability for Pb(2+) ion on Fe oxyhydroxide phase was probably responsible for the high concentration of Pb in Fe/Mn oxyhydroxide phase. Increasing concentrations of Cu in organic phases with the increasing Cu loading suggest that enough binding sites were available for Cu in the organic binding phases of the sediments. This study also describes the influence of nature of sedimentary organic carbon (terrestrial and marine derived OC) in controlling these metal distribution and speciation in marine sediment. PMID:26490921

  11. Phase relations and adiabats in boiling seafloor geothermal systems

    Science.gov (United States)

    Bischoff, James L.; Pitzer, Kenneth S.

    1985-11-01

    Observations of large salinity variations and vent temperatures in the range of 380-400°C suggest that boiling or two-phase separation may be occurring in some seafloor geothermal systems. Consideration of flow rates and the relatively small differences in density between vapors and liquids at the supercritical pressures at depth in these systems suggests that boiling is occurring under closed-system conditions. Salinity and temperature of boiling vents can be used to estimate the pressure-temperature point in the subsurface at which liquid seawater first reached the two-phase boundary. Data are reviewed to construct phase diagrams of coexisting brines and vapors in the two-phase region at pressures corresponding to those of the seafloor geothermal systems. A method is developed for calculating the enthalpy and entropy of the coexisting mixtures, and results are used to construct adiabats from the seafloor to the P-T two-phase boundary. Results for seafloor vents discharging at 2300 m below sea level indicate that a 385°C vent is composed of a brine (7% NaCl equivalent) in equilibrium with a vapor (0.1% NaCl). Brine constitutes 45% by weight of the mixture, and the fluid first boiled at approximately 1 km below the seafloor at 415°C, 330 bar. A 400°C vent is primarily vapor (88 wt.%, 0.044% NaCl) with a small amount of brine (26% NaCl) and first boiled at 2.9 km below the seafloor at 500°C, 520 bar. These results show that adiabatic decompression in the two-phase region results in dramatic cooling of the fluid mixture when there is a large fraction of vapor.

  12. Relativity implications of the quantum phase: A review of reciprocal relativity of noninertial states

    CERN Document Server

    Low, Stephen G

    2009-01-01

    The quantum phase requires projective representations that are equivalent to the unitary representations of the group's central extension. The Weyl-Heisenberg group is a central extension of the abelian translation group on extended phase space. Its automorphism group, that is the largest group preserving the Weyl-Heisenberg algebra, is the central extension of (essentially) the inhomogeneous symplectic group acting on extended phase space. This inhomogeneous symplectic group is the largest group for which the projective representations define Heisenberg commutation relations that are preserved under all transformations of the representation. This leads us to define the Born orthogonal metric on extended phase space for relativistic concepts of time and causality. This is the only new physical postulate of the theory. The resulting homogeneous group is a. This defines the reciprocal relativity theory of noninertial states in which proper time is affected by noninertial motion and the inertial frame is relativ...

  13. Theoretical Hammett Plot for the Gas-Phase Ionization of Benzoic Acid versus Phenol: A Computational Chemistry Lab Exercise

    Science.gov (United States)

    Ziegler, Blake E.

    2013-01-01

    Computational chemistry undergraduate laboratory courses are now part of the chemistry curriculum at many universities. However, there remains a lack of computational chemistry exercises available to instructors. This exercise is presented for students to develop skills using computational chemistry software while supplementing their knowledge of…

  14. Factors related to the economic sustainability of two-year chemistry-based technology training programs

    Science.gov (United States)

    Backus, Bridgid A.

    Two-year chemistry-based technology training (CBTT) programs in the U.S. are important in the preparation of the professional technical workforce. The purpose of this study was to identify, examine, and analyze factors related to the economic sustainability of CBTT programs. A review of literature identified four clustered categories of 31 sub-factors related to program sustainability. Three research questions relating to program sustainability were: (1) What is the relative importance of the identified factors?, (2) What differences exist between the opinions of administrators and faculty?, and (3) What are the interrelationships among the factors? In order to answer these questions, survey data gathered from CBTT programs throughout the United States were analyzed statistically. Conclusions included the following: (1) Rank order of the importance to sustainability of the clustered categories was: (1) Partnerships, (2) Employer and Student Educational Goals, (3) Faculty and Their Resources, and (4) Community Perceptions and Marketing Strategies. (2) Significant correlations between ratings of sustainability and the sub-factors included: degree of partnering, college responsiveness, administration involvement in partnerships, experiential learning opportunities, employer input in curriculum development, use of skill standards, number of program graduates, student job placement, professional development opportunities, administrator support, presence of a champion, flexible scheduling, program visibility, perception of chemical technicians, marketing plans, and promotion to secondary students. (3) Faculty and administrators differed significantly on only two sub-factor ratings: employer assisted curriculum development, and faculty workloads. (4) Significant differences in ratings by small program faculty and administrators and large program faculty and administrators were indicated, with most between small program faculty and large program administrators. The study

  15. Progress report 1987-1988. Reactor Chemistry Department

    International Nuclear Information System (INIS)

    Review of the activities performed by the Reactor Chemistry Department of the National Atomic Energy Commission of Argentina during 1987-1988. This department provides services and assistance in all matters related to water chemistry and nuclear reactors chemistry, in all their phases: design, construction, commissioning and decommissioning. The appendix includes information on the Reactor Chemistry Department staff, its publications, services, seminars, courses and conferences performed during 1987-1988. (Author)

  16. Glycol-Water Interactions and co-existing phases and Temperature Dependent Solubility. An Example Of Carbon-Hydrogen Chemistry In Water

    CERN Document Server

    Michael, Fredrick

    2010-01-01

    Recently there has been great interest in Glycol-Water chemistry and solubility and temperature dependent phase dynamics. The Glycol-Water biochemistry of interactions is present in plant biology and chemistry, is of great interest to chemical engineers and biochemists as it is a paradigm of Carbon-Hydrogen Water organic chemistry. There is an interest moreover in formulating a simpler theory and computation model for the Glycol-Water interaction and phase dynamics, that is not fully quantum mechanical yet has the high accuracy available from a fully quantum mechanical theory of phase transitions of fluids and Fermi systems. Along these lines of research interest we have derived a Lennard-Jones -like theory of interacting molecules-Water in a dissolved adducts of Glycol-Water system interacting by Hydrogen bonds whose validity is supported at the scale of interactions by other independent molecular dynamics investigations that utilize force fields dependent on their experimental fittings to the Lennard-Jones ...

  17. Relative success in college chemistry for students who experienced a high-school course in chemistry and those who had not

    Science.gov (United States)

    Yager, Robert E.; Snider, Bill; Krajcik, Joseph

    A total of 53 high-ability students who had completed the eleventh year in high school enrolled in a standard college chemistry course at the University of Iowa. Half of them had completed a high-school course in chemistry and half had not. After 2 months of instruction during a summer session, there was no difference between groups as to attitude toward chemistry, performance on the ACS-NSTA Chemistry Achievement Examination, final examination for the course, and course grade. There was a great difference in the amount of time required of tutors; the students who had not completed high-school chemistry spent more time in studying and with tutors.

  18. PhasePlot: A Software Program for Visualizing Phase Relations Computed Using Thermochemical Models and Databases

    Science.gov (United States)

    Ghiorso, M. S.

    2011-12-01

    A new software program has been developed for Macintosh computers that permits the visualization of phase relations calculated from thermodynamic data-model collections. The data-model collections of MELTS (Ghiorso and Sack, 1995, CMP 119, 197-212), pMELTS (Ghiorso et al., 2002, G-cubed 3, 10.1029/2001GC000217) and the deep mantle database of Stixrude and Lithgow-Bertelloni (2011, GJI 184, 1180-1213) are currently implemented. The software allows users to enter a system bulk composition and a range of reference conditions and then calculate a grid of phase relations. These relations may be visualized in a variety of ways including phase diagrams, phase proportion plots, and contour diagrams of phase compositions and abundances. Results may be exported into Excel or similar spreadsheet applications. Flexibility in stipulating reference conditions permit the construction of temperature-pressure, temperature-volume, entropy-pressure, or entropy-volume display grids. Calculations on the grid are performed for fixed bulk composition or in open systems governed by user specified constraints on component chemical potentials (e.g., specified oxygen fugacity buffers). The calculation engine for the software is optimized for multi-core compute architectures and is very fast, allowing a typical grid of 64 points to be calculated in under 10 seconds on a dual-core laptop/iMac. The underlying computational thermodynamic algorithms have been optimized for speed and robust behavior. Taken together, both of these advances facilitate in classroom demonstrations and permit novice users to work with the program effectively, focusing on problem specification and interpretation of results rather than on manipulation and mechanics of computation - a key feature of an effective instructional tool. The emphasis in this software package is graphical visualization, which aids in better comprehension of complex phase relations in multicomponent systems. Anecdotal experience in using Phase

  19. A solid phase extraction based non-disruptive sampling technique to investigate the surface chemistry of macroalgae.

    Science.gov (United States)

    Cirri, Emilio; Grosser, Katharina; Pohnert, Georg

    2016-01-01

    The surface chemistry of aquatic organisms determines their biotic interactions. Metabolites in the spatially limited laminar boundary layer mediate processes, such as antifouling, allelopathy and chemical defense against herbivores. However, very few methods are available for the investigation of such surface metabolites. An approach is described in which surfaces are extracted by means of C18 solid phase material. By powdering wet algal surfaces with this material, organic compounds are adsorbed and can be easily recovered for subsequent liquid chromatography/mass spectrometry (LC/MS) and gas chromatography/mass spectrometry (GC/MS) investigations. The method is robust, picks up metabolites of a broad polarity range and is easy to handle. It is more universal compared to established solvent dipping protocols and it does not cause damage to the test organisms. A protocol is introduced for the macroalgae Fucus vesiculosus, Caulerpa taxifolia and Gracilaria vermiculophylla, but it can be easily transferred to other aquatic organisms. PMID:26795737

  20. Validation and application of a solid phase chemistry method for preparation of high effective specific activity technetium-99m radiopharmaceuticals

    International Nuclear Information System (INIS)

    Solid phase chemistry with UltraLinkTM Iodoacetyl gel was investigated as a method for removing excess ligand present in preparations of diaminedithiol (DADT) 99mTc radiopharmaceuticals. The process was optimized and tested under 99mTc labeling conditions with 2,2,4,9,9-pentamethyl-4,7-diaza-1,10-decanedithiol (N-methyl-DADT), 1, and 4-(1-(2'-methoxyphenyl) piperazinylbutyl)-2,2,9,9-tetramethyl-4,7-diaza-1,10-decanedithiol (DADT-4C-MPP), 2, a serotonin receptor-binding ligand. The results illustrated that this gel removed ≥99.9% excess ligand used in labeling reactions, and was comparable to the level of purification usually obtained by the more labor intensive method of HPLC

  1. The role of energetic processing on solid-phase chemistry in star forming regions

    Science.gov (United States)

    Palumbo, M. E.; Urso, R. G.; Kaňuchová, Z.; Scirè, C.; Accolla, M.; Baratta, G. A.; Strazzulla, G.

    2016-05-01

    It is generally accepted that complex molecules observed in star forming regions are formed in the solid phase on icy grain mantles and are released to the gas-phase after desorption of icy mantles. Most of our knowledge on the physical and chemical properties of ices in star forming regions is based on the comparison between observations and laboratory experiments performed at low temperature (10-100 K). Here we present some recent laboratory experiments which show the formation of (complex) molecular species after ion bombardment of simple ices.

  2. Phase Spaces in Special Relativity: Towards Eliminating Gravitational Singularities

    CERN Document Server

    Danenhower, Peter

    2007-01-01

    This paper shows one way to construct phase spaces in special relativity by expanding Minkowski Space. These spaces appear to indicate that we can dispense with gravitational singularities. The key mathematical ideas in the present approach are to include a complex phase factor, such as, e^{i\\phi} in the Lorentz transformation and to use both the proper time and the proper mass as parameters. To develop the most general case, a complex parameter \\sigma=s+im, is introduced, where s is the proper time, and m is the proper mass, and \\sigma and {\\sigma}/{|\\sigma|} are used to parameterize the position of a particle (or reference frame) in space-time-matter phase space. A new reference variable, u={m}/{r}, is needed (in addition to velocity), and assumed to be bounded by 0 and {c^{2}}/{G}=1, in geometrized units. Several results are derived: The equation E=mc^2 apparently needs to be modified to E^2={s^2c^{10}}/{G^2}+m^2c^4, but a simpler (invariant) parameter is the "energy to length" ratio, which is {c^4}/{G} fo...

  3. Environmental mobility of cobalt-Influence of solid phase characteristics and groundwater chemistry

    International Nuclear Information System (INIS)

    The adsorption of cobalt on samples from a potential waste repository site in an arid region was investigated in batch experiments, as a function of various solution phase parameters including the pH and ionic strength. The samples were characterized using a range of techniques, including BET surface area measurements, total clay content and quantitative X-ray diffraction. The statistical relationships between the measured cobalt distribution coefficients (Kd values) and the solid and liquid phase characteristics were assessed. The sorption of cobalt increased with the pH of the aqueous phase. In experiments with a fixed pH value, the measured Kd values were strongly correlated to the BET surface area, but not to the amount of individual clay minerals (illite, kaolinite or smectite). A further set of sorption experiments was undertaken with two samples of distinctive mineralogy and surface area, and consequently different sorption properties. A simple surface complexation model (SCM) that conceptualized the surface sites as having equivalent sorption properties to amorphous Fe-oxide was moderately successful in explaining the pH dependence of the sorption data on these samples. Two different methods of quantifying the input parameters for the SCM were assessed. While a full SCM for cobalt sorption on these complex environmental substrates is not yet possible, the basic applicability and predictive capability of this type of modeling is demonstrated. A principal requirement to further develop the modeling approach is adequate models for cobalt sorption on component mineral phases of complex environmental sorbents.

  4. NATIONAL SURFACE WATER SURVEY: EASTERN LAKE SURVEY (PHASE 1 - SYNOPTIC CHEMISTRY). QUALITY ASSURANCE REPORT

    Science.gov (United States)

    The report provides an overview of the quality assurance activities and results of the Eastern Lake Survey - Phase I. The quality assurance program used a combination of blank, duplicate, and audit samples to provide an external check on the data quality of 32 physiochemical para...

  5. Introducing phase transitions to quantum chemistry: from Trouton's rule to first principles vaporization entropies.

    Science.gov (United States)

    Spickermann, Christian; Lehmann, Sebastian B C; Kirchner, Barbara

    2008-06-28

    In the present study, we employ quantum cluster equilibrium calculations on a small water cluster set in order to derive thermochemical equilibrium properties of the liquid phase as well as the liquid-vapor phase transition. The focus is set on the calculation of liquid phase entropies, from which entropies of vaporization at the normal boiling point of water are derived. Different electronic structure methods are compared and the influences of basis set size and of cooperative effects are discussed. In line with a previous study on the subject [B. Kirchner, J. Chem. Phys. 123, 204116 (2005)], we find that the neglect of cooperativity leads to large errors in the equilibrium cluster populations as well as in the obtained entropy values. In contrast, a correct treatment of the intermolecular many-body interaction yields liquid phase entropies and phase transition entropies being in very good agreement with the experimental reference, thus demonstrating that the quantum cluster equilibrium partition function intrinsically accounts for the shortcomings of the ideal gas partition function often employed in first principles entropy calculations. Comparing the calculated vaporization entropies to the value predicted by Trouton's rule, it is observed that for entropy calculations the consideration of intracluster cooperative effects is more important than the explicit treatment of the intercluster association even in a highly associated liquid such as water. The decomposition of entropy into contributions due to different degrees of freedom implies the need for the accurate treatment of particle indistinguishability and free volume of translation, whereas minor influences should be expected from the vibrational and rotational degrees of freedom and none from the electronic degrees of freedom. PMID:18618941

  6. Study of Heterogeneouse Processes Related to the Chemistry of Tropospheric Oxidants and Aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Davidovits, Paul; Worsnop, D R; Jayne, J T; Colb, C E

    2013-02-13

    The objective of the studies was to elucidate the heterogeneous chemistry of tropospheric aerosols. Experiments were designed to measure both specifically needed parameters, and to obtain systematic data required to build a fundamental understanding of the nature of gas-surface physical and chemical interactions

  7. Supramolecular chemistry: from aromatic foldamers to solution-phase supramolecular organic frameworks.

    Science.gov (United States)

    Li, Zhan-Ting

    2015-01-01

    This mini-review covers the growth, education, career, and research activities of the author. In particular, the developments of various folded, helical and extended secondary structures from aromatic backbones driven by different noncovalent forces (including hydrogen bonding, donor-acceptor, solvophobicity, and dimerization of conjugated radical cations) and solution-phase supramolecular organic frameworks driven by hydrophobically initiated aromatic stacking in the cavity of cucurbit[8]uril (CB[8]) are highlighted. PMID:26664626

  8. How Science/Technology/Society relations are approached in the contents of organic functions in high school chemistry

    Directory of Open Access Journals (Sweden)

    Carmem Lúcia Costa Amaral

    2009-03-01

    Full Text Available This paper aimed to verify how the relation between Science/Technology/Society (STS is present in Chemistry textbooks recommended by the Brazilian Ministry of Education. The interest in textbooks is due to the fact that they constitute important resources used by teachers to prepare their classes. Thus, researches in this area are necessary to indicate how the authors could improve the quality of their books. We believe that one way to do this is the introduction of the STS relation, which took place because of the necessity in establishing new ways of teaching, specially the teaching of science. One of the goals of STS education is to create conditions to develop abilities and competences that qualify the students for discussions concerning scientific and technologic questions of everyday life. The analysis of testbooks used the descriptors and indicators developed by Fracalanza and Megid-Neto (2006 as reference. In order to carry out the study, we chose the area of Organic Chemistry, more specifically contents referring to organic functions, with great use in society. In general, the results showed that STS relations are not totally observed in the investigated contents, contributing to the development of Chemistry classes through activities apart from the students social context.

  9. Preanalytical quality improvement. In pursuit of harmony, on behalf of European Federation for Clinical Chemistry and Laboratory Medicine (EFLM) Working group for Preanalytical Phase (WG-PRE)

    DEFF Research Database (Denmark)

    Lippi, G.; Banfi, G.; Church, S.;

    2015-01-01

    ). Although laboratory medicine seems less vulnerable than other clinical and diagnostic areas, the chance of errors is not negligible and may adversely impact on quality of testing and patient safety. This article, which continues a biennial tradition of collective papers on preanalytical quality improvement......, is aimed to provide further contributions for pursuing quality and harmony in the preanalytical phase, and is a synopsis of lectures of the third European Federation of Clinical Chemistry and Laboratory Medicine (EFLM)-Becton Dickinson (BD) European Conference on Preanalytical Phase meeting entitled......Laboratory diagnostics develop through different phases that span from test ordering (pre-preanalytical phase), collection of diagnostic specimens (preanalytical phase), sample analysis (analytical phase), results reporting (postanalytical phase) and interpretation (post-postanalytical phase...

  10. Phase Chemistry and Thermochemstry on Coordination Behavior of Zinc Chloride with Leucine

    Institute of Scientific and Technical Information of China (English)

    高胜利; 陈三平; 等

    2003-01-01

    The solubility property of the ZnCl2-Leu-H2O(Leu=L-a-leucine) system at 298.15K in the whole concentration range was investigatey by the semimicro-phase equilibrium method.The corresponding solubility diagram and refractive index diagram were constructed.The results indicated that there was one complex formed in this system.namely,Zn(Leu)Cl2.The complex is congruently soluble in water.Based on Phase equilibrium data,the complex was prepared.Its composition and properties were characterized by chemical analysis,elemental analysis,IR spectra,and TG-DTG.The thermochemical properties of coordination reaction of zinc chloride with L-a-leucine were investigated by a microcalorimeter.The enthalpies of solution of L-a-leucine in water and its zinc complex at infinite dilution and the enthalpy change of solid-liquid reaction wrer determined at 298.15K.The enthalpy change of soild phase reaction and the standard enthalpy of formation of zinc complex were claculated.On the basis of experimental and calculated results,three thermodynamic parameters(the activation enthalpy,the activation entropy and the activation free energy),the rate constant and three kinetic parameters(the activation energy,the preexponential constant and the reaction order) of the reaction,and the standard enthalpy of formation of Zn(Leu)2+(aq) were obtained.The results showed that the title reaction took place easily at studied temperature.

  11. The effect of multilayer ice chemistry on gas-phase deuteration in starless cores

    CERN Document Server

    Sipilä, O; Taquet, V

    2016-01-01

    Aims. We aim to investigate whether a multilayer ice model can be as successful as a bulk ice model in reproducing the observed abundances of various deuterated gas-phase species toward starless cores. Methods. We calculate abundances for various deuterated species as functions of time adopting fixed physical conditions. We also estimate abundance gradients by adopting a modified Bonnor-Ebert sphere as a core model. In the multilayer ice scenario, we consider desorption from one or several monolayers on the surface. Results. We find that the multilayer model predicts abundances of $\\rm DCO^+$ and $\\rm N_2D^+$ that are about an order of magnitude lower than observed, caused by the trapping of CO and $\\rm N_2$ into the grain mantle. As a result of the mantle trapping, deuteration efficiency in the gas phase increases and we find stronger deuterium fractionation in ammonia than what has been observed. Another distinguishing feature of the multilayer model is that $\\rm D_3^+$ becomes the main deuterated ion at hi...

  12. Chemistry, phase formation, and catalytic activity of thin palladium-containing oxide films synthesized by plasma-assisted physical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Anders, Andre

    2010-11-26

    The chemistry, microstructure, and catalytic activity of thin films incorporating palladium were studied using scanning and transmission electron microscopies, X-ray diffraction, spectrophotometry, 4-point probe and catalytic tests. The films were synthesized using pulsed filtered cathodic arc and magnetron sputter deposition, i.e. techniques far from thermodynamic equilibrium. Catalytic particles were formed by thermally cycling thin films of the Pd-Pt-O system. The evolution and phase formation in such films as a function of temperature were discussed in terms of the stability of PdO and PtO2 in air. The catalytic efficiency was found to be strongly affected by the chemical composition, with oxidized palladium definitely playing a major role in the combustion of methane. Reactive sputter deposition of thin films in the Pd-Zr-Y-O system allowed us forming microstructures ranging from nanocrystalline zirconia to palladium nanoparticles embedded in a (Zr,Y)4Pd2O matrix. The sequence of phase formation is put in relation to simple thermodynamic considerations.

  13. Gas chemistry, boiling and phase segregation in a geothermal system, Hellisheidi, Iceland

    Science.gov (United States)

    Scott, Samuel; Gunnarsson, Ingvi; Arnórsson, Stefán; Stefánsson, Andri

    2014-01-01

    The geochemistry of aquifer fluids of the Hellisheidi geothermal system, southwest Iceland, was studied. Based on samples of vapor and liquid from well discharge fluids, the aquifer fluid compositions at the depth of the geothermal system were reconstructed taking into account the highly variable degree of excess well discharge enthalpy, where the enthalpy of the discharge is significantly higher than that of vapor-saturated liquid at the measured aquifer temperature. Decreasing concentrations of non-volatile components such as Si in the total well discharge suggest that the main cause of elevated discharge enthalpies is liquid-vapor phase segregation, i.e. the retention of liquid in the aquifer rock due to its adhesion onto mineral surfaces. Moreover, the slightly lower than equilibrium calculated concentrations of H2 and H2S in some of the hottest and highest-enthalpy wells is considered to be caused by conductive heat transfer from the rocks to the fluids. Alternatively, the cause may lie in the selection of the phase segregation conditions. The calculated concentrations of volatile species in the aquifer fluid are very sensitive to the assumed phase segregation conditions while non-volatiles are not greatly affected by this model parameter. In general, the level of uncertainty does not contradict previous findings of a close approach to fluid-mineral equilibrium at aquifer temperatures above 250 °C. The CO2 concentrations were observed to fall below equilibrium with respect to the most likely mineral buffers, suggesting a possible source control. Elevated H2 concentrations indicate a small equilibrium vapor fraction in aquifer fluids (∼0.2% by mass or ∼3% by volume). Previous conceptual models of the Hengill volcanic area (e.g. Bödvarsson et al., 1990) have implied a central magmatic heat source underlying the Hengill central volcano. Instead, a new conceptual model of the Hellisheidi system is proposed that features two main regions of fluid upflow

  14. Interdependence of phase chemistry, microstructure and oxygen fugacity in titanate nuclear waste ceramics

    International Nuclear Information System (INIS)

    Titanate ceramic waste forms were prepared using several combinations of calcination atmosphere (N2, N2-3.5% H2, H2) and metallic buffer (Ni, Fe, Ti, Al) to examine the dependence of microstructure and durability upon oxygen activity. It was found that the microstructures and phase assemblages were mostly insensitive to the fabrication method, although in detail some systematic changes were recognized. The correlation between aqueous durability and oxygen fugacity was not straightforward due to density variations in the hot-pressed ceramics. These fluctuations in density dominated the dissolution characteristics of the waste forms and sometimes obscured the more subtle changes associated with redox potential. It is concluded that although the best durability is achieved at lower fugacities (i.e. Ti metal buffer and H2 calcination atmosphere), a satisfactory product can be produced using any of the preparative routes examined providing the material is near theoretical density. 25 refs., 15 figs., 6 tabs

  15. Uranium fluoride chemistry. Part 1. The gas phase reaction of uranium hexafluoride with alcohols

    International Nuclear Information System (INIS)

    The reaction between uranium hexafluoride (UF6) and simple alcohols in the gas phase was observed to proceed by way of three possible reaction pathways involving dehydration, deoxygenative fluorination, and ether formation. These reactions can best be explained by assuming that alcohols first react with UF6 to afford the alkoxy uranium pentafluoride intermediate ROUF5, which reacts further to give the dehydration, deoxygenative fluorination, and ether products. In each of the above three reaction pathways, UF6 is transformed to UOF4, which being as reactive toward alcohols as UF6, reacts further with the alcohol in question to finally afford the unreactive uranyl fluoride (UO2F2). 6 refs., 2 tabs

  16. Gas Phase Chemistry and Molecular Complexity: How Far Do They Go?

    Science.gov (United States)

    Balucani, Nadia

    2016-07-01

    The accumulation of organic molecules of increasing complexity is believed to be an important step toward the emergence of life. But how massive organic synthesis could occur in primitive Earth, i.e. a water-dominated environment, is a matter of debate. Two alternative theories have been suggested so far: endogenous and exogenous synthesis. In the first theory, the synthesis of simple organic molecules having a strong prebiotic potential (simple prebiotic molecules SPMs, such as H2CO, HCN, HC3N, NH2CHO) occurred directly on our planet starting from simple parent molecules of the atmosphere, liquid water and various energy sources. Miller's experiment was a milestone in this theory, but it was later recognized that the complexity of a planet cannot be reproduced in a single laboratory experiment. Some SPMs have been identified in the N2-dominated atmosphere of Titan (a massive moon of Saturn), which is believed to be reminiscent of the primitive terrestrial atmosphere. As such, the atmosphere of Titan represents a planetary scale laboratory for the comprehension of SPM formation in an environment close enough to primitive Earth and is the current frontier in the endogenous theory exploration. In the exogenous theory, SPMs came from space, the carriers being comets, asteroids and meteorites. The rationale behind this suggestion is that plenty of SPMs have been observed in interstellar clouds (ISCs), including star-forming regions, and in small bodies like comets, asteroids and meteorites. Therefore, the basic idea is that SPMs were formed in the solar nebula, preserved during the early phases of the Solar System formation in the body of comets/asteroids/meteorites and finally delivered to Earth by cometary and meteoritic falls. In this contribution, the status of our knowledge on how SPMs can be formed in the gas phase, either in the primitive terrestrial atmosphere or in the cold nebula from which the Solar System originated, will be presented. Particular attention

  17. Domain-Specific Expertise of Chemistry Teachers on Context-Based Education about Macro-Micro Thinking in Structure-Property Relations

    Science.gov (United States)

    Dolfing, Ria; Bulte, Astrid M. W.; Pilot, Albert; Vermunt, Jan D.

    2012-01-01

    This study aims to determine and describe the new domain-specific expertise of experienced chemistry teachers in teaching an innovative context-based unit about macro-micro thinking in structure-property relations. The construct of "teachers' domain-specific expertise" was used to analyse the new repertoire chemistry teachers need to acquire to…

  18. Water chemistry in 179 randomly selected Swedish headwater streams related to forest production, clear-felling and climate.

    Science.gov (United States)

    Löfgren, Stefan; Fröberg, Mats; Yu, Jun; Nisell, Jakob; Ranneby, Bo

    2014-12-01

    From a policy perspective, it is important to understand forestry effects on surface waters from a landscape perspective. The EU Water Framework Directive demands remedial actions if not achieving good ecological status. In Sweden, 44 % of the surface water bodies have moderate ecological status or worse. Many of these drain catchments with a mosaic of managed forests. It is important for the forestry sector and water authorities to be able to identify where, in the forested landscape, special precautions are necessary. The aim of this study was to quantify the relations between forestry parameters and headwater stream concentrations of nutrients, organic matter and acid-base chemistry. The results are put into the context of regional climate, sulphur and nitrogen deposition, as well as marine influences. Water chemistry was measured in 179 randomly selected headwater streams from two regions in southwest and central Sweden, corresponding to 10 % of the Swedish land area. Forest status was determined from satellite images and Swedish National Forest Inventory data using the probabilistic classifier method, which was used to model stream water chemistry with Bayesian model averaging. The results indicate that concentrations of e.g. nitrogen, phosphorus and organic matter are related to factors associated with forest production but that it is not forestry per se that causes the excess losses. Instead, factors simultaneously affecting forest production and stream water chemistry, such as climate, extensive soil pools and nitrogen deposition, are the most likely candidates The relationships with clear-felled and wetland areas are likely to be direct effects. PMID:25260924

  19. XI International conference Problems of solvation and complex formation in solutions, and VI Conference of young scientists Theoretical and experimental chemistry of liquid-phase systems (Krestovsky readings). Summary of reports

    International Nuclear Information System (INIS)

    The collection contains materials of plenary, sectional and poster sessions, presented at the XI International conference Problems of solvation and complex formation in solutions, and VI Conference of young scientists Theoretical and experimental chemistry of liquid-phase systems (Krestovsky readings). Theoretical questions and new experimental methods of chemistry of solutions, structure and dynamics of molecular and ion-molecular systems in solution and at the phase boundary; modern aspects of applied chemistry of solutions are discussed

  20. Cluster Chemistry

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    @@ Cansisting of eight scientists from the State Key Laboratory of Physical Chemistry of Solid Surfaces and Xiamen University, this creative research group is devoted to the research of cluster chemistry and creation of nanomaterials.After three-year hard work, the group scored a series of encouraging progresses in synthesis of clusters with special structures, including novel fullerenes, fullerene-like metal cluster compounds as well as other related nanomaterials, and their properties study.

  1. Chemistry of the scandium-benzyne ion in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Yongqinq Huang; Hill, Y.D.; Sodupe, M.; Bauschlicher, C.W. Jr.; Freiser, B.S. (Purdue Univ., West Lafayette, IN (United States) NASA Ames Research Center, Moffet Field, CA (United States))

    1991-10-02

    The reactant ion, ScC[sub 6]H[sub 4][sup +], was prepared from the dehydrogenation of benzene by Sc[sup +]. ScC[sub 6]H[sub 4][sup +] undergoes an unusual hydrogenation reaction with H[sub 2] and D[sub 2], as well as H/D exchange with the latter. Its reactions with a number of oxygen-containing species, XO, give ScO[sup +]. The ability to form stable C[sub 6]H[sub 4]X neutral products from benzyne is a key factor in making this reaction exothermic. With the exception of methane, ScC[sub 6]H[sub 4] reacts with all of the alkanes and alkenes studied to form a wide variety of product ions. Sc[sup +]-styrene is formed from the reaction with ethane and propane. Sc[sup +]-indane is also formed from the reaction with propane. The product ion ScC[sub 8]H[sub 10][sup +] from n-butane is Sc[sup +]-ethylbenzene. A prominent ion, ScC[sub 9]H[sub 7][sup +], is formed from butadiene. Its frequent occurrence, unusual formulation, and resistance to fragmentation all indicate a high stability, with its structure most likely being that of the indenylscandium cation. D[sup 0](Sc[sup +]-benzyne) = 88 [plus minus] 5kcal/mol was determined indirectly from the photodissociation threshold for loss of H[sub 2] from Sc[sup +]-benzene and from the observation that Sc[sup +] exothermically dehydrogenates benzene to form Sc[sup +]-benzyne. Theoretical study indicates that the gas-phase structure is analogous to that of solid-phase mononuclear transition-metal-benzyne complexes observed crystallographically in which the metal center is coplanar with the benzyne ring and inserted symmetrically into the C-C triple bond forming a benzometallacyclopropene. The theoretical bond energy for the planar singlet D[sup 0](Sc[sup +]-C[sub 6]H[sub 4]) = 94 kcal/mol is in good agreement with experiment.

  2. Gas phase chemistry during electron assisted chemical vapor deposition (EACVD) of diamond films

    International Nuclear Information System (INIS)

    Diamond films were deposited in electron assisted chemical vapor deposition (EACVD) reactor using two source mixtures of CH4-H2 and C2H5OH-H2, respectively. The plasma gas composition during diamond growing was investigated in situ using optical emission spectroscopy (OES). In two cases of C2H2OH-H2 and CH4-H2 plasma, it was shown that CH and CH+ were all important precursor species in the diamond deposition reaction while the yields of poor diamond films corresponded to the presence of the C2 emission line. The difference between these two cases was that some oxygen-containing species (CH2O, CHO and O2) were detected in the C2H5OH-H2 plasma. The presence of these products may maintain the quality of the deposited diamond films while increasing carbon source concentration, and the growth rate was thus enhanced. These results imply that the increase in the growth rate of diamond film using C2H5OH-H2 mixture is primarily due to a change in gas phase environment

  3. Einsteinium chemistry in the gas phase: exploring the divalent character of heavy actinides

    International Nuclear Information System (INIS)

    The first chemical studies of the monopositive einsteinium ion, Es+, in the gas phase have been carried out, and its behavior compared to those for other actinide ions, with a particular focus on Bk+. The yield of laser-ablated EsO+ indicates that the Es+-O bond energy is significantly smaller than that of Bk+-O. Fluorination of Es+ and Bk+ through F-abstraction from hexafluoropropene demonstrated clearly the stability of the divalent state of Es: whereas by this process both BkF+ and BkF2+ are produced, only the ''divalent'' EsF+ product is formed. The reaction of Es+ with several different alkenes produced only small yields of adducts (e.g., EsC4H8+). These adducts are the first organoeinsteinium complexes to be identified. Whereas Es+ was inert towards 1,5-cyclooctadiene, in contrast Bk+ dehydrogenated this substrate to give BkC8H8+, demonstrating the greater activation activity of Bk+ than Es+ towards alkenes. The chemical behaviors observed in these studies are consistent with the predicted electronic structure and energetics of Es+, and the results obtained are discussed in the context of systematic trends across the actinide series. (orig.)

  4. Phase relations in the forsterite-diopside-jadeite system.

    Science.gov (United States)

    Butvina, V.; Litvin, Yu.

    2009-04-01

    solidus in this system). Due to this fact forsterite vanishes in subsolidus in the region of compositions rather enriched by jadeite component. The performed experimental investigations testify to complex topological relations of phases in this system at close solidus temperatures what needs further studies. The experimental investigations done earlier and referring to this system (Gasparik & Litvin, 1997) testify to the appearance of a new phase of the composition Na2Mg2Si2O7, which role in the formation of subliquidus and subsolidus assemblages must be more studied. Nevertheless, the obtained preliminary experimental data contain constructive data that make it possible to consider the basic problem of this work and start experimental investigations of liquidus phase relations of the system forsterite-diopside-jadeite. The system forsterite-diopside. The experiments in this section are given at pressure of 7 GPa in the range of temperatures 1600-17000C. The system is pseudobinary due to the appearance of orthopyroxene component that forms an independent phase. According to the preliminary data liquidus assemblages of this system at 7 GPa are Fo + L и DiSS + L, but the type of melting is eutectic. It agrees with the above investigations at pressure of 3 GP (Davis, 1963) where some pseudobinarity of the system forsterite-diopside caused by the appearance of orthopyroxene minal in clinopyroxene solid solution can be also seen. The system forsterite-jadeite-diopside. The experimental data and conclusions obtained for the boundary systems make it possible to start investigating liquidus surface for fusibility diagram of the ternary system forsterite-jadeite-diopside at P 7 GPa. For the experimental study polythermic sections of forsterite-(jadeite50diopside50) and forsterite-(jadeite25diopside75) have been chosen. The obtained data testify to the fact that olivine vanishing and garnet formation are realized in both sections. The problem of further investigations is to search

  5. PWR water chemistry controls: a perspective on industry initiatives and trends relative to operating experience and the EPRI PWR water chemistry guidelines

    International Nuclear Information System (INIS)

    An effective PWR water chemistry control program must address the following goals: Minimize materials degradation (e.g., PWSCC, corrosion of fuel, corrosion damage of steam generator (SG) tubes); Maintain fuel integrity and good performance; Minimize corrosion product transport (e.g., transport and deposition on the fuel, transport into the SGs where it can foul tube surfaces and create crevice environments for the concentration of corrosive impurities); Minimize dose rates. Water chemistry control must be optimized to provide overall improvement considering the sometimes variant constraints of the goals listed above. New technologies are developed for continued mitigation of materials degradation, continued fuel integrity and good performance, continued reduction of corrosion product transport, and continued minimization of plant dose rates. The EPRI chemistry program, in coordination with other EPRI programs, strives to improve these areas through application of chemistry initiatives, focusing on these goals. This paper highlights the major initiatives and issues with respect to PWR primary and secondary system chemistry and outlines the recent, on-going, and proposed work to effectively address them. These initiatives are presented in light of recent operating experience, as derived from EPRI's PWR chemistry monitoring and assessment program, and EPRI's water chemistry guidelines. (author)

  6. Near-explicit Gas-phase Chemistry Coupled with Extensive Aqueous Mechanism: Looking at Ethanol (E85) Exhaust in a Fog

    Science.gov (United States)

    Ginnebaugh, D. L.; Jacobson, M. Z.

    2011-12-01

    We combine a near-explicit gas-phase chemical mechanism with an extensive aqueous mechanism in a chemical solver to examine the effects of ethanol (E85) versus gasoline on the fate of pollutants in the presence of a fog. We use the Master Chemical Mechanism (MCM, version 3.1, Leeds University) and the Chemical Aqueous Phase Radical Mechanism, CAPRAM 3.0, with the SMVGEAR II chemical ordinary differential solver to provide the speed necessary to simulate complex chemistry. The MCM has over 13, 500 organic reactions and 4,600 species, while CAPRAM treats aqueous chemistry among 390 species and 829 reactions (including 51 gas-to-aqueous phase reactions). We validate a simplified version of the model against results from a comprehensive intercomparison by Barth et al (2003). In previous work on ethanol (E85), we analyzed the temperature-dependence of ethanol and gasoline exhaust chemistry and its impact on urban air pollution considering only gas-phase chemistry. In addition to the air pollution findings, we verified that using the MCM with SMVGEAR is practical in a 3-D model. Here, we extend our study to include aqueous chemistry in the presence of a fog. We investigate the impact aqueous reactions have on unburned ethanol and acetaldehyde mixing ratios in the atmosphere in particular because acetaldehyde is an ozone precursor and carcinogen, and aqueous oxidation has potential to speed the conversion of unburned ethanol to acetaldehyde. Acetaldehyde also forms acetic acid in aqueous solution. Acetic acid vapor is an eye, nose, and lung irritant, so both species contribute negatively to human health. We look at the impact of fog liquid water content and temperature on the degradation of emitted aromatic and other species as well, from both gasoline and E85.

  7. Water chemistry in secondary side of cne candu steam generators and their related degradation processes

    International Nuclear Information System (INIS)

    This paper presents a brief overview of steam generator functional parameters of nuclear power plants how use PWR (Pressurized Water Reactor) and PHWR (Pressurized Heavy Water Reactor) reactors, followed by a description of fundamental aspects on steam generator degradation and water chemistry in the secondary side, and also, water chemistry improvement by controlling ph. During operating life, cooling radioactive contamination occurs, but water conditions must be maintained inside specific ranges. Feedwater must be maintained as free from impurities as possible. This requirement involves careful attention to the entire system through which the water flows, either in the form of steam or water, for even though water is used as feedwater be pure at the same time of its entry into the system, it may absorb impurities from the various parts of the installation. Specific attention should be directed to possible points of water leakage from the service water system, as in the main and auxiliary condensers. Feedwater must be treated to maintain the required water conditions. As the concentration of the impurities in deposits increase, the ph can shift locally in these areas to acidic or alkaline conditions, entering in a ph range where initiation of corrosion phenomena cannot be longer excluded. By maintaining of sufficiently reducing conditions, the occurrence of certain corrosion mechanisms will be excluded (like pitting), but certain forms of steam generator tube corrosion may still occur. (authors)

  8. Relating groundwater and sediment chemistry to microbial characterization at a BTEX-contaminated site

    International Nuclear Information System (INIS)

    The National Center for Manufacturing Science is investigating bioremediation of petroleum hydrocarbon at a site in Belleville, Michigan. As part of this study we examined the microbial communities to help elucidate biodegradative processes currently active at the site. We observed high densities of aerobic hydrocarbon degraders and denitrifiers in the less-contaminated sediments. Low densities of iron and sulfate reducers were measured in the same sediments. In contrast, the highly-contaminated sediments showed low densities of aerobic hydrocarbon degraders and denitrifiers and high densities of iron and sulfate reducers. Methanogens were also found in these highly-contaminated sediments. These contaminated sediments also showed a higher biomass, by phospholipid fatty acids, and greater ratios of phospholipid fatty acids which indicate stress within the microbial community. Aquifer chemistry analyses indicated that the more-contaminated area was more reduced and had lower sulfate than the less-contaminated area. These conditions suggest that the subsurface environment at the highly-contaminated area had progressed into sulfate reduction and methanogensis. The less-contaminated area, although less reduced, also appeared to be progressing into primarily iron- and sulfate-reducing microbial communities. The proposed treatment to stimulate bioremediation includes addition of oxygen and nitrate. Groundwater chemistry and microbial analyses revealed significant differences resulted from the injection of dissolved oxygen and nitrate in the subsurface. These differences included increases in pH and Eh and large decreases in BTEX, dissolved iron, and sulfate concentrations at the injection well

  9. The gas phase ion/molecule chemistry of four carbanions generated from vinylene carbonate and its methyl and dimethyl derivatives

    Science.gov (United States)

    Robinson, Marin S.; Breitbeil, Fred W.

    1992-09-01

    The gas phase ion/molecule chemistry of four carbanions generated by the reaction of vinylene carbonate, and its methyl and dimethyl derivatives with hydroxide ion has been investigated. From the parent the sole product is the ketenyl anion, HC[triple bond; length as m-dash]C---O-, arising from vinylic proton abstraction and loss of CO2. From the dimethyl derivative, abstraction of an allylic proton from one of the methyl groups followed by loss of CO2 leads exclusively to CH2=CC(O)CH3. Both pathways are observed for the monomethyl derivative, leading to a mixture of the ions CH3C[triple bond; length as m-dash]C---O- and CH2=CCHO. The ketenyl and methyl ketenyl ions do not exchange hydrogen for deuterium with D2O or CH3OD, but they do react with CS2 and COS to form the corresponding thioketenyl anions, HC[triple bond; length as m-dash]C---S- and CH3C=C---S-. The ions CH2=CC(O)CH3 and CH2=CCHO exchange one and three hydrogen atoms for deuterium atoms with D2O respectively, and react with CS2 to form thioketenyl anions by addition and loss of thioformaldehyde. Possible mechanisms for these reactions are discussed.

  10. The Atmospheric Circulation of a Nine-hot-Jupiter Sample: Probing Circulation and Chemistry over a Wide Phase Space

    Science.gov (United States)

    Kataria, Tiffany; Sing, David K.; Lewis, Nikole K.; Visscher, Channon; Showman, Adam P.; Fortney, Jonathan J.; Marley, Mark S.

    2016-04-01

    We present results from an atmospheric circulation study of nine hot Jupiters that compose a large transmission spectral survey using the Hubble and Spitzer Space Telescopes. These observations exhibit a range of spectral behavior over optical and infrared wavelengths, suggesting diverse cloud and haze properties in their atmospheres. By utilizing the specific system parameters for each planet, we naturally probe a wide phase space in planet radius, gravity, orbital period, and equilibrium temperature. First, we show that our model “grid” recovers trends shown in traditional parametric studies of hot Jupiters, particularly equatorial superrotation and increased day–night temperature contrast with increasing equilibrium temperature. We show how spatial temperature variations, particularly between the dayside and nightside and west and east terminators, can vary by hundreds of kelvin, which could imply large variations in Na, K, CO and {{{CH}}}4 abundances in those regions. These chemical variations can be large enough to be observed in transmission with high-resolution spectrographs, such as ESPRESSO on VLT, METIS on the E-ELT, or MIRI and NIRSpec aboard JWST. We also compare theoretical emission spectra generated from our models to available Spitzer eclipse depths for each planet and find that the outputs from our solar-metallicity, cloud-free models generally provide a good match to many of the data sets, even without additional model tuning. Although these models are cloud-free, we can use their results to understand the chemistry and dynamics that drive cloud formation in their atmospheres.

  11. The current-phase relation of a mechanically controllable breakjunction

    International Nuclear Information System (INIS)

    In order to determine the current-phase relation (CPR) of a mechanically controllable break (MCB) junction an adjustable SQUID has been developed. A ring, interrupted by a MCB junction, is cut out of a thin niobium foil using laser cutting techniques. In this SQUID the critical current can be varied continuously by adjusting the contact size of the junction. A new technique has been developed which enables us to measure directly the CPR. Superconducting current leads are attached on either side of the contact in order to determine the selfinductance of the ring. The CPR has been investigated at 4.2 K and at 1.3 K in a range of normal resistances which is estimated to be between 0.5 and 8 kΩ. A deviation from the pure sinusoidal CPR is found at 4.2 K while the CPR at 1.3 K seems to be nearly sinusoidal. It is striking that the CPRs at 4.2 K have a maximum in the current at values slightly smaller than π/2, while theories predict it to be between π/2 and π for superconducting pointcontacts with three-dimensional banks in this temperature range. (orig.)

  12. Mid-Ocean Ridge Hydrothermal Vent Fluid Chemistry at Ultrafast Spreading Rates: Control by Phase Separation and Water-Rock Equilibrium

    Science.gov (United States)

    O'Grady, K. M.; Von Damm, K. L.

    2001-12-01

    Phase separation, overprinted by water-rock equilibration are the major controls on the chemical composition of hydrothermal vent fluids sampled from two morphologically distinct areas (18\\deg 24-26'S and 21\\deg 24-27'S) along the ultrafast spreading ( ~15 cm/yr full rate) Southern East Pacific Rise (SEPR) during the 1998 SouEPR Cruise. This conclusion, along with the growing evidence that phase separation and water-rock equilibrium also control the composition of previously sampled hydrothermal vent fluids from slower-spreading ridges, indicates that to a first approximation neither spreading rate nor ridge morphology can be directly related to hydrothermal fluid compositions. Hydrothermal fluids from ultrafast spreading centers therefore do not form a unique subset in the global range of known chemical compositions. Previous geophysical surveys and submersible observations suggested that the hydrothermal system located at 21\\deg 24-27'S, the SouEPR Area, was dominated by tectonic activity (Renard et al., 1985; Tufar, 1995; Krasnov et al., 1997). Submersible observations and hydrothermal vent fluid chemistry indicated that the N. Hump Area, experienced volcanic activity shortly before the 1993 NADUR Cruise (Charlou et al., 1996). The N. Hump Area vent fluids sampled during the 1998 SouEPR Cruise displayed a relatively uniform chlorinity (616-670 mmol/kg Cl) that is greater than seawater. The Si and Cl data from the N. Hump Area vent fluids suggest reaction zone conditions up to ~360 bars (~1 km below the seafloor) and ~430\\deg C, indicating supercritical phase separation. The unusually large chlorinity variation (113-803 mmol/kg Cl) in the SouEPR Area hydrothermal vent fluids covers almost the entire range of sampled mid-ocean ridge (MOR) hydrothermal vent fluid chemistries worldwide (30.5-1245 mmol/kg Cl). The Si and Cl data from the SouEPR Area vent fluids suggest reaction zone conditions up to ~410 bars ( ~1.3 km below the seafloor) and ~450\\deg C. The

  13. Chemistry, coeliac-toxicity and detection of gluten and related prolamins in foods.

    Science.gov (United States)

    Skerritt, J H; Devery, J M; Hill, A S

    1991-01-01

    Some recent advances in the understanding of the chemistry of gluten proteins and its relationship to the toxicity of different fractions in coeliac disease (gluten intolerance) is reviewed. Most recent studies on gluten toxicity have used in vitro analyses of cellular immune activation by gluten fractions and peptides. Our work indicates that gliadin is the most active of the different protein families found within the wheat grain and that a specific peptide sequence located in the amino terminus domain of alpha-gliadin and containing the sequence proline-serine-glutamine-glutamine was most active. Improvement in the dietary management of coeliac disease is possible by use of test kits for the detection of gluten in foods. Both laboratory kits and home test kits (suitable for use by individual coeliacs) are available and reliably detect gluten from wheat, rye and barley even after cooking or baking. PMID:1923557

  14. Review and needs in actinide chemistry in relation with biological purposes

    International Nuclear Information System (INIS)

    In case of accidental release of radionuclides in the environment, actinides could occur and may present an healthy risk for human beings. In order to study their behavior in human organism (metabolism, retention, excretion), it is of prime importance to know solution actinide chemistry, and more particularly thermodynamic constants, which will allow to determine their speciation: speciation governs biological availability and toxicity of elements and is also of great interest for decorporation purposes. In this framework, a CEA working group on speciation has been created in order to share data both on thermodynamic constants and on speciation analytical methods, interesting chemists, environmentalists and biologists. It has been focused, in a first time, on actinides. The purpose of this paper is to present the state of the art on actinide speciation within biological media and to focus on the lack of information in order to orientate future research. (authors)

  15. Review and needs in actinide chemistry in relation with biological purposes

    Energy Technology Data Exchange (ETDEWEB)

    Ansoborlo, E.; Moulin, V.; Bion, L.; Doizi, D.; Moulin, C.; Cote, G.; Madic, C.; Van der Lee, J

    2004-07-01

    In case of accidental release of radionuclides in the environment, actinides could occur and may present an healthy risk for human beings. In order to study their behavior in human organism (metabolism, retention, excretion), it is of prime importance to know solution actinide chemistry, and more particularly thermodynamic constants, which will allow to determine their speciation: speciation governs biological availability and toxicity of elements and is also of great interest for decorporation purposes. In this framework, a CEA working group on speciation has been created in order to share data both on thermodynamic constants and on speciation analytical methods, interesting chemists, environmentalists and biologists. It has been focused, in a first time, on actinides. The purpose of this paper is to present the state of the art on actinide speciation within biological media and to focus on the lack of information in order to orientate future research. (authors)

  16. SRNL PHASE II SHELF LIFE STUDIES - SERIES 1 ROOM TEMPERATURE AND HIGH RELATIVE HUMIDITY

    Energy Technology Data Exchange (ETDEWEB)

    Mickalonis, J.; Duffey, J.

    2012-09-12

    The Savannah River National Laboratory (SRNL) Phase II, Series 1 shelf-life corrosion testing for the Department of Energy Standard 3013 container is presented and discussed in terms of the localized corrosion behavior of Type 304 stainless steel in contact with moist plutonium oxide and chloride salt mixtures and the potential impact to the 3013 inner container. This testing was designed to address the influence of temperature, salt composition, initial salt moisture, residual stress and type of oxide/salt contact on the relative humidity inside a 3013 container and the initiation and propagation of localized corrosion, especially stress corrosion cracking. The integrated plan is being conducted by Los Alamos National Laboratory and SRNL. SRNL is responsible for conducting a corrosion study in small scale vessels containing plutonium oxide and chloride salts under conditions of humidity, temperature and oxide/salt compositions both within the limits of 3013 storage conditions as well as beyond the 3013 storage requirements to identify margins for minimizing the initiation of stress corrosion cracking. These worst case conditions provide data that bound the material packaged in 3013 containers. Phase I of this testing was completed in 2010. The Phase II, Series 1 testing was performed to verify previous results from Phase I testing and extend our understanding about the initiation of stress corrosion cracking and pitting that occur in 304L under conditions of room temperature, high humidity, and a specific plutonium oxide/salt chemistry. These results will aid in bounding the safe storage conditions of plutonium oxides in 3013 containers. A substantial change in the testing was the addition of the capability to monitor relative humidity during test exposure. The results show that under conditions of high initial moisture ({approx}0.5 wt%) and room temperature stress corrosion cracking occurred in 304L teardrop coupons in contact with the oxide/salt mixture at times

  17. Hydrogen and related materials at high density: Physics, chemistry and planetary implications

    Science.gov (United States)

    Hemley, R. J.; Mao, H. K.; Duffy, T. S.; Goncharov, A.; Vos, W.; Zha, C. S.; Eggert, J. H.; Li, M.; Hanfland, M.

    1994-01-01

    Recent studies of low-Z molecular materials including hydrogen to multimegabar pressures (less than 300 GPa) have uncovered a range of phenomena relevant to understanding the nature of the interiors of the outer planets and their satellites. Synchrotron x ray diffraction measurements (to 42 GPa) have been used to determine the crystal structure of the solid (hexagonal-close packed) and equation of state. Sound velocities in fluid and solid hydrogen (to 24 GPa) have been inverted to obtain elastic constants and aggregate bulk and shear moduli. In addition, an improved intermolecular potential has been determined which fits both static and shock-wave data. Use of the new potential for the molecular envelope of Jupiter suggests the need for major revisions of existing Jovian models or a reanalysis of reported free oscillations for the planet. Studies at higher pressures (greater than 100 GPa) reveal a sequence of pressure-induced symmetry-breaking transitions in molecular hydrogen, giving rise to three high-pressure phases (1, 2, and 3). Phase 1 is the rotationally disordered hcp phase which persists from low pressure to well above 100 GPa at high temperature (e.g., 300 K). Phase 2 is a low-temperature, high-pressure phase (transition at 100 GPa and 77 K in H2) with spectral features indicative of partial rotational ordering and crystallographic distortion. The transition to Phase 3 at 150 GPa is accompanied by a weakening of the molecular bond, gradual changes in orientational ordering, strong enhancement of the infrared intramolecular vibrational absorption, and strong intermolecular interactions similar to those of ambient-pressure network solids. Studies of the phase diagram reveal a triple point near 130 K and 160 GPa. Higher pressure measurements of vibrational spectra place a lower bound of approximately 250 GPa on the predicted transition pressure for dissociation of molecular hydrogen to form a monatomic metal.

  18. Phase spaces related to standard classical $r$-matrices

    OpenAIRE

    Zakrzewski, S.

    1995-01-01

    Fundamental representations of real simple Poisson Lie groups are Poisson actions with a suitable choice of the Poisson structure on the underlying (real) vector space. We study these (mostly quadratic) Poisson structures and corresponding phase spaces (symplectic groupoids).

  19. 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

    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...... 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...

  20. PWR Secondary Water Chemistry Control Status: A Summary of Industry Initiatives, Experience and Trends Relative to the EPRI PWR Secondary Water Chemistry Guidelines

    International Nuclear Information System (INIS)

    The latest revision of the EPRI Pressurized Water Reactor (PWR) Secondary Water Chemistry Guidelines was issued in February 2009. The Guidelines continue to focus on minimizing stress corrosion cracking (SCC) of steam generator tubes, as well as minimizing degradation of other major components / subsystems of the secondary system. The Guidelines provide a technically-based framework for a plant-specific and effective PWR secondary water chemistry program. With the issuance of Revision 7 of the Guidelines in 2009, many plants have implemented changes that allow greater flexibility on startup. For example, the previous Guidelines (Revision 6) contained a possible low power hold at 5% power and a possible mid power hold at approximately 30% power based on chemistry constraints. Revision 7 has established a range over which a plant-specific value can be chosen for the possible low power hold (between 5% and 15%) and mid power hold (between 30% and 50%). This has provided plants the ability to establish significant plant evolutions prior to reaching the possible power hold; such as establishing seal steam to the condenser, placing feed pumps in service, or initiating forward flow of heater drains. The application of this flexibility in the industry will be explored. This paper also highlights the major initiatives and industry trends with respect to PWR secondary chemistry; and outlines the recent work to effectively address them. These will be presented in light of recent operating experience, as derived from EPRI's PWR Chemistry Monitoring and Assessment (CMA) program (which contains more than 400 cycles of operating chemistry data). (authors)

  1. Interfacial Chemistry and the Design of Solid-Phase Nucleic Acid Hybridization Assays Using Immobilized Quantum Dots as Donors in Fluorescence Resonance Energy Transfer

    OpenAIRE

    Ulrich J. Krull; W. Russ Algar

    2011-01-01

    The use of quantum dots (QDs) as donors in fluorescence resonance energy transfer (FRET) offer several advantages for the development of multiplexed solid-phase QD-FRET nucleic acid hybridization assays. Designs for multiplexing have been demonstrated, but important challenges remain in the optimization of these systems. In this work, we identify several strategies based on the design of interfacial chemistry for improving sensitivity, obtaining lower limits of detection (LOD) and enabling th...

  2. Seedling mycorrhizal type and soil chemistry are related to canopy condition of Eucalyptus gomphocephala.

    Science.gov (United States)

    Ishaq, Lily; Barber, Paul A; Hardy, Giles E St J; Calver, Michael; Dell, Bernard

    2013-07-01

    The health of Eucalyptus gomphocephala is declining within its natural range in south-western Australia. In a pilot study to assess whether changes in mycorrhizal fungi and soil chemistry might be associated with E. gomphocephala decline, we set up a containerized bioassay experiment with E. gomphocephala as the trap plant using intact soil cores collected from 12 sites with E. gomphocephala canopy condition ranging from healthy to declining. Adjacent soil samples were collected for chemical analysis. The type of mycorrhiza (arbuscular or ectomycorrhizal) formed in containerized seedlings predicted the canopy condition of E. gomphocephala at the sites where the cores were taken. Ectomycorrhizal fungi colonization was higher in seedling roots in soil taken from sites with healthy canopies, whereas colonization by arbuscular mycorrhizal fungi dominated in roots in soil taken from sites with declining canopies. Furthermore, several soil chemical properties predicted canopy condition and the type of mycorrhizal fungi colonizing roots. These preliminary findings suggest that large-scale studies should be undertaken in the field to quantify those ectomycorrhiza (ECM) fungi sensitive to E. gomphocephala canopy decline and whether particular ECM fungi are bioindicators of ecosystem health. PMID:23314749

  3. Characterizing the gas phase ion chemistry of an ion trap mobility spectrometry based explosive trace detector using a tandem mass spectrometer.

    Science.gov (United States)

    Kozole, Joseph; Tomlinson-Phillips, Jill; Stairs, Jason R; Harper, Jason D; Lukow, Stefan R; Lareau, Richard T; Boudries, Hacene; Lai, Hanh; Brauer, Carolyn S

    2012-09-15

    A commercial-off-the-shelf (COTS) ion trap mobility spectrometry (ITMS) based explosive trace detector (ETD) has been interfaced to a triple quadrupole mass spectrometer (MS/MS) for the purpose of characterizing the gas phase ion chemistry intrinsic to the ITMS instrument. The overall objective of the research is to develop a fundamental understanding of the gas phase ionization processes in the ITMS based ETD to facilitate the advancement of its operational effectiveness as well as guide the development of next generation ETDs. Product ion masses, daughter ion masses, and reduced mobility values measured by the ITMS/MS/MS configuration for a suite of nitro, nitrate, and peroxide containing explosives are reported. Molecular formulas, molecular structures, and ionization pathways for the various product ions are inferred using the mass and mobility data in conjunction with density functional theory. The predominant product ions are identified as follows: [TNT-H](-) for trinitrotoluene (TNT), [RDX+Cl](-) for cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), [NO(3)](-) for ethylene glycol dinitrate (EGDN), [NG+NO(3)](-) for nitroglycerine (NG), [PETN+NO(3)](-) for pentaerythritol tetranitrate (PETN), [HNO(3)+NO(3)](-) for ammonium nitrate (NH(4)NO(3)), [HMTD-NC(3)H(6)O(3)+H+Cl](-) for hexamethylene triperoxide diamine (HMTD), and [(CH(3))(2)CNH(2)](+) for triacetone triperoxide (TATP). The predominant ionization pathways for the formation of the various product ions are determined to include proton abstraction, ion-molecule attachment, autoionization, first-order and multi-order thermolysis, and nucleophilic substitution. The ion trapping scheme in the reaction region of the ITMS instrument is shown to increase predominant ion intensities relative to the secondary ion intensities when compared to non-ion trap operation. PMID:22967626

  4. Particle-Phase Chemistry of Secondary Organic Material: Modeled Compared to Measured O:C and H:C Elemental Ratios Provide Constraints

    Science.gov (United States)

    Chen, Q.; Liu, Y.; Donahue, N. M.; Shilling, J. E.; Martin, S. T.

    2011-12-01

    Secondary organic material (SOM) produced by the oxidation of biogenic volatile organic compounds is a major global contributor to the mass concentrations of organic components of atmospheric particles. Chemical mechanisms of SOM production are typically developed in focused laboratory studies but widely used in the complex modeling context of the atmosphere. Given this extrapolation, it is crucial to use multidimensional data constraints for testing the accuracy of the chemical mechanisms. Particle mass yield is a typical standard for model-measurement comparison. Particle composition expressed as O:C and H:C elemental ratios can serve as a higher dimensional constraint. A paradigm that uses the two constraints is presented in this study for SOM production from an important C5-C10-C15 terpene sequence, namely isoprene, α-pinene, and β-caryopyhllene. The model MCM-SIMPOL is introduced based on the Master Chemical Mechanism (MCM v3.2) and a group contribution method for vapor pressures (SIMPOL). The O:C and H:C ratios of the SOM are measured using an Aerosol Mass Spectrometer (AMS). Detailed SOM-specific AMS calibrations indicate that published O:C and H:C ratios for SOM are systematically too low. Overall, the measurement-model gap was small for particle mass yield but significant for particle-average elemental composition. The implication is that a key chemical pathway is missing from the chemical mechanism. The data can be explained by the particle-phase homolytic decomposition of organic hydroperoxides and subsequent alkyl-radical-promoted oligomerization. For climate-related modeling such as the aerosol direct effect, mass-based modeling is the norm. In this regard, the model might be concluded as acceptably accurate based on the one-dimensional model-measurement comparison on yield; yet, the further analysis proves that the model mechanism is missing important particle-phase chemistry that possibly controls the physical properties of the particles.

  5. Thermodynamic and transport properties of uranium dioxide and related phases

    International Nuclear Information System (INIS)

    The high melting point of uranium dioxide and its stability under irradiation have led to its use as a fuel in a variety of types of nuclear reactors. A wide range of chemical and physical studies has been stimulated by this circumstances and by the complex nature of the uranium dioxide phase itself. The boundaries of this phase widen as the temperature is increased; at 2000 deg. K a single, homogeneous phase exists from U2.27 to a hypostoichiometric (UO2-x) composition, depending on the oxygen potential of the surroundings. Since there is often an incentive to operate a reactor at the maximum practicable heat rating and, therefore, maximum thermal gradient in the fuel, the determination of the physical properties of the UO2-x phase becomes a matter of great technological importance. In addition a complex sequence of U-O phases may be formed during the preparation of powder feed material or during the sintering process; these affect the microstructure and properties of the final product and have also received much attention. 184 refs, 33 figs, 15 tabs

  6. Recent advances in the field of recoil chemistry

    International Nuclear Information System (INIS)

    Recent advances in the field of recoil chemistry are summarized and discussed. As important aids to furthering our knowledge of complex systems, the role is emphasized of new techniques such as vapour-phase chromatography, ion exchange and paper electrophoresis. An attempt is made to relate current work in recoil chemistry to other fields of investigation. (author)

  7. Boronyl chemistry: the BO group as a new ligand in gas-phase clusters and synthetic compounds.

    Science.gov (United States)

    Zhai, Hua-Jin; Chen, Qiang; Bai, Hui; Li, Si-Dian; Wang, Lai-Sheng

    2014-08-19

    Boronyl (BO) is a monovalent σ radical with a robust B≡O triple bond. Although BO/BO(-) are isovalent to CN/CN(-) and CO, the chemistry of boronyl has remained relatively unknown until recently, whereas CN/CN(-) and CO are well-known inorganic ligands. Further analogy may be established for BO versus H or Au ligands, which are all monovalent σ radicals. This Account intends to provide an overview of research activities over the past few years that are relevant to the development of boronyl chemistry, in particular, in size-selected gaseous clusters containing BO. The systems covered herein include transition metal boronyl clusters, carbon boronyl clusters, boron oxide clusters and boron boronyl complexes, the boronyl boroxine, and the first synthetic Pt-BO bulk compound. In these boronyl clusters and compounds, the BO groups show remarkable structural and chemical integrity as a ligand. Among transition metal boronyls, gold monoboronyl clusters Aun(BO)(-) and Aun(BO) (n = 1-3) have been characterized, and they are shown to possess electronic and structural properties similar to the corresponding Au(n+1)(-) and Au(n+1) bare clusters, demonstrating the BO/Au analogy. The Au-B bonding in the Au-BO clusters is highly covalent. A recent advance in boronyl chemistry is the successful synthesis and isolation of the first boronyl compound, trans-[(Cy3P)2BrPt(BO)]. This unique Pt-BO compound and other potential transition metal boronyl compounds may find applications in catalysis and as chemical building blocks. Carbon boronyl clusters versus boron carbonyl clusters is a topic of interest in designing new aromatic complexes. Experimental and theoretical data obtained to date show that carbon boronyl clusters are generally far more stable than their boron carbonyl counterparts, highlighting the potency of boronyl as a ligand in aromatic compounds. Notably, in light of the BO/H analogy, the perfectly hexagonal (CBO)6 cluster is a carbon boronyl analogue of benzene. The BO

  8. A new approach for the synthesis of O-glycopeptides through a combination of solid-phase glycosylation and fluorous tagging chemistry (SHGPFT).

    Science.gov (United States)

    Liu, Bo; Zhang, Fa; Zhang, Yan; Liu, Gang

    2014-03-28

    Glycoproteins and glycopeptides play important roles in various physiological and pathophysiological processes. Efficient preparation of glycopeptides with a specific structure is one of the pivotal areas in current chemistry research. In this article, a new SHGPFT approach to the synthesis and efficient purification of O-glycosylated peptides is developed by combining a solid-phase glycosylation and a light-fluorous glycosyl donor protocol. The desired product is finally isolated from the side products in the cleaved mixture by an efficient fluorous solid-phase extraction (F-SPE) step. PMID:24519332

  9. Domain-specific expertise of chemistry teachers on context-based education about macro-micro thinking in structure-property relations

    OpenAIRE

    Dolfing, R.; Bulte, A.M.W.; Pilot, A.; Vermunt, J. D.

    2012-01-01

    This study aims to determine and describe the new domain-specific expertise of experienced chemistry teachers in teaching an innovative context-based unit about macro– micro thinking in structure–property relations. The construct of ‘teachers’ domain-specific expertise’ was used to analyse the new repertoire chemistry teachers need to acquire to teach a context-based unit and achieve the intended effects of the curriculum innovation. A phenomenological approach of exploration and verification...

  10. Introducing Organic Chemistry Students to Natural Product Isolation Using Steam Distillation and Liquid Phase Extraction of Thymol, Camphor, and Citral, Monoterpenes Sharing a Unified Biosynthetic Precursor

    Science.gov (United States)

    McLain, Katherine A.; Miller, Kenneth A.; Collins, William R.

    2015-01-01

    Plants have provided and continue to provide the inspiration and foundation for modern medicines. Natural product isolation is a key component of the process of drug discovery from plants. The purpose of this experiment is to introduce first semester undergraduate organic chemistry students, who have relatively few lab techniques at their…

  11. Phase relation between global temperature and atmospheric carbon dioxide

    OpenAIRE

    Stallinga, Peter; Khmelinskii, Igor

    2013-01-01

    The primary ingredient of Anthropogenic Global Warming hypothesis is the assumption that atmospheric carbon dioxide variations are the cause for temperature variations. In this paper we discuss this assumption and analyze it on basis of bi-centenary measurements and using a relaxation model which causes phase shifts and delays.

  12. Investigation of Attitudes of Students in The Programs of Class Teaching, and Science Teaching Towards Chemistry Lesson, and The Relation Between Their Multiple Intelligence Fields and Their Success in Chemistry and Language Lessons

    Directory of Open Access Journals (Sweden)

    Hasan ÖZYILDIRIM

    2005-06-01

    Full Text Available The basis of Multiple Intelligence Theory contains development and learning during life time. According to this theory all human have different intelligences which are verbal-linguistic, logical-mathematical, visual-spatial, bodily-kinesthetic, musical, interpersonal, intrapersonal and naturalist intelligences in varying amounts.In this study, the attitude toward Chemistry Lesson, the Multiple Intelligence Fields of the 1st class students in the program of Class Teaching and Science Teaching at Trakya University, Faculty of Education, and the relation between their attitudes, their multiple intelligence fields and their success in Chemistry and Turkish Language Lessons were investigated.In order to find out the intelligence fields of students the inventory of multiple intelligence taken from Saban (2002 was used. And the chemistry lesson attitude scale developed by Morgil etc. (2000 was utilized to establish their attitudes toward chemistry lesson.The data obtained were evaluated in SPSS 11.0 package program, and variation analysis, t-test and correlation analyses for all data were applied.As a result of research it was found that students were positive in their attitude toward chemistry lesson and their intelligence fields were expanded through developed medium-level as homogenous to all intelligence fields.The significant differences were found out between students’ intelligence fields regarding their main branches., and a relationship existed between students’ attitude toward chemistry lesson and their logical/mathematical and verbal/linguistic of intelligence fields, and between students’ success in chemistry lesson and logical/ mathematical field of intelligence.

  13. Predicting and Mitigating Corrosion Related Damage in Geothermal Facilities, Phase-I

    Energy Technology Data Exchange (ETDEWEB)

    M. Shirmohamadi; S. Bratt; J. Ridgely

    2000-08-25

    Corrosion related damage (CRD) is probably the most important and costly damage mechanism for components operating in geothermal fields. This problem is further complicated as steam chemistry in such fields changes continuously with season, time, and load. Unfortunately, such changes are not predictable. The problem is further complicated in the area where early condensate (first moisture) forms. The chemistry of these first droplets is significantly different from that of built steam and this, again, cannot be predicted with reasonable accuracy. Therefore, a formidable challenge facing the geothermal field operators remains in knowing the chemistry of the condensate and, more importantly, how it affects specific field equipment such as rotor, piping, valves, etc. This project showed that testing in such an environment is feasible and concluded that continuous monitoring of steam conditions is needed to detect and prevent conditions leading to CRD of components. This project also developed tools and techniques for continuous monitoring of corrosion potential and detection of pitting events.

  14. The phase stability of Ca2TiO4 and related Ruddlesden-Popper phases

    Science.gov (United States)

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

    2015-11-01

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

  15. [Highly selective analysis of biogenic-related compounds utilizing fluorous chemistry].

    Science.gov (United States)

    Hayama, Tadashi

    2015-01-01

    Perfluoroalkyl-containing compounds are highly fluorous, meaning that they have a remarkable affinity for one another and effectively exclude non-fluorous species. Utilizing this unique property, we have developed a fluorous derivatization with a liquid chromatographic analysis method for highly selective analysis of target analytes. Although most previous methods focused on extremely sensitive detection-oriented derivatization, the fluorous derivatization method involves highly specific separation for analytes. This method includes perfluoroalkylation of analytes with a fluorous reagent, and separation of the derivatives using a perfluoroalkyl-modified stationary phase LC column. The derivatives can be selectively retained on the fluorous-phase LC column, whereas the non-fluorous derivatives are poorly retained under the same separation conditions. The combination of this method with LC-tandem mass spectrometry (MS/MS) is very useful for complex biological sample analysis, because matrix-induced suppression effects, which are a common problem in LC-MS/MS analysis arising from components of a biological endogenous matrix, have not been observed. We have successfully applied this method to precise and accurate LC-MS/MS analysis of some biogenic compounds, such as sialic acids and biogenic amines, in complex biological samples. PMID:25747214

  16. Bismuthates: BaBiO3 and related superconducting phases

    International Nuclear Information System (INIS)

    Highlights: • BaBiO3 has the perovskite structure, but tilting of the BiO6 octahedra destroy the ideal cubic symmetry except at temperatures above 820 K. BaBiO3 is a diamagnetic semiconductor due to a CDW, which is equivalent to a Ba2Bi3+Bi5+O6 representation. • Recent calculations and experimental results confirm that there is no significant deviation from the oxidation states of 3+ and 5+. • Superconductivity with a Tc as high as 13 K occurs for BaPb1−xBixO3 phases where the 6s band is about 25% filled, and superconductivity with a Tc as high as 34 K occurs for Ba1−xKxBiO3 phases where the 6s band is about 35% filled. • These two solid solutions can have cubic, tetragonal, or orthorhombic symmetry. • However, superconductivity has only been observed when the symmetry is tetragonal. - Abstract: BaBiO3 has the perovskite structure, but tilting of the BiO6 octahedra destroy the ideal cubic symmetry except at temperatures above 820 K. BaBiO3 is a diamagnetic semiconductor due to a charge density wave (CDW), which is equivalent to a Ba2Bi3+Bi5+O6 representation. Recent calculations and experimental results confirm that there is no significant deviation from the oxidation states of 3+ and 5+. Superconductivity with a Tc as high as 13 K occurs for BaPb1−xBixO3 phases where the 6s band is about 25% filled, and superconductivity with a Tc as high as 34 K occurs for Ba1−xKxBiO3 phases where the 6s band is about 35% filled. Structures in these two solid solutions can have cubic, tetragonal, orthorhombic, or monoclinic symmetry. However, superconductivity has only been observed when the symmetry is tetragonal

  17. Topology and phase transitions II. Theorem on a necessary relation

    International Nuclear Information System (INIS)

    In this second paper, we prove a necessity theorem about the topological origin of phase transitions. We consider physical systems described by smooth microscopic interaction potentials VN(q), among N degrees of freedom, and the associated family of configuration space submanifolds {Mv}velementofR, with Mv={q element of RN|VN(q)≤v}. On the basis of an analytic relationship between a suitably weighed sum of the Morse indexes of the manifolds {Mv}velementofR and thermodynamic entropy, the theorem states that any possible unbound growth with N of one of the following derivatives of the configurational entropy S(-)(v)=(1/N)log∫MvdNq, that is of |∂kS(-)(v)/∂vk|, for k=3,4, can be entailed only by the weighed sum of Morse indexes. Since the unbound growth with N of one of these derivatives corresponds to the occurrence of a first- or of a second-order phase transition, and since the variation of the Morse indexes of a manifold is in one-to-one correspondence with a change of its topology, the Main Theorem of the present paper states that a phase transition necessarily stems from a topological transition in configuration space. The proof of the theorem given in the present paper cannot be done without Main Theorem of (paper I)

  18. Quantum chemical study of relative reactivities of a series of amines and nitriles - Relevance to prebiotic chemistry

    Science.gov (United States)

    Loew, G. H.; Berkowitz, D.; Chang, S.

    1975-01-01

    Using the Iterative Extended Huckel Theory (IEHT) calculations of the electron distribution and orbital energies of a series of thirteen amines, nitriles and amino-nitriles relevant to prebiotic and cosmo-chemistry have been carried out. Ground state properties such as the energy and nature of the highest occupied (HOMO) and lowest empty (LEMO) molecular orbitals, net atomic charges and number of nonbonding electrons have been identified as criteria for correlating the relative nucleophilicity of amine and nitrile nitrogens and the electrophilicity of nitrile and other unsaturated carbon atoms. The results of such correlations can be partially verified by known chemical behavior of these compounds and are used to predict and understand their role in prebiotic organic synthesis.

  19. Students’ interest and experiences in physics and chemistry related themes: Reflections based on a ROSE-survey in Finland

    Directory of Open Access Journals (Sweden)

    Jari Lavonen

    2008-01-01

    Full Text Available Interest in physics and chemistry topics and out-of-school experiences of Finnish secondary school students (n=3626, median age 15 were surveyed using the international ROSE questionnaire. Based on explorative factor analysis the scores of six out-of-school experience factors (indicating how often students had done something outside of school and eight topic factors (indicating how interested students were in learning about something were studied. The students had a lot of out-of-school experiences in simple measuring and observing and in ICT use, but they had few science and technology related hobbies and activities or experiences of camping. Several gender differences were found. Observing natural phenomena and collecting objects was the most important factor correlating with the topic factors. Factors measuring experiences of ICT use and the use of mechanical tools had the lowest correlations with the topic factors. Based on the results, the implications for science education will be discussed.

  20. Structure, chemistry, and growth mechanisms of photovoltaic quality thin-film Cu(In,Ga)Se2 grown from a mixed-phase precursor

    International Nuclear Information System (INIS)

    The formation chemistry and growth dynamics of thin-film CuInSe2 grown by physical vapor deposition have been considered along the reaction path leading from the CuxSe:CuInSe2 two-phase region to single-phase CuInSe2. The (Cu2Se)β(CuInSe2)1-β (02:CuxSe phase separation is identified and occurs primarily normal to the substrate plane at free surfaces. Single-phase CuInSe2 is created by the conversion of the CuxSe into CuInSe2 upon exposure to In and Se activity. Noninterrupted columnar growth continues at substrate temperatures above 500 degree C. The addition of In in excess of that required for conversion produces an In-rich near-surface region with a CuIn3Se5 surface chemistry. A model is developed that describes the growth process. The model provides a vision for the production of thin-film CuInSe2 in industrial scale systems. Photovoltaic devices incorporating Ga with total-area efficiencies of 14.4%--16.4% have been produced by this process and variations on this process

  1. Aromatic Amino Acids and Related Substances: Chemistry, Biology, Medicine, and Application

    Science.gov (United States)

    On the occasion of the "Transdisciplinary International Conference on Aromatic Amino Acids and Related Substances," the organizing committee honors and thanks the expert participants from many areas of aromatic amino acid (AAA)3 research. In this transdisciplinary meeting, "aromatic paradigms" were ...

  2. Topology and Phase Transitions: Theorem on a necessary relation

    OpenAIRE

    Roberto FranzosiDipartimento di fisica Universita' di Pisa, INFN Sez. di Pisa e INFM Unita' di Pisa, Italy; Marco Pettini(Osservatorio Astrofisico di Arcetri, Firenze, Italy;); Lionel Spinelli(CPT-CNRS, Luminy, Marseille, France)

    2015-01-01

    An emended and improved version of the present paper has been archived in math-ph/0505057, and a preliminary account of its content has been published in Phys.Rev.Lett. 92, 60601, (2004). Moreover, in order to prove the relevance of topology for phase transition phenomena in a broad domain of physically interesting cases, we have proved another theorem which is reported in math-ph/0505058 and which is crucially based on the result of the paper archived in math-ph/0505057.

  3. Perspective: Water cluster mediated atmospheric chemistry

    International Nuclear Information System (INIS)

    The importance of water in atmospheric and environmental chemistry initiated recent studies with results documenting catalysis, suppression and anti-catalysis of thermal and photochemical reactions due to hydrogen bonding of reagents with water. Water, even one water molecule in binary complexes, has been shown by quantum chemistry to stabilize the transition state and lower its energy. However, new results underscore the need to evaluate the relative competing rates between reaction and dissipation to elucidate the role of water in chemistry. Water clusters have been used successfully as models for reactions in gas-phase, in aqueous condensed phases and at aqueous surfaces. Opportunities for experimental and theoretical chemical physics to make fundamental new discoveries abound. Work in this field is timely given the importance of water in atmospheric and environmental chemistry.

  4. Shallow fractionation signature of phase chemistry in Taburiente lavas, La Palma, Canary Islands: Results of MELTS modeling

    Science.gov (United States)

    Guetschow, H. A.; Nelson, B. K.

    2002-12-01

    Depth of crystal fractionation influences the chemical evolution of ocean island basalts and has significant implications for the physical structures of these volcanoes. In contrast to dominantly shallow systems such as Hawaii, a range of fractionation depths have been reported for Canary Islands lavas. Magmas erupted on La Palma preserve fluid- and melt-inclusion evidence for high-pressure (> 10 kbar) crystallization (Klügel et al., 1998; Hansteen et al., 1998; Nikogosian et al., 2002). If high-pressure fractional crystallization were an early and dominant process, it would generate specific patterns in rock and phase chemistry of eruptive sequences. Alkalic basalts from Taburiente volcano display coherent major element trends consistent with evolution dominated by fractional crystallization while their phenocryst compositions, trace elements, and isotopic trends require mixing between multiple sources. The current model confirms the importance of both fractionation and mixing to achieve the full range of lavas observed. A low-pressure (1 kbar) thermodynamic fractional crystallization model performed with the MELTS (Ghiorso and Sack, 1995) software closely reproduces major element trends from two stratigraphic sequences. This model also predicts the observed sequence of groundmass clinopyroxene compositions and phenocryst zoning reversals. In all low pressure simulations, olivine remains a modally significant liquidus phase during the first 20% and last 30% of the crystallization sequence, resulting in a negative correlation between the CaO and Fo content of olivine. These results are consistent with the presence of olivine phenocrysts that bear petrographic evidence of early crystallization, as well as observed compositional trends of groundmass olivine and clinopyroxene in Taburiente lavas. MELTS models that include an initial period of high pressure (12 kbar) clinopyroxene fractionation produce major element trends comparable to the low pressure model, but

  5. Privileged scaffolds or promiscuous binders: a comparative study on rhodanines and related heterocycles in medicinal chemistry.

    Science.gov (United States)

    Mendgen, Thomas; Steuer, Christian; Klein, Christian D

    2012-01-26

    Rhodanines and related five-membered heterocycles with multiple heteroatoms have recently gained a reputation of being unselective compounds that appear as "frequent hitters" in screening campaigns and therefore have little value in drug discovery. However, this judgment appears to be based mostly on anecdotal evidence. Having identified various rhodanines and related compounds in screening campaigns, we decided to perform a systematic study on their promiscuity. An amount of 163 rhodanines, hydantoins, thiohydantoins, and thiazolidinediones were synthesized and tested against several targets. The compounds were also characterized with respect to aggregation and electrophilic reactivity, and the binding modes of rhodanines and related compounds in published X-ray cocrystal structures were analyzed. The results indicate that the exocyclic, double bonded sulfur atom in rhodanines and thiohydantoins, in addition to other structural features, offers a particularly high density of interaction sites for polar interactions and hydrogen bonds. This causes a promiscuous behavior at concentrations in the "screening range" but should not be regarded as a general knockout criterion that excludes such screening hits from further development. It is suggested that special criteria for target affinity and selectivity are applied to these classes of compounds and that their exceptional and potentially valuable biomolecular binding properties are consequently exploited in a useful way. PMID:22077389

  6. Student-generated questions during chemistry lectures: Patterns, self-appraisals, and relations with motivational beliefs and achievement

    Science.gov (United States)

    Bergey, Bradley W.

    Self-generated questions are a central mechanism for learning, yet students' questions are often infrequent during classroom instruction. As a result, little is known about the nature of student questioning during typical instructional contexts such as listening to a lecture, including the extent and nature of student-generated questions, how students evaluate their questions, and the relations among questions, motivations, and achievement. This study examined the questions undergraduate students (N = 103) generated during 8 lectures in an introductory chemistry course. Students recorded and appraised their question in daily question logs and reported lecture-specific self-efficacy beliefs. Self-efficacy, personal interest, goal orientations, and other motivational self-beliefs were measured before and after the unit. Primary analyses included testing path models, multiple regressions, and latent class analyses. Overall, results indicated that several characteristics of student questioning during lectures were significantly related to various motivations and achievement. Higher end-of-class self-efficacy was associated with fewer procedural questions and more questions that reflected smaller knowledge deficits. Lower exam scores were associated with questions reflecting broader knowledge deficits and students' appraisals that their questions had less value for others than for themselves. Individual goal orientations collectively and positively predicted question appraisals. The questions students generated and their relations with motivational variables and achievement are discussed in light of the learning task and academic context.

  7. The physical chemistry of nucleation of sub-micrometer non-oxide ceramic powders via sub-oxide vapor-phase reduction reaction

    International Nuclear Information System (INIS)

    Fine ceramic powders (< 500 nm) exhibit exceptional physical and mechanical properties in engineered structural ceramics. The production of fine powders, in particular the non-oxide ceramics, via a cheaper route than the organic solvent route has been rather elusive. This paper examines the physical chemistry of sub-oxide vapor-phase reduction reaction for the nucleation of non-oxide ceramic phase. Well known vapor species eg SiO and BO in the production of technical ceramic powders (SiC, BN) are particularly discussed for understanding the nucleation process of SiC and BN ceramic phases respectively. The regimes of partial pressures and temperatures are particularly identified. The calculated nucleation rate as a function of the temperature is compared with the experimental results on powder morphology. The production of amorphous and nanocrystalline h-BN powders is discussed in the context of substrate structure and thermodynamic parameters

  8. Reptilian chemistry: Characterization of a family of dianeackerone-related steroidal esters from a crocodile secretion

    Science.gov (United States)

    Yang, Zhicai; Whyte, Authrine; Attygalle, Athula B.; Weldon, Paul J.; Eisner, Thomas; Meinwald, Jerrold

    1999-01-01

    The African dwarf crocodile, Osteolaemus tetraspis (Crocodilidae, Reptilia), possesses a pair of skin glands, the paracloacal glands, the secretion of which is thought to be used to mark nest sites or attract mates. Ten aromatic steroidal esters were isolated from this secretion and characterized on the basis of NMR spectroscopic investigations, electrospray ionization-MS analyses, and chemical degradation. These esters, which account for more than 90% of the paracloacal glandular secretion, are derived from either cholesterol or cholestanol, esterified with a C-20 or C-22 acid closely related to dianeackerone, the only significant volatile compound found in this secretion. PMID:10535907

  9. Ruthenium Tetroxide and Perruthenate Chemistry. Recent Advances and Related Transformations Mediated by Other Transition Metal Oxo-species

    Directory of Open Access Journals (Sweden)

    Vincenzo Piccialli

    2014-05-01

    Full Text Available In the last years ruthenium tetroxide is increasingly being used in organic synthesis. Thanks to the fine tuning of the reaction conditions, including pH control of the medium and the use of a wider range of co-oxidants, this species has proven to be a reagent able to catalyse useful synthetic transformations which are either a valuable alternative to established methods or even, in some cases, the method of choice. Protocols for oxidation of hydrocarbons, oxidative cleavage of C–C double bonds, even stopping the process at the aldehyde stage, oxidative cleavage of terminal and internal alkynes, oxidation of alcohols to carboxylic acids, dihydroxylation of alkenes, oxidative degradation of phenyl and other heteroaromatic nuclei, oxidative cyclization of dienes, have now reached a good level of improvement and are more and more included into complex synthetic sequences. The perruthenate ion is a ruthenium (VII oxo-species. Since its introduction in the mid-eighties, tetrapropylammonium perruthenate (TPAP has reached a great popularity among organic chemists and it is mostly employed in catalytic amounts in conjunction with N-methylmorpholine N-oxide (NMO for the mild oxidation of primary and secondary alcohols to carbonyl compounds. Its use in the oxidation of other functionalities is known and recently, its utility in new synthetic transformations has been demonstrated. New processes, synthetic applications, theoretical studies and unusual transformations, published in the last eight years (2006–2013, in the chemistry of these two oxo-species, will be covered in this review with the aim of offering a clear picture of their reactivity. When appropriate, related oxidative transformations mediated by other metal oxo-species will be presented to highlight similarities and differences. An historical overview of some aspects of the ruthenium tetroxide chemistry will be presented as well.

  10. Relating sulfide mineral zonation and trace element chemistry to subsurface processes in the Reykjanes geothermal system, Iceland

    Science.gov (United States)

    Libbey, R. B.; Williams-Jones, A. E.

    2016-01-01

    The nature and distribution of sulfide minerals and their trace element chemistry in the seawater-dominated Reykjanes geothermal system was determined through the study of cuttings and core from wells that intersect different regions of the hydrothermal cell, from the near surface to depths of > 3000 m. The observed sulfide mineral zonation and trace element enrichment correlate well with the present-day thermal structure of the system. Isocubanite and pyrrhotite are confined to the deep, low permeability regions, whereas an assemblage of chalcopyrite and pyrite predominates in the main convective upflow path. The presence of marcasite in the uppermost regions of the system reflects weakly acidic conditions (pH geothermal system was derived from a mixture of basaltic and reduced seawater sources. Petrographic evidence suggests that seawater-derived hydrothermal fluids have altered primary igneous sulfides in the host rocks, a process that has been proposed as a major control of aqueous sulfide production in mid-ocean ridge environments. Calculations show that igneous sulfides in the host basalts likely account for less than 5% of the total available ore metal budget in the system, however, their contribution to fluid metal budgets is probably significant because of their relatively high solubility. The processes documented by this study are likely analogous to those operating in the feeder and deep reaction zones of mid-ocean ridge seafloor hydrothermal systems. The results show that sulfide mineral zonation and trace element chemistry vary as a function of physicochemical parameters that are relevant to the characterization and exploration of geothermal energy resources.

  11. Low-temperature structural phase transitions in crystalline bromo and iodo 9-hydroxyphenalenone derivatives: Quantum chemistry employment

    Science.gov (United States)

    Dolin, S. P.; Khrulev, A. A.; Polyakov, E. V.; Mikhailova, T. Yu.; Levin, A. A.

    The model approaches and quantum chemical calculations are employed to explain the peculiarities of the ferroelectric behavior of new ?zero-dimensional? H-bonded materials, i.e., 5-bromo and 5-iodo derivatives of 9-hydroxyphenalenone (9HPO) and its deuteroxy analogue (9DPO). The tunneling parameters ? (H/D) and the Ising model coupling parameters Jij are evaluated and discussed. Analysis of these parameters for the hydroxy and deuteroxy species demonstrates the quantum paraelectric behavior of both Br and I 9HPO derivatives due to the large values of the ?(H)/J0 relation, where J0 is the molecular field parameter describing the coupling of any given H-bond proton with all rest ones. In contrast, small values ?(D)/J0 for their 9DPO analogues favor the low-temperature structural phase transition into an ordered phase, which has a rather antiferroelectric than ferroelectric character. The estimates obtained and the resulting conclusions are in line with the overall observed trends in behavior of the substances under examination that emerge from the available experimental data.

  12. Secondary soil phases controlling surface water chemistry during experimental acidification at the Bear Brook Watershed in Maine, USA

    Czech Academy of Sciences Publication Activity Database

    Navrátil, Tomáš; Norton, S. A.; Fernandez, I. J.; Diehl, M.

    Santa Cruz : University of Santa Cruz, 2006 - (Crow, S.). s. 158-158 [BIOGEOMON. 25.6.2006-30.6.2006, Santa Cruz, California] Institutional research plan: CEZ:AV0Z30130516 Keywords : experimental acidification * streamwater * chemistry * aluminum * sulfate Subject RIV: DD - Geochemistry

  13. How subtle is the "terroir" effect? Chemistry-related signatures of two "climats de Bourgogne".

    Directory of Open Access Journals (Sweden)

    Chloé Roullier-Gall

    Full Text Available The chemical composition of grape berries is influenced by various environmental conditions often considered to be representative of a "terroir". If grapes from a given terroir are assumed to reflect this origin in their chemical compositions, the corresponding wine should also reflect it. The aim of this work was therefore to reveal the "terroir" expression within the chemodiversity of grapes and related wines, using ultrahigh-resolution mass spectrometry. Grapes and corresponding wines, from two distinct - though very proximate - terroirs of Burgundy were analyzed over three vintages (2010, 2011 and 2012. Ultrahigh-resolution mass spectrometry and ultra-high performance liquid chromatography were used as untargeted and targeted approaches to discriminate complex chemical fingerprints for vintages, classes (wines, skins or musts, and terroirs. Statistical analyses revealed that even if vintages have the most significant impact on fingerprints, the most significant terroir differences are seen in the grapes of a given vintage.

  14. Elementary physical chemistry

    CERN Document Server

    Linder, Bruno

    2010-01-01

    This book is designed for a one-semester course, for undergraduates, not necessarily chemistry majors, who need to know something about physical chemistry. The emphasis is not on mathematical rigor, but subtleties and conceptual difficulties are not hidden. It covers the essential topics in physical chemistry, including the state of matter, thermodynamics, chemical kinetics, phase and chemical equilibria, introduction to quantum theory, and molecular spectroscopy.

  15. A RECENT ACCRETION BURST IN THE LOW-MASS PROTOSTAR IRAS 15398-3359: ALMA IMAGING OF ITS RELATED CHEMISTRY

    International Nuclear Information System (INIS)

    Low-mass protostars have been suggested to show highly variable accretion rates throughout their evolution. Such changes in accretion, and related heating of their ambient envelopes, may trigger significant chemical variations on different spatial scales and from source-to-source. We present images of emission from C17O, H13CO+, CH3OH, C34S and C2H toward the low-mass protostar IRAS 15398-3359 on 0.''5 (75 AU diameter) scales with the Atacama Large Millimeter/submillimeter Array at 340 GHz. The resolved images show that the emission from H13CO+ is only present in a ring-like structure with a radius of about 1-1.''5 (150-200 AU) whereas the CO and other high dipole moment molecules are centrally condensed toward the location of the central protostar. We propose that HCO+ is destroyed by water vapor present on small scales. The origin of this water vapor is likely an accretion burst during the last 100-1000 yr increasing the luminosity of IRAS 15398-3359 by a factor of 100 above its current luminosity. Such a burst in luminosity can also explain the centrally condensed CH3OH and extended warm carbon-chain chemistry observed in this source and furthermore be reflected in the relative faintness of its compact continuum emission compared to other protostars

  16. Controlling Nonspecific Protein Adsorption in a Plug-Based Microfluidic System by Controlling Interfacial Chemistry Using Fluorous-Phase Surfactants

    OpenAIRE

    Roach, L. Spencer; Song, Helen; Ismagilov, Rustem F.

    2005-01-01

    Control of surface chemistry and protein adsorption is important for using microfluidic devices for biochemical analysis and high-throughput screening assays. This paper describes the control of protein adsorption at the liquid-liquid interface in a plug-based microfluidic system. The microfluidic system uses multiphase flows of immiscible fluorous and aqueous fluids to form plugs, which are aqueous droplets that are completely surrounded by fluorocarbon oil and do not come into direct contac...

  17. Numerical analysis of relative phase and amplitude at the interaction two solitons in optical fibers

    Directory of Open Access Journals (Sweden)

    Jakšić Branimir

    2011-01-01

    Full Text Available In this paper presented the analysis propagation solitons pair in optical fiber from the standpoint of relative amplitude and relative phase. Consider the influence of changes relative phase and amplitude in the interaction of two solitons in optical fibers. Shows the simulation (in the space-time domain of movement solitons pairs in optical fiber with the change of these two parameters.

  18. 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.

  19. Identifying Biotic Integrity and Water Chemistry Relations in Nonwadeable Rivers of Wisconsin: Toward the Development of Nutrient Criteria

    Science.gov (United States)

    Weigel, Brian M.; Robertson, Dale M.

    2007-10-01

    We sampled 41 sites on 34 nonwadeable rivers that represent the types of rivers in Wisconsin, and the kinds and intensities of nutrient and other anthropogenic stressors upon each river type. Sites covered much of United States Environmental Protection Agency national nutrient ecoregions VII—Mostly Glaciated Dairy Region, and VIII—Nutrient Poor, Largely Glaciated upper Midwest. Fish, macroinvertebrates, and three categories of environmental variables including nutrients, other water chemistry, and watershed features were collected using standard protocols. We summarized fish assemblages by index of biotic integrity (IBI) and its 10 component measures, and macroinvertebrates by 2 organic pollution tolerance and 12 proportional richness measures. All biotic and environmental variables represented a wide range of conditions, with biotic measures ranging from poor to excellent status, despite nutrient concentrations being consistently higher than reference concentrations reported for the regions. Regression tree analyses of nutrients on a suite of biotic measures identified breakpoints in total phosphorus (~0.06 mg/l) and total nitrogen (~0.64 mg/l) concentrations at which biotic assemblages were consistently impaired. Redundancy analyses (RDA) were used to identify the most important variables within each of the three environmental variable categories, which were then used to determine the relative influence of each variable category on the biota. Nutrient measures, suspended chlorophyll a, water clarity, and watershed land cover type (forest or row-crop agriculture) were the most important variables and they explained significant amounts of variation within the macroinvertebrate ( R 2 = 60.6%) and fish ( R 2 = 43.6%) assemblages. The environmental variables selected in the macroinvertebrate model were correlated to such an extent that partial RDA analyses could not attribute variation explained to individual environmental categories, assigning 89% of the

  20. Interfacial Chemistry and the Design of Solid-Phase Nucleic Acid Hybridization Assays Using Immobilized Quantum Dots as Donors in Fluorescence Resonance Energy Transfer

    Directory of Open Access Journals (Sweden)

    Ulrich J. Krull

    2011-06-01

    Full Text Available The use of quantum dots (QDs as donors in fluorescence resonance energy transfer (FRET offer several advantages for the development of multiplexed solid-phase QD-FRET nucleic acid hybridization assays. Designs for multiplexing have been demonstrated, but important challenges remain in the optimization of these systems. In this work, we identify several strategies based on the design of interfacial chemistry for improving sensitivity, obtaining lower limits of detection (LOD and enabling the regeneration and reuse of solid-phase QD-FRET hybridization assays. FRET-sensitized emission from acceptor dyes associated with hybridization events at immobilized QD donors provides the analytical signal in these assays. The minimization of active sensing area reduces background from QD donor PL and allows the resolution of smaller amounts of acceptor emission, thus lowering the LOD. The association of multiple acceptor dyes with each hybridization event can enhance FRET efficiency, thereby improving sensitivity. Many previous studies have used interfacial protein layers to generate selectivity; however, transient destabilization of these layers is shown to prevent efficient regeneration. To this end, we report a protein-free interfacial chemistry and demonstrate the specific detection of as little as 2 pmol of target, as well as an improved capacity for regeneration.

  1. Water chemistry experiences with VVERs at Kudankulam

    International Nuclear Information System (INIS)

    Kudankulam Nuclear Power Project - 1 and 2 (Kudankulam NPP - 1 and 2) are pressurised water cooled VVERs of 1000 MWe each. Kudankulam NPP Unit - 1 is presently on its first cycle of operation and Kudankulam NPP Unit - 2 is on the advanced stage of commissioning with the successful completion of hot run related Functional tests. Water Chemistry aspects during various phases of commissioning of Kudankulam NPP Unit - 1 such as Hot Run, Boric acid flushing, initial fuel Loading (IFL), First approach to Criticality (FAC) are discussed. The main objectives of the use of controlled primary water chemistry programme during the hot functional tests are reviewed. The importance of the relevant water chemistry parameters were ensured to have the quality of the passive layer formed on the primary coolant system surfaces. The operational experiences during the 1st cycle of operation of primary water chemistry, radioactivity transport and build-up are presented. The operational experience of some VVER units in the field of the primary water chemistry, radioactivity transport and build-up are presented as a comparison to VVER at Kudankulam NPP. The effects of the initial passivated layer formed on metal surfaces during hot run, activated corrosion products levels in the primary coolant under controlled water chemistry regime and the contamination/radiation situation are discussed. This report also includes the water chemistry related issues of secondary water systems. (author)

  2. A RECENT ACCRETION BURST IN THE LOW-MASS PROTOSTAR IRAS 15398-3359: ALMA IMAGING OF ITS RELATED CHEMISTRY

    Energy Technology Data Exchange (ETDEWEB)

    Jørgensen, Jes K.; Brinch, Christian; Lindberg, Johan E.; Bisschop, Suzanne E. [Niels Bohr Institute, University of Copenhagen, Juliane Maries Vej 30, DK-2100 Copenhagen Ø. (Denmark); Visser, Ruud; Bergin, Edwin A. [Department of Astronomy, University of Michigan, 500 Church Street, Ann Arbor, MI 48109-1042 (United States); Sakai, Nami; Yamamoto, Satoshi [Department of Physics, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan); Harsono, Daniel; Van Dishoeck, Ewine F.; Persson, Magnus V., E-mail: jeskj@nbi.dk [Leiden Observatory, Leiden University, P.O. Box 9513, NL-2300 RA Leiden (Netherlands)

    2013-12-20

    Low-mass protostars have been suggested to show highly variable accretion rates throughout their evolution. Such changes in accretion, and related heating of their ambient envelopes, may trigger significant chemical variations on different spatial scales and from source-to-source. We present images of emission from C{sup 17}O, H{sup 13}CO{sup +}, CH{sub 3}OH, C{sup 34}S and C{sub 2}H toward the low-mass protostar IRAS 15398-3359 on 0.''5 (75 AU diameter) scales with the Atacama Large Millimeter/submillimeter Array at 340 GHz. The resolved images show that the emission from H{sup 13}CO{sup +} is only present in a ring-like structure with a radius of about 1-1.''5 (150-200 AU) whereas the CO and other high dipole moment molecules are centrally condensed toward the location of the central protostar. We propose that HCO{sup +} is destroyed by water vapor present on small scales. The origin of this water vapor is likely an accretion burst during the last 100-1000 yr increasing the luminosity of IRAS 15398-3359 by a factor of 100 above its current luminosity. Such a burst in luminosity can also explain the centrally condensed CH{sub 3}OH and extended warm carbon-chain chemistry observed in this source and furthermore be reflected in the relative faintness of its compact continuum emission compared to other protostars.

  3. Thermodynamic Phase Relations in the MgO-FeO-SiO2 System in the Lower Mantle

    Science.gov (United States)

    Wolf, A. S.; Caracas, R.; Asimow, P. D.

    2008-12-01

    The perovskite (Pv) to post-perovskite (PPv) phase transition at pressures near the Earth's core-mantle boundary (CMB) is currently the favored candidate for explaining most, if not all, of the peculiarities of the D" layer (~200 km region above core) [1, 2]. Additionally, the pressure- and temperature-dependence of this phase boundary in the Earth provides the possibility of an important new thermo-barometer at the bottom of the convecting mantle. The post-perovskite phase boundary in pure MgSiO3 is fairly well known, but the experimental and calculated results on the partitioning of Fe among the stable coexisting phases and its influence on the transition pressure are currently contradictory [3, 4, 5, 6]. Using density functional theory (DFT), we investigate the MgO-FeO-SiO2 ternary system over the temperatures and pressures relevant to the core-mantle boundary. We use DFT to calculate the energies of the relevant stable phases (Pv, PPv, (Mg,Fe)O magnesio-wustite, and SiO2 stishovite) for a range of Fe compositions along the Mg-Fe binary. These results are fit with a Vinet equation of state, allowing us to parameterize the effect of both pressure and Fe composition. The effect of temperature is modeled using a Grüneisen thermal correction, where the vibrational heat capacities are determined using DFT perturbation calculations and the quasi-harmonic approximation. These pressure-, temperature-, and composition-dependent equations of state are then used to explore the predicted phase relations. The results of this investigation are a complete thermodynamic description of the stable phases for this simplified chemistry and a theoretical prediction for iron partioning in the lower mantle. In particular, we find that there may be a coincidence point (azeotrope) on the Pv-PPv phase loop, across which the sense of Fe-partitioning changes sign, as well as significant immiscibility between Mg-rich and Fe-rich post-perovskite. These findings help explain many of the

  4. Uncertainty Assessment of Interpolation-Based Three Phase Relative Permeability Models

    Science.gov (United States)

    Ranaee, Ehsan; Giovanni, Porta; Monica, Riva; Alberto, Guadagnini

    2013-04-01

    A major element affecting uncertainty associated with prediction of three-phase flow in reservoirs is the parameterization of relative permeability. The latter are typically obtained through interpolation of two phase relative permeability data because of intrinsic difficulties related to direct measurements. Here, we discuss and analyze the saturation history dependency of water, oil and gas relative permeabilities and distinguish key features of three- and two- phase flow configurations. We start by investigating the advantages and limitations of several methodologies available in the literature and widely adopted in three-phase flow simulation. This analysis is performed by comparing model outcomes against experimental data published in the literature. The results provided by considering Corey-type equations as input to the aforesaid models is compared against the use of linear interpolation of two-phase measurements from oil-water and oil-gas environment. Our results show that available models typically fail to reproduce the set of experimental results ever the full range of saturations. This analysis suggests that not only saturation history but also wettability, residual oil and trapping behavior of oil during drainage and imbibition are key elements distinguishing between the physics of two- and three-phase settings. These effects should be taken in account to predict three-phase relative permeability. We then propose an alternative formulation to compute oil relative permability under three-phase conditions. Our model takes into account (i) the dependence of three-phase oil relative permeability on the saturation path, and (ii) the effect of wettability observed for three-phase systems. The model is based on a sigmoid-type interpolation of the oil relative permeability-saturation data in a two-phase oil-water system. Three-phase oil relative permeability is then computed through an additional interpolation between the oil-water effective sigmoid curve and

  5. Gas Hydrate Stability and Sampling: The Future as Related to the Phase Diagram

    OpenAIRE

    E. Dendy Sloan; Amadeu K. Sum; Koh, Carolyn A.

    2010-01-01

    The phase diagram for methane + water is explained, in relation to hydrate applications, such as in flow assurance and in nature. For natural applications, the phase diagram determines the regions for hydrate formation for two- and three-phase conditions. Impacts are presented for sample preparation and recovery. We discuss an international study for “Round Robin†hydrate sample preparation protocols and testing.

  6. Gas Hydrate Stability and Sampling: The Future as Related to the Phase Diagram

    Directory of Open Access Journals (Sweden)

    E. Dendy Sloan

    2010-12-01

    Full Text Available The phase diagram for methane + water is explained, in relation to hydrate applications, such as in flow assurance and in nature. For natural applications, the phase diagram determines the regions for hydrate formation for two- and three-phase conditions. Impacts are presented for sample preparation and recovery. We discuss an international study for “Round Robin” hydrate sample preparation protocols and testing.

  7. Gas hydrate stability and sampling: the future as related to the phase diagram

    Energy Technology Data Exchange (ETDEWEB)

    Sloan, E. D.; Koh, C. A.; Sum, A. K. [Center for Hydrate Research, Chemical Engineering Department, Colorado School of Mines, 1500 Illinois Street, Golden, CO 80401 (United States)

    2010-12-15

    The phase diagram for methane plus water is explained, in relation to hydrate applications, such as in flow assurance and in nature. For natural applications, the phase diagram determines the regions for hydrate formation for two- and three-phase conditions. Impacts are presented for sample preparation and recovery. We discuss an international study for 'Round Robin' hydrate sample preparation protocols and testing. (authors)

  8. Task-and phase-related changes in cortico-muscular coherence

    DEFF Research Database (Denmark)

    Masakado, Yoshihisa; Nielsen, Jens Bo

    2008-01-01

    -level tonic dorsiflexion. In all subjects coherence disappeared during the ramp phase for both isometric and quasi-isotonic contraction. Coherence at other frequencies was also not observed in any of the subjects during the ramp phase. During the hold phase at the stronger level of contraction coherence...... reappeared quickly and had the same size as at the low level of contraction. However, a significantly larger level of coherence was found during quasi-isotonic than during the isometric contraction. This demonstrates that cortico-muscular coherence in the 15-35 Hz frequency band is phase- and task......-related. The decrease in 15-35 Hz coherence during the ramp phase may be related to event-related desynchronization of EEG activity. The larger level of coherence during quasi-isotonic contraction may reflect a higher demand of precise control of the joint position. It may also reflect a greater need for...

  9. Describing the direct and indirect radiative effects of atmospheric aerosols over Europe by using coupled meteorology-chemistry simulations: a contribution from the AQMEII-Phase II exercise

    Science.gov (United States)

    Jimenez-Guerrero, Pedro; Balzarini, Alessandra; Baró, Rocío; Curci, Gabriele; Forkel, Renate; Hirtl, Marcus; Honzak, Luka; Langer, Matthias; Pérez, Juan L.; Pirovano, Guido; San José, Roberto; Tuccella, Paolo; Werhahn, Johannes; Zabkar, Rahela

    2014-05-01

    The study of the response of the aerosol levels in the atmosphere to a changing climate and how this affects the radiative budget of the Earth (direct, semi-direct and indirect effects) is an essential topic to build confidence on climate science, since these feedbacks involve the largest uncertainties nowadays. Air quality-climate interactions (AQCI) are, therefore, a key, but uncertain contributor to the anthropogenic forcing that remains poorly understood. To build confidence in the AQCI studies, regional-scale integrated meteorology-atmospheric chemistry models (i.e., models with on-line chemistry) that include detailed treatment of aerosol life cycle and aerosol impacts on radiation (direct effects) and clouds (indirect effects) are in demand. In this context, the main objective of this contribution is the study and definition of the uncertainties in the climate-chemistry-aerosol-cloud-radiation system associated to the direct radiative forcing and the indirect effect caused by aerosols over Europe, using an ensemble of fully-coupled meteorology-chemistry model simulations with the WRF-Chem model run under the umbrella of AQMEII-Phase 2 international initiative. Simulations were performed for Europe for the entire year 2010. According to the common simulation strategy, the year was simulated as a sequence of 2-day time slices. For better comparability, the seven groups applied the same grid spacing of 23 km and shared common processing of initial and boundary conditions as well as anthropogenic and fire emissions. With exception of a simulation with different cloud microphysics, identical physics options were chosen while the chemistry options were varied. Two model set-ups will be considered here: one sub-ensemble of simulations not taking into account any aerosol feedbacks (the baseline case) and another sub-ensemble of simulations which differs from the former by the inclusion of aerosol-radiation feedback. The existing differences for meteorological

  10. High-pressure phase relations of CsD2PO4

    International Nuclear Information System (INIS)

    The high-pressure phase diagram of CsD2PO4 to 4.5 GPa and temperatures between 0 and 4700C is reported. Comparisons are made with CsH2PO4 and correlated with the isotope effect on the high-temperature high-pressure phase relations of KH2PO4

  11. 77 FR 73586 - Further Inquiry Into Issues Related to Mobility Fund Phase II

    Science.gov (United States)

    2012-12-11

    ... COMMISSION 47 CFR Part 1 Further Inquiry Into Issues Related to Mobility Fund Phase II AGENCY: Federal... (202) 418-0660. SUPPLEMENTARY INFORMATION: This is a summary of the Commission's Further Inquiry Into... process, the Commission should modify the performance metrics applicable to Phase II support...

  12. 76 FR 55947 - Industrial Relations Promotion Project, Phase II in Vietnam

    Science.gov (United States)

    2011-09-09

    ... of the Secretary Industrial Relations Promotion Project, Phase II in Vietnam AGENCY: Bureau of... implementing a program to strengthen compliance with international labor standards in Vietnam, focusing... has the recognized authority and capacity to fulfill the intent of the IRRP Phase II in Vietnam....

  13. 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.

  14. The effect of saturation path on three-phase relative permeability

    Science.gov (United States)

    Kianinejad, Amir; Chen, Xiongyu; DiCarlo, David A.

    2015-11-01

    Simulation and fluid flow prediction of many petroleum-enhanced oil recovery methods as well as environmental processes such as carbon dioxide (CO2) geological storage or underground water resources remediation requires accurate modeling and determination of relative permeability under different saturation histories. Based on this critical need, several three-phase relative permeability models were developed to predict relative permeability; however, for practical purposes most of them require a variety of parameters introducing undesired complexity to the models. In this work, we attempt to find out if there is a simpler way to express this functionality. To do so, we experimentally measure three-phase, water/oil/gas, relative permeability in a 1 m long water-wet sand pack, under several saturation flow paths to cover the entire three-phase saturation space. We obtain the in situ saturations along the sand pack using a CT scanner and then determine the relative permeabilities of liquid phases directly from the measured in situ saturations using an unsteady state method. The measured data show that at a specific saturation, the oil relative permeability varies significantly (up to two orders of magnitude), depending on the path through saturation space. The three-phase relative permeability data are modeled using standard relative permeability models, Corey-type, and Saturation Weighted Interpolation (SWI). Our measured data suggest that three-phase oil relative permeability in water-wet media is only a function of its own saturation if the residual oil saturation is treated as a function of two saturations. We determine that residual saturation is the key parameter in modeling three-phase relative permeability (effect of saturation history).

  15. Soil bacterial and archaeal communities of the Stringer Creek Watershed in relation to soil moisture, chemistry, and gas fluxes

    Science.gov (United States)

    Jones, R. T.; Du, Z.; Riveros-Iregui, D.; Dore, J. E.; Emanuel, R. E.; McGlynn, B. L.; McDermott, T.; Li, X.

    2013-12-01

    The Stringer Creek watershed within the Tenderfoot Creek Experimental Forest (Montana) is a highly instrumented watershed with long-term hydrologic and gas flux measurements, and is an ideal study system to incorporate microbiological characterizations into landscape scale hydrological and biogeochemical studies. As a first attempt to determine how hydrological processes, soil chemistry, and gas fluxes are correlated with bacterial and archaeal lineages in soil, we collected soil samples across the watershed (July 9 - 11, 2012) and used barcoded high-throughput DNA sequencing to characterize the bacterial and archaeal communities. Soils were collected adjacent to gas well sites at 5 cm, 20 cm, and 50 cm depths, corresponding to the depths of the wells. Gas measurements included CO2, CH4, O2, and N2O; soil measurements included water content, % carbon, and % nitrogen. We analyzed 775,000 16S rRNA gene sequences from 28 soil samples. Relative abundances of certain microbial lineages or groups (e.g. methanotrophs, methanogens, Acidobacteria, Bacteroidetes, Firmicutes, Proteobacteria, etc.) varied significantly with CO2, CH4, and O2 concentrations. Furthermore, beta-diversity analyses showed that microbial community composition was significantly governed by water content, % nitrogen, and % carbon; community composition also significantly varied with CO2, CH4, and O2 concentrations. Together, our results suggest that soil environmental factors such as water content, % carbon, and % nitrogen affect microbial community composition, and that microbial community composition correlates with CO2, O2, and CH4 concentrations. Future work will focus on characterizing microbial communities across the entire summer season as soil conditions drastically change from fully saturated to very dry.

  16. Relative Phase Dependence of Double Ionization in a Synthesized Laser Pulse

    International Nuclear Information System (INIS)

    We investigate the double ionization process of a three-dimensional model atom interacting with a synthesized laser pulse and explore the mechanism of non-sequential double ionization varying with the value of relative phase. The result shows that the recollision probability decreases when the value of the relative phase increases. The momentum spectra of electrons in the sequential ionization region are also illustrated. (atomic and molecular physics)

  17. Relative Phase Dependence of Double Ionization in a Synthesized Laser Pulse

    Institute of Scientific and Technical Information of China (English)

    WANG Yuan-Sheng; XIA Chang-Long; GUO Jing; LIU Xue-Shen

    2011-01-01

    @@ We investigate the double ionization process of a three-dimensional model atom interacting with a synthesized laser pulse and explore the mechanism of non-sequential double ionization varying with the value of relative phase.The result shows that the recollision probability decreases when the value of the relative phase increases.The momentum spectra of electrons in the sequential ionization region are also illustrated.

  18. Electroweak phase transition and some related phenomena – a brief review

    Indian Academy of Sciences (India)

    BUDDHADEB GHOSH

    2016-09-01

    In this article, we give a bird’s eye view of the research on electroweak phase transition and some related phenomena, viz., cosmological baryogenesis, electroweak bubble dynamics and generation of gravitationalwaves. Our presentation revolves around the observation that a strong first-order electroweak phase transition cannot be obtained in the Standard Model for experimentally favoured Higgs mass and hence the cosmologicalevents associated with this kind of phase transition cannot be explained in this model. However, this phase transition can be achieved in a number of beyond Standard Models. As a prototype case, we consider the littlest Higgs model with T parity and show the results of some calculations within this model.

  19. Mathematical problems for chemistry students

    CERN Document Server

    Pota, Gyorgy

    2006-01-01

    Mathematical Problems for Chemistry Students has been compiled and written (a) to help chemistry students in their mathematical studies by providing them with mathematical problems really occurring in chemistry (b) to help practising chemists to activate their applied mathematical skills and (c) to introduce students and specialists of the chemistry-related fields (physicists, mathematicians, biologists, etc.) into the world of the chemical applications. Some problems of the collection are mathematical reformulations of those in the standard textbooks of chemistry, other

  20. Comparative analysis of meteorological performance of coupled chemistry-meteorology models in the context of AQMEII phase 2

    Science.gov (United States)

    Air pollution simulations critically depend on the quality of the underlying meteorology. In phase 2 of the Air Quality Model Evaluation International Initiative (AQMEII-2), thirteen modeling groups from Europe and four groups from North America operating eight different regional...

  1. Complex chemistry

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-06-15

    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.

  2. Complex chemistry

    International Nuclear Information System (INIS)

    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.

  3. A new method for the experimental determination of three-phase relative permeabilities

    International Nuclear Information System (INIS)

    Petroleum reservoirs under primary, secondary or tertiary recovery processes usually experience simultaneous flow of three fluids phases (oil, water and gas). Reports on some mathematical models for calculating three-phase relative permeability are available in the Literature. Nevertheless, many of these models were designed based on certain experimental conditions and reservoir rocks and fluids. Therefore, special care has to be taken when applying them to specific reservoirs. At the laboratory level, three-phase relative permeability can be calculated using experimental unsteady-state or steady state methodologies. This paper proposes an unsteady-state methodology to evaluate three-phase relative permeability using the equipment available at the petrophysical analysis Laboratory of the Instituto Colombiano del Petroleo (ICP) of Ecopetrol S.A. Improvements to the equipment were effected in order to achieve accuracy in the unsteady-state measurement of three-phase relative permeability. The target of improvements was directed toward to the attainment of two objectives:1) the modification of the equipment to obtain more reliable experimental data and 2) the appropriate interpretation of the data obtained. Special attention was given to the differential pressure and uncertainty measurement in the determination of fluid saturation in the rock samples. Three experiments for three-phase relative permeability were conducted using a sample A and reservoir rock from the Colombian Foothills. Fluid tests included the utilization of synthetic brine, mineral oil, reservoir crude oil and nitrogen. Two runs were conducted at the laboratory conditions while one run was conducted at reservoir conditions. Experimental results of these tests were compared using 16 mathematical models of three-phase relative permeability. For the three-phase relative permeability to oil, the best correlations between experimental data and tests using Blunt, Hustad Hasen, and Baker's models were

  4. 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...

  5. 晶体化学新领域——高压相变晶体化学%New Special Field of Crystal Chemistry: High-Pressure Phase Transition Crystal Chemistry

    Institute of Scientific and Technical Information of China (English)

    施倪承; 李国武; 马喆生; 熊明

    2011-01-01

    用X射线衍射的方法衡量原子及离子的尺寸并测定其晶体结构是人类进入微观世界最为关键的一步.在通常的温度和压力下各种原子及离子的结合方式及排布规则已在晶体化学中得到详尽的阐述.笔者着重探讨了在高压下离子化合物及矿物的晶体化学特点.在高压下随着压力的增加,氧化物及硅酸盐中阳离子会发生从低配位数多面体向高配位数的多面体的迁移.这种迁移是由于阴阳离子半径比值改变所致.计算了不同的SiO2多形中氧和硅的离子半径,表明氧离子半径随压力增加而不断缩小,硅离子半径却随着压力的增加及相变的发生而逐渐增大,这种现象可能是由于离子化合物向金属相转变的结果.%The method which use X ray diffraction to measure the size of atom and ion and determine crystal structure is most important step for mankind get into microscopic view world. At usual temperature and pressure, the connection pattern and the arrangement rule of various atom and ion have already elaborated in the crystal chemistry in detail. In this paper, the study on the crystal chemistry characteristics of ionic compounds and minerals was emphasized under high pressure. Under high pressure when the pressure increases, the cations of silicon in oxide or silicate minerals occurred migration from low coordination number polyhedra to high coordination number polyhedra. This migration is due to the change with radius ratio of cations to anions. Under high pressure the ionic radii of oxygen and silicon have been calculated for different SiO2 polymorphs. It is indicated that the ionic radius of oxygen is decreasing gradually with the increase of pressure, but the cation radius of silicon is increasing with the increase of pressure and the occurrence of phase transitions. This kind of phenomenon may be due to the transition from ionic compounds to metallic phases under high pressure.

  6. Combinatorial Solid-Phase Synthesis of Balanol Analogues

    DEFF Research Database (Denmark)

    Nielsen, John; Lyngsø, Lars Ole

    1996-01-01

    The natural product balanol has served as a template for the design and synthesis of a combinatorial library using solid-phase chemistry. Using a retrosynthetic analysis, the structural analogues have been assembled from three relatively accessible building blocks. The solid-phase chemistry inclu...

  7. Mathematical Thinking in Chemistry

    OpenAIRE

    José L. Villaveces; Guillermo Restrepo

    2012-01-01

    Mathematical chemistry is often thought to be a 20th-century subdiscipline of chemistry, but in this paper we discuss several early chemical ideas and some landmarks of chemistry as instances of the mathematical way of thinking; many of them before 1900. By the mathematical way of thinking, we follow Weyl's description of it in terms of functional thinking, i.e. setting up variables, symbolizing them, and seeking for functions relating them. The cases we discuss are Plato's triangles, Geoffro...

  8. Identification and Characterization of Chemistry of Different Radicals in Mainstream Gas- phase Cigarette Smoke by ESI-MS method

    CERN Document Server

    Nejad, Maryam Abili

    2010-01-01

    We have investigated some of the free radicals in cigarette smoke. Free radicals in the gas phase, mainstream cigarette smoke have been trapped directly by using a nitroxide probe, 3- amino- 2, 2, 5, 5- tetramethyl-1- pyrrolidinyloxy (3AP) which is supported on a solid phase, derivatized by fluorescamine, and analyzed by electrospray ionization mass spectrometry (EI- MS). We have identified some specific radicals in cigarette smoke mainstream gas phase derived from nicotine, isoprene, and glucose radicals which may be produced by reactions of OH radical through H-abstraction or addition reactions. Nicotine may undergo both OH radical addition and abstraction. However nicotine shows more tendencies to react with hydrogen abstraction from methyl group on nicotine. The addition reaction of OH radical with nicotine may happen on double bond of 6 member ring of nicotine. Isoprene and glucose react with OH radical by addition and abstraction reaction, respectively. In order to confirm the results obtained for the i...

  9. The redox chemistry of neptunium in γ-irradiated aqueous nitric acid in the presence of an organic phase

    International Nuclear Information System (INIS)

    The radiolytic changes in oxidation state for solutions of initially Np(V) and/or Np(VI) were investigated by gamma-irradiation in conjunction with UV/Vis spectroscopy of the aqueous phase. Samples were irradiated in varying concentrations of nitric acid, and with or without the presence of 30 % TBP in dodecane. At short irradiation times Np(V) was oxidized to Np(VI), even in the presence of the organic phase. Upon the radiolytic production of sufficient amounts of nitrous acid, reduction of Np(VI) to Np(V) occurred in both phases. This was accompanied by stripping of the previously extracted Np(VI). Nitric acid concentrations of 6 M mitigated this reduction. (author)

  10. Age-hardening and related phase transformation in an experimental Ag-Cu-Pd-Au alloy

    International Nuclear Information System (INIS)

    The age-hardening behaviour, phase transformation and related microstructural changes of an experimental Ag-Cu-Pd-Au alloy were examined by means of hardness test, X-ray diffraction (XRD), scanning electron microscopic (SEM) observations and electron probe microanalysis (EPMA). The specimen alloy showed apparent age-hardenability at the aging temperatures of 350 deg. C and 400 deg. C. By aging the solution-treated specimen at 400 deg. C, two phases of the Ag-rich α1 phase and the Pd-containing Cu-rich α2 phase were transformed into four phases of the Ag-rich α1' phase, the Cu-rich α2' phase, the CsCl-type CuPd phase and the AuCu(I) ordered phase. Microstructure of the solution-treated specimen consisted of the Ag-rich α1 matrix, Cu-rich α2 particle-like structures of various sizes and the lamellar structure of the α1 and α2 phases. When the peak hardness was obtained, the very fine lamellar structure consisting of the Ag-rich α1' and Cu-rich α2' phases was newly formed in the matrix. By further aging, the very fine lamellar structure grew and coarsened apparently, and the matrix was covered with the coarsened lamellar structure. The hardness increase was considered to be caused mainly by the diffusion and precipitation of Cu from the Ag-rich α1 matrix, and the hardness decrease in the latter stage of age-hardening process was caused by the coarsening of the very fine lamellar structure. The CsCl-type CuPd phase and the AuCu(I) ordered phase did not contribute to the hardness increase

  11. 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.;

    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 (Batstone et al., 2012). Indeed, future modelling needs, such as a plant-wide phosphorus (P) description...... presented and interfaced with industry standard models. The module involves extensive consideration of non-ideality by 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...... 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 be...

  12. The Chemistry and Pharmacology of Anatoxin-a and Related Homotropanes with respect to Nicotinic Acetylcholine Receptors

    Directory of Open Access Journals (Sweden)

    Timothy Gallagher

    2006-04-01

    Full Text Available Abstract: This chapter covers the chemistry and nicotinic pharmacology of naturally occurring homotropane alkaloids, with an emphasis of anatoxin-a. In addition to anatoxin-a, homoanatoxin and pinnamine, as well as the major classes of synthetic derivatives of anatoxin-a including UB-165, are discussed.

  13. Application of Liquid-Phase Deposition in Analytical Chemistry%液相沉积法(LPD)在分析化学中的应用

    Institute of Scientific and Technical Information of China (English)

    余琼卫; 冯钰锜

    2011-01-01

    Liquid phase deposition (LPD) technique, developed from wet chemical processing, is a new thin film-forming method to create thin oxide films from aqueous solutions. Due to the distinguishing characteristic of LPD, it has received increasing interest in recent years and been widely used in many fields, especially in the preparation of functional oxide coatings for integrated circuit, metal oxide semiconducting nanomaterials, biosensor, photocatalysis and antibacterial materials. In current review, we first briefly introduced the basic principles and characteristics of LPD and then summarized previous empirical studies for the preparation of metal oxide thin films fabricated by using LPD technique. Furthermore, the applications of LPD method in analytical chemistry, such as the preparation of separation media for chromatography and solid-phase extraction, chemical sensors and composited electrodes, are discussed in detail. At last, the future development and application of LPD in analytical chemistry is prospected.%液相沉积法(LPD)是湿化学法中发展起来的一种全新成膜方法,现已广泛应用于集成电路、金属-氧化物半导体、生物传感器、光催化及抗菌材料领域功能性薄膜的制备.本文简要介绍了液相沉积法的原理、特点及采用LPD法制备的多种金属氧化物薄膜,并详细综述了近年来液相沉积技术在分析化学领域中的应用,主要包括LPD在制备分离介质、化学传感器、复合电极等材料中的应用,并对LPD法在分析化学中的未来发展趋势进行了展望.

  14. Density Functional Computations and Mass Spectrometric Measurements. Can this Coupling Enlarge the Knowledge of Gas-Phase Chemistry?

    Science.gov (United States)

    Marino, T.; Russo, N.; Sicilia, E.; Toscano, M.; Mineva, T.

    A series of gas-phase properties of the systems has been investigated by using different exchange-correlation potentials and basis sets of increasing size in the framework of Density Functional theory with the aim to determine a strategy able to give reliable results with reasonable computational efforts.

  15. Berry phase effects in the dynamics of Dirac electrons in doubly special relativity framework

    International Nuclear Information System (INIS)

    We consider the Doubly Special Relativity (DSR) generalization of Dirac equation in an external potential in the Magueijo-Smolin base. The particles obey a modified energy-momentum dispersion relation. The semiclassical diagonalization of the Dirac Hamiltonian reveals the intrinsic Berry phase effects in the particle dynamics

  16. Global OZone Chemistry And Related trace gas Data records for the Stratosphere (GOZCARDS): methodology and sample results with a focus on HCl, H2O, and O3

    OpenAIRE

    L. Froidevaux; Anderson, J.; Wang, H.-J.; Fuller, R. A.; M. J. Schwartz; Santee, M. L.; Livesey, N.J.; Pumphrey, H. C.; Bernath, P. F.; Russell, J. M.; M. P. McCormick

    2015-01-01

    We describe the publicly available data from the Global OZone Chemistry And Related trace gas Data records for the Stratosphere (GOZCARDS) project and provide some results, with a focus on hydrogen chloride (HCl), water vapor (H2O), and ozone (O3). This data set is a global long-term stratospheric Earth system data record, consisting of monthly zonal mean time series starting as early as 1979. The data records are based on high-quality measurements from several NASA satellite i...

  17. Teacher Didactic Content Knowledge and its relation with the utilization of practical activities in chemistry classes: A study with expert teachers of the Angolan educational system

    OpenAIRE

    Laurinda Baca; Marcos Onofre; Fátima Paixão

    2014-01-01

    This study was developed within the Angolan educational system, with chemistry expert teachers who teach the 7th grade (12 years old). Aiming to characterize the didactic content knowledge and relate it with the quality of teaching and with the development of practical activities that ensure the active participation of students in the construction of knowledge, we observed and analyzed the classes of a group of expert teachers, specifically in the content of chemical reactions and chemical...

  18. Period-Luminosity Relations for Cepheid Variables: From Mid-Infrared to Multi-Phase

    CERN Document Server

    Ngeow, Chow-Choong; Bellinger, Earl P; Marconi, Marcella; Musella, Ilaria; Cignoni, Michele; Lin, Ya-Hong

    2012-01-01

    This paper discusses two aspects of current research on the Cepheid period-luminosity (P-L) relation: the derivation of mid-infrared (MIR) P-L relations and the investigation of multi-phase P-L relations. The MIR P-L relations for Cepheids are important in the James Webb Space Telescope era for the distance scale issue, as the relations have potential to derive the Hubble constant within ~ 2% accuracy - a critical constraint in precision cosmology. Consequently, we have derived the MIR P-L relations for Cepheids in the Large and Small Magellanic Clouds, using archival data from Spitzer Space Telescope. We also compared currently empirical P-L relations for Cepheids in the Magellanic Clouds to the synthetic MIR P-L relations derived from pulsational models. For the study of multi-phase P-L relations, we present convincing evidence that the Cepheid P-L relations in the Magellanic Clouds are highly dynamic quantities that vary significantly when considered as a function of pulsational phase. We found that there ...

  19. A model of the gas-phase chemistry of boron nitride CVD from BCl3 and NH3

    International Nuclear Information System (INIS)

    The kinetics of gas-phase reactions occurring during the CVD of boron nitride (BN) from BCl3 and NH3 are investigated using an elementary reaction mechanism whose rate constants were obtained from theoretical predictions and literature sources. Plug-flow calculations using this mechanism predict that unimolecular decomposition of BCl3 is not significant under typical CVD conditions, but that some NH3 decomposition may occur, especially for deposition occurring at atmospheric pressure. Reaction of BCl3 with NH3 is rapid under CVD conditions and yields species containing both boron and nitrogen. One of these compounds, Cl2BNH2, is predicted to be a key gas-phase precursor to BN

  20. Gas-phase chemistry during the conversion of cyclohexane to carbon: Flow reactor studies at low and intermediate pressure

    Energy Technology Data Exchange (ETDEWEB)

    Osterheld, T.H.; Allendorf, M.D.; Larson, R.

    1995-07-01

    The gas-phase branching during the conversion of cyclohexane to solid carbon has been measured in a high-temperature-flow reactor. The experiments show that cyclohexane decomposes into a broad distribution of hydrocarbons that further decompose into the more kinetically stable products hydrogen, methane, acetylene, ethylene, benzene, and PAH. At 1363 K, the evolution to these species occurs quickly. We also observe the buildup of significant amounts of aromatic molecules at later stages in the decomposition, with as much as 15% of the total carbon in PAH and 25% in benzene. At later stages, the gas-phase molecules react slowly, even though the system is not at equilibrium, because of their kinetic stability and the smaller radical pool. The decomposition does not appear to depend sensitively on pressure in the regime of 25 to 250 torr. Thus, to a first approximation, these results can be extrapolated to atmospheric pressure.

  1. Implications of three phase bone scintigraphy for the diagnosis of bisphosphonate related osteonecrosis of the jaw

    International Nuclear Information System (INIS)

    Bisphosphonate (BP) related osteonecrosis of the jaw (BRONJ) is a well known serious complication of BP treatment. This study was undertaken to evaluate the diagnostic usefulness of three phase bone scintigraphy in patients with BRONJ. Forty one patients (48 lesions)with clinically proven BRONJ (2 males, 39 females, age 74.3±6.7 years)under went Tc 99m HDP bone scintigraphy. Visual interpretation and semiquantitative analysis of uptakes using lesion to contralateral uptake ratios during the blood pool phase (BUR)and during the osseous phase (OUR)were performed, and relations were sought between these and various clinical parameters. Three phase bone scintigraphy showed increased perfusion and blood pooling in 21 (63.6%)and 27 (81.8%)of 33 lesions, respectively. The osseous phase was positive for 45 (93.8%)of the 48 lesions. Of the four inflammatory clinical parameters of BRONJ [pus discharge, pain, swelling, and erythrocyte sedimentation rate (ESR)], patients with three or more parameters had more positive findings in vascular and blood pool phase images (p=0.033, p=0.027). By semiquantitative analysis, patients with a positive ESR had statistically higher BUR and OUR (both p<0.001). Higher stage BRONJ lesions had higher OUR than lower stage lesions (p=0.003). In addition, bone scintigraphy revealed three clinically covert BRONJ lesions without bone exposure, and four patients were up staged based on bone scintigraphy. Bone scintigraphy provides a relatively sensitive means of detecting BRONJ, so it was helpful for accurate BRONJ staging. Furthermore, Increased uptakes in vascular and blood pool phases of three phase bone scintigraphy were related to the inflammatory activity of BRONJ

  2. Variability for phase transition among races of maize and related wild forms

    OpenAIRE

    Revilla Temiño, Pedro; Velasco Pazos, Pablo; Malvar Pintos, Rosa Ana; Soengas Fernández, María del Pilar; Ordás Pérez, Amando

    2000-01-01

    Variability for the timing of vegetative phase change has been related to disease and pest resistance and to agronomic performance and could be a useful indirect selection criterion. Our objective was to determine the variability for phase transition among populations from historical races of maize (Zea mays L.) and wild species and subspecies of Zea. Principal component and cluster analysis were made on morphological and anatomical traits of maize races and populations and the wild species a...

  3. Preparation of 183,184Re samples for modelling a rapid gas phase chemistry of Nielsbohrium (Ns), element 107

    International Nuclear Information System (INIS)

    Chemical gas phase reactions of the heavier group 7 elements in the system O2/H2O are presumably best suited for a separation of Nielsbohrium from the lighter transactinides. We expect a higher reaction velocity using the more reactive gas system O3/H2O2. For the experimental verification of this idea we prepared 183Re/184Re samples for thermochromatography experiments with both gas systems. (author) 8 refs

  4. Asymmetric current-phase relation due to spin-orbit interaction in semiconductor nanowire Josephson junction

    Energy Technology Data Exchange (ETDEWEB)

    Yokoyama, Tomohiro; Eto, Mikio [Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan); Nazarov, Yuli V. [Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft, The Netherlands (Netherlands)

    2013-12-04

    We theoretically study the current-phase relation in semiconductor nanowire Josephson junction in the presence of spin-orbit interaction. In the nanowire, the impurity scattering with strong SO interaction is taken into account using the random matrix theory. In the absence of magnetic field, the Josephson current I and phase difference φ between the superconductors satisfy the relation of I(φ) = –I(–φ). In the presence of magnetic field along the nanowire, the interplay between the SO interaction and Zeeman effect breaks the current-phase relation of I(φ) = –I(–φ). In this case, we show that the critical current depends on the current direction, which qualitatively agrees with recent experimental findings.

  5. Secondary Physics, Chemistry, and Biology (PCB) Teachers’ Views about In-service Training Related to Curricular Change

    OpenAIRE

    Fatih Çağlayan Mercan

    2015-01-01

    In Turkey the Physics, Chemistry and Biology (PCB) curricula were renewed in 2008. However, little in-service training for teachers has been conducted to disseminate the ideas in the new curricula. The purpose of this study was to investigate PCB teachers’ views on in-service training, which may serve as the base knowledge of educational change in Turkey that can be used in further curricular development. In Istanbul 99 teachers voluntarily participated in this qualitative case study. Data we...

  6. Fuel chemistry and pellet-clad interaction related to high burnup fuel. Proceedings of the technical committee

    International Nuclear Information System (INIS)

    The purpose of the meeting was to review new developments in clad failures. Major findings regarding the causes of clad failures are presented in this publication, with the main topics being fuel chemistry and fission product behaviour, swelling and pellet-cladding mechanical interaction, cladding failure mechanism at high burnup, thermal properties and fuel behaviour in off-normal conditions. This publication contains 17 individual presentations delivered at the meeting; each of them was indexed separately

  7. Effects of relative phase on transient evolution in an open resonant ladder-type atomic system

    Institute of Scientific and Technical Information of China (English)

    Yang Yan-Ling; Liu Zhong-Bo; Wang Lei; Tong Dian-Min; Fan Xi-Jun

    2009-01-01

    In an open ladder-type resonant atomic system, variation in relative phase between probe and driving fields does not affect the transient evolution of populations, but it has remarkable effects on gain and dispersion of the probe field. No matter whether an incoherent pump is present or absent, transient and stationary gains without inversion (GWI) always can be obtained by choosing an appropriate value of the relative phase. When the incoherent pump is absent, the values of transient and stationary GWIs are much larger and the time interval required to reach the stationary value is longer than those when the incoherent pump is present. Varying the exit rate and the ratio between injection rates can obviously change the phase-dependent GWI. In addition, in the transient evolution process, the phenomenon of high dispersion (refractive index) without absorption occurs at some values of relative phase. In the corresponding closed system, the stationary GWI can be obtained by choosing an appropriate value of relative phase only when incoherent pump exists, moreover the gain is smaller than that in the open system.

  8. 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....

  9. 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

  10. On-line detection in liquid phase with PTR-MS : fundamentals and applications in chemistry and biology

    International Nuclear Information System (INIS)

    PTR-MS (proton transfer reaction mass spectrometry) is a unique and by now well-established technology for trace gas analysis. Nevertheless, it has one considerable drawback, namely that it can only detect volatile compounds in the gas phase. Although it is possible to detect many volatile organic compounds (VOCs) in liquids via headspace analysis, such analysis is not possible for trace compounds with a high Henry’s law constant (e.g. explosives, PCB's) when they are present at low concentrations. Consequently in the course of this thesis I tried to develop and to explore a new solution which we call direct aqueous injection (DAI). (author)

  11. Preparation of {sup 183,184}Re samples for modelling a rapid gas phase chemistry of Nielsbohrium (Ns), element 107

    Energy Technology Data Exchange (ETDEWEB)

    Eichler, R.; Gaeggeler, H.W.; Eichler, B.; Tuerler, A. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-09-01

    Chemical gas phase reactions of the heavier group 7 elements in the system O{sub 2}/H{sub 2}O are presumably best suited for a separation of Nielsbohrium from the lighter transactinides. We expect a higher reaction velocity using the more reactive gas system O{sub 3}/H{sub 2}O{sub 2}. For the experimental verification of this idea we prepared {sup 183}Re/{sup 184}Re samples for thermochromatography experiments with both gas systems. (author) 8 refs.

  12. STOMP Subsurface Transport Over Multiple Phases Version 1.0 Addendum: ECKEChem Equilibrium-Conservation-Kinetic Equation Chemistry and Reactive Transport

    Energy Technology Data Exchange (ETDEWEB)

    White, Mark D.; McGrail, B. Peter

    2005-12-01

    flow and transport simulator, STOMP (Subsurface Transport Over Multiple Phases). Prior to these code development activities, the STOMP simulator included sequential and scalable implementations for numerically simulating the injection of supercritical CO2 into deep saline aquifers. Additionally, the sequential implementations included operational modes that considered nonisothermal conditions and kinetic dissolution of CO2 into the saline aqueous phase. This addendum documents the advancement of these numerical simulation capabilities to include reactive transport in the STOMP simulator through the inclusion of the recently PNNL developed batch geochemistry solution module ECKEChem (Equilibrium-Conservation-Kinetic Equation Chemistry). Potential geologic reservoirs for sequestering CO2 include deep saline aquifers, hydrate-bearing formations, depleted or partially depleted natural gas and petroleum reservoirs, and coal beds. The mechanisms for sequestering carbon dioxide in geologic reservoirs include physical trapping, dissolution in the reservoir fluids, hydraulic trapping (hysteretic entrapment of nonwetting fluids), and chemical reaction. This document and the associated code development and verification work are concerned with the chemistry of injecting CO2 into geologic reservoirs. As geologic sequestration of CO2 via chemical reaction, namely precipitation reactions, are most dominate in deep saline aquifers, the principal focus of this document is the numerical simulation of CO2 injection, migration, and geochemical reaction in deep saline aquifers. The ECKEChem batch chemistry module was developed in a fashion that would allow its implementation into all operational modes of the STOMP simulator, making it a more versatile chemistry component. Additionally, this approach allows for verification of the ECKEChem module against more classical reactive transport problems involving aqueous systems.

  13. Modeling of the gas-phase chemistry in C-H-O gas mixtures for diamond chemical vapor deposition

    Science.gov (United States)

    Petherbridge, James R.; May, Paul W.; Ashfold, Michael N. R.

    2001-05-01

    The boundaries of the diamond deposition region in the C-H-O (Bachmann) atomic phase composition diagram have been reproduced successfully for 38 different C, H, and O containing gas mixtures using the CHEMKIN computer package, together with just two criteria—a minimum mole fraction of methyl radicals [CH3] and a limiting value of the [H]/[C2H2] ratio. The diamond growth/no-growth boundary coincides with the line along which the input mole fractions of C and O are equal. For every gas mixture studied, no-growth regions are found to coincide with a negligible (<10-10) mole fraction of CH3 radicals, while for gas mixtures lying within the diamond growth region the CH3 mole fraction is ˜10-7. Each no-growth→diamond growth boundary is seen to be accompanied by a 2-3 order of magnitude step in CH3 mole fraction. The boundary between diamond and nondiamond growth is less clearly defined, but can be reproduced by assuming a critical, temperature dependent [H]/[C2H2] ratio (0.2, in the case that Tgas=2000 K) that reflects the crucial role of H atoms in the etching of nondiamond phases. The analysis allows prediction of the composition process window for good quality diamond growth for all stable input gas mixtures considered in this study.

  14. Role of Fe substitution and quenching rate on the formation of various quasicrystalline and related phases

    Indian Academy of Sciences (India)

    Varsha Khare; R S Tiwari; O N Srivastava

    2001-06-01

    We have investigated Fe substituted versions of the quasicrystalline (qc) alloy corresponding to Al65Cu20(Cr, Fe)15 with special reference to the possible occurrence of various quasicrystalline and related phases. Based on the explorations of various compositions it has been found that alloy compositions Al65Cu20Cr12Fe3 and Al65Cu20Cr9Fe6 exhibit interesting structural phases and features at different quenching rates. At higher quenching rates (wheel speed ∼ 25 m/sec) all the alloys exhibit icosahedral phase. For Al65Cu20Cr12Fe3 alloy, however, both the icosahedral and even the decagonal phases get formed at higher quenching rates. At higher quenching rate, alloy having Fe 3 at% exhibits two bcc phases, bccI ( = 8.9 Å) and bccII ( = 15.45 Å). The orientation relationships between icosahedral and crystalline phases are: Mirror plane ∥[001]bcc I and [351]bcc II, 5-fold ∥ [113]bcc II and 3-fold ∥ [110]bcc II. At lower quenching rate, the alloy having Fe 6 at% exhibits orthorhombic phase ( = 23.6 Å, = 12.4 Å, = 20.1 Å). Some prominent orientation relationships of the orthorhombic phase with decagonal phase have also been reported. At lower quenching rate (∼ 10 m/sec), the alloy (Al65Cu22Cr9Fe6) shows the presence of diffuse scattering of intensities along quasiperiodic direction of the decagonal phase. For making the occurrence of the sheets of intensities intelligible, a model based on the rotation and shift of icosahedra has been put forward.

  15. Intra-field variability in microbial community associated with phase-separation-controlled hydrothermal fluid chemistry in the Mariner field, the southern Lau Basin

    Science.gov (United States)

    Takai, K.; Ishibashi, J.; Lupton, J.; Ueno, Y.; Nunoura, T.; Hirayama, H.; Horikoshi, K.; Suzuki, R.; Hamasaki, H.; Suzuki, Y.

    2006-12-01

    A newly discovered hydrothermal field called the Mariner field at the northernmost central Valu Fa Ridge (VFR) in the Lau Basin was explored and characterized by geochemical and microbiological surveys. The hydrothermal fluid (max. 365 u^C) emitting from the most vigorous vent site (Snow chimney) was boiling just beneath the seafloor at a water depth of 1908 m and two end-members of hydrothermal fluid were identified. Mineral and fluid chemistry of typical brine-rich (Snow chimney and Monk chimney) and vapor-rich (Crab Restaurant chimney) hydrothermal fluids and the host chimney structures were analyzed. Microbial community structures in three chimney structures were also investigated by culture-dependent and - independent analyses. The 16S rRNA gene clone analysis revealed that both bacterial and archaeal rRNA gene communities at the chimney surface zones were different among three chimneys. The bacterial and archaeal rRNA gene communities of the Snow chimney surface were very similar with those in the dead chimneys, suggesting concurrence of metal sulfide deposition at the inside and weathering at the surface potentially due to its large structure and size. Cultivation analysis demonstrated the significant variation in culturability of various microbial components, particularly of thermophilic H2- and/or S-oxidizing chemolithoautotrophs such as the genera Aquifex and Persephonella, among the chimney sites. The culturability of these chemolithoautotrophs might be associated with the input of gaseous energy and carbon sources like H2S, H2 and CH4 from the hydrothermal fluids, and might be affected by phase-separation- controlled fluid chemistry. In addition, inter-fields comparison of microbial community structures determined by cultivation analysis revealed novel characteristics of the microbial communities in the Mariner field of the Lau Basin among the global deep-sea hydrothermal systems.

  16. The overall elastoplastic stress-strain relations of dual-phase metals

    Science.gov (United States)

    Weng, G. J.

    T WO SIMPLE, albeit approximate, theories are developed to estimate the stress-strain relations of dual-phase metals of the inclusion-matrix type, where both phases are capable of undergoing plastic flow. The first one is based upon Hill's recognition of a weakening constraint power in a plastically deforming matrix, whereas the second one is based on Kröner's elastic constraint in the treatment of the single inclusion-matrix interaction. The inclusion-inclusion interaction at finite concentration is accounted for by the Mori-Tanaka method in both cases. Consistent with the known elastic behavior, the first theory discloses that the geometrical arrangement of the constituents has a significant influence on the overall elastoplastic response. When the harder phase takes the position of the matrix the composite is far Stiffer than that when it takes the position of inclusions. The strong elastic constraint associated with the second theory tends to provide an upper-bound type of estimate regardless of whether the matrix is the harder phase or the softer, and, therefore, it is suggested that this theory be used only for the class of composites whose matrix is the harder phase. Both theories are finally applied to predict the stress-strain relations of dual-phase stainless steels, and the results are found to be in satisfactory agreement with the test data.

  17. Adapting relative phase of bimanual isometric force coordination through scaling visual information intermittency.

    Science.gov (United States)

    Lafe, Charley W; Pacheco, Matheus M; Newell, Karl M

    2016-06-01

    Visual information plays an adaptive role in the relation between bimanual force coupling and error corrective processes of isometric force control. In the present study, the evolving distribution of the relative phase properties of bimanual isometric force coupling was examined by scaling within a trial the temporal feedback rate of visual intermittency (short to long presentation intervals and vice versa). The force error (RMSE) was reduced, and time-dependent irregularity (SampEn) of the force output was increased with greater amounts of visual information (shorter intermittency). Multi-stable coordination patterns of bimanual isometric force control were differentially shifted toward and away from the intrinsic dynamics by the changing the intermittency of visual information. The distribution of Hilbert transformed relative phase values showed progressively a predominantly anti-phase mode under less intermittent visual information to predominantly an in-phase mode with limited (almost no) visual information. Correlation between the hands showed a continuous reduction, rather than abrupt "transition," with increase in visual information, although no mean negative correlation was realized, despite the tendency towards an anti-phase distribution. Lastly, changes in both the performance outcome and bimanual isometric force coordination occurred at visual feedback rates faster than the minimal visual processing times established from single limb movement and isometric force protocols. PMID:27017544

  18. Single-mode squeezed vacuum states as approximate Schroedinger phase cats: relation to SU(1, 1) phase operators

    International Nuclear Information System (INIS)

    We study the eigenstates of the square of the phase operator for a single-mode field, and show that they are given as superpositions of macroscopically distinguishable phase states, which we call Schroedinger phase cats, the phase states being eigenstates of the phase operator. Those solutions that are also eigenstates of the parity operator with even parity are shown to be very similar to the squeezed vacuum states over a range of relevant parameters. Thus, it is possible to consider some squeezed vacuum states as approximate Schroedinger phase-cat states. We discuss the connections to the phase states of the SU(1, 1) phase operators for various realizations and representations

  19. Progress report 1981-1982. Reactor Chemistry Department

    International Nuclear Information System (INIS)

    Review of the activities performed by the Reactor Chemistry Department of the National Atomic Energy Commission of Argentina during 1981-1982. This Department provides services and assistance in all matters related to water chemistry and nuclear reactors chemistry, in all their phases: design, construction, commissioning and decommissioning. During this period, the following tasks were performed: study of the metallic oxide-water interphases; determination of the goethite and magnetite surficial charges; synthesis of the monodispersed nickel ferrites; study of the iron oxides dissolution mechanism in presence of different complexing agents; chemical decontamination of structural metals; thermodynamics of the water-nitrogen system; physico-chemical studies of aqueous solutions at high temperatures; hydrothermal decomposition of ionic exchange resines and study of the equilibria of the anionic exchange for the chemistry of pressurized reactor's primary loops. The appendix includes information on the Reactor Chemistry Department staff, its publications, services, seminars, courses and conferences performed during 1981-1982. (R.J.S.)

  20. The atmospheric circulation of a nine-hot Jupiter sample: Probing circulation and chemistry over a wide phase space

    CERN Document Server

    Kataria, Tiffany; Lewis, Nikole K; Visscher, Channon; Showman, Adam P; Fortney, Jonathan J; Marley, Mark S

    2016-01-01

    We present results from an atmospheric circulation study of nine hot Jupiters that comprise a large transmission spectral survey using the Hubble and Spitzer Space Telescopes. These observations exhibit a range of spectral behavior over optical and infrared wavelengths which suggest diverse cloud and haze properties in their atmospheres. By utilizing the specific system parameters for each planet, we naturally probe a wide phase space in planet radius, gravity, orbital period, and equilibrium temperature. First, we show that our model "grid" recovers trends shown in traditional parametric studies of hot Jupiters, particularly equatorial superrotation and increased day-night temperature contrast with increasing equilibrium temperature. We show how spatial temperature variations, particularly between the dayside and nightside and west and east terminators, can vary by hundreds of K, which could imply large variations in Na, K, CO and CH4 abundances in those regions. These chemical variations can be large enough...

  1. Solar forced Dansgaard-Oeschger events and their phase relation with solar proxies

    CERN Document Server

    Braun, H; Chialvo, D R

    2008-01-01

    North Atlantic climate during glacial times was characterized by large-amplitude switchings, the Dansgaard-Oeschger (DO) events, with an apparent tendency to recur preferably in multiples of about 1470 years. Recent work interpreted these intervals as resulting from a subharmonic response of a highly nonlinear system to quasi-periodic solar forcing plus noise. This hypothesis was challenged as inconsistent with the observed variability in the phase relation between proxies of solar activity and Greenland climate. Here we reject the claim of inconsistency by showing that this phase variability is a robust, generic feature of the nonlinear dynamics of DO events, as described by a model. This variability is expected from the fact that the events are threshold crossing events, resulting from a cooperative process between the periodic forcing and the noise. This process produces a fluctuating phase relation with the periodic forcing, consistent with proxies of solar activity and Greenland climate.

  2. Hydrothermal Phase Relations Among Uranyl Minerals at the Nopal I Analog Site

    International Nuclear Information System (INIS)

    Uranyl mineral paragenesis at Nopal I is an analog of spent fuel alteration at Yucca Mountain. Petrographic studies suggest a variety of possible hydrothermal conditions for uranium mineralization at Nopal I. Calculated equilibrium phase relations among uranyl minerals show uranophane stability over a broad range of realistic conditions and indicate that uranyl mineral variety reflects persistent chemical potential heterogeneity. (author)

  3. On the relation between the geometric phase and the Schwinger term

    International Nuclear Information System (INIS)

    In second quantization an m-particle and n-antiparticle state picks up the sum of geometric phases for each individual mode after parallel transport along a closed curve in parameter space. The transport of the vacuum implies in addition the occurrence of a Schwinger term. Depending on the transformation considered various relations between the two types of obstructions result. 6 refs. (Authors)

  4. Geometric Phases for Photons in an Optical Fibre and Some Related Predictions

    Institute of Scientific and Technical Information of China (English)

    高孝纯

    2002-01-01

    We propose a quantum electrodynamic model for the description of the time evolution of the quantum states of the photons in an optical fibre. By means of this model, we are able to make three interesting predicticons related to the geometric phases for photons.

  5. Luminosity-peak energy relation in the decay phases of gamma-ray burst pulses

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Using time-resolved spectral data for a sample of 30 pulses in 27 bright GRBs detected with CGRO/BATSE, we investigate the luminosity-peak energy relation (L-E p relation) in the decay phases of these pulses. A tight L-E p relation is found for most of the pulses, but its power law index is various among pulses, which is normally distributed at 1.84±0.60(1σ) for the pulses in our sample, roughly consistent with the L-E p relation within a GRB and the isotropic gamma-ray energy-E p relation among GRBs. The large scatter of the power law index cannot be explained with both the statistical or observational effects and it may be an intrinsic feature, indicating that no universal L-E p relation would be expected among GRBs/pulses. This may strongly weaken the cosmological use of this relation.

  6. Chemistry in Protoplanetary Disks: the gas-phase CO/H2 ratio and the Carbon reservoir

    CERN Document Server

    Reboussin, L; Guilloteau, S; Hersant, F; Dutrey, A

    2015-01-01

    The gas mass of protoplanetary disks, and the gas-to-dust ratio, are two key elements driving the evolution of these disks and the formation of planetary system. We explore here to what extent CO (or its isotopologues) can be used as a tracer of gas mass. We use a detailed gas-grain chemical model and study the evolution of the disk composition, starting from a dense pre-stellar core composition. We explore a range of disk temperature profiles, cosmic rays ionization rates, and disk ages for a disk model representative of T Tauri stars. At the high densities that prevail in disks, we find that, due to fast reactions on grain surfaces, CO can be converted to less volatile forms (principally s-CO$_2$, and to a lesser extent s-CH$_4$) instead of being evaporated over a wide range of temperature. The canonical gas-phase abundance of 10$^{-4}$ is only reached above about 30-35 K. The dominant Carbon bearing entity depends on the temperature structure and age of the disk. The chemical evolution of CO is also sensit...

  7. Host-Guest Chemistry in the Gas Phase: Complex Formation of Cucurbit[6]uril with Proton-bound Water Dimer

    Science.gov (United States)

    Noh, Dong Hun; Lee, Shin Jung C.; Lee, Jong Wha; Kim, Hugh I.

    2014-03-01

    The hydration of cucurbit[6]uril (CB[6]) in the gas phase is investigated using electrospray ionization traveling wave ion mobility mass spectrometry (ESI-TWIM-MS). Highly abundant dihydrated and tetrahydrated species of diprotonated CB[6] are found in the ESI-TWIM-MS spectrum. The hydration patterns of the CB[6] ion and the dissociation patterns of the hydrated CB[6] ion indicate that two water molecules are bound to each other, forming a water dimer in the CB[6] complex. Ion mobility studies combined with the structures calculated by density functional theory suggest that the proton-bound water dimer is present as a Zundel-like structure in the CB[6] portal, forming a hydrogen bond network with carbonyl groups of the CB[6]. When a large guest molecule is bound to a CB[6] portal, water molecules cannot bind to the portal. In addition, the strong binding energy of the water dimer blocks the portal, hindering the insertion of the long alkyl chain of the guest molecule into the CB[6] cavity. With small alkali metal cations, such as Li+ and Na+, a single water molecule interacts with the CB[6] portal, forming hydrogen bonds with the carbonyl groups of CB[6]. A highly stable Zundel-like structure of the proton-bound water dimer or a metal-bound water molecule at the CB[6] portal is suggested as an initial hydration process for CB[6], which is only dissolved in aqueous solution with acid or alkali metal ions.

  8. Cyclodextrin chemistry

    International Nuclear Information System (INIS)

    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

  9. Tropospheric Halogen Chemistry

    Science.gov (United States)

    von Glasow, R.; Crutzen, P. J.

    2003-12-01

    hydrocarbons. Loss of ozone by catalytic reactions involving halogen radicals lowers the concentrations of the hydroxyl radical OH and thus the oxidation power of the atmosphere. Figure 1 shows these and other relevant halogen-related processes schematically. The sum of particulate and gaseous halogen concentrations maximize in the marine troposphere. Important for our climate - via feedback with cloud microphysics mainly in the large regions of marine stratocumulus - are links between halogen chemistry and the sulfur cycle. HOBraq and HOClaq can increase the liquid phase oxidation of S(IV) to S(VI), while BrO can decrease the most important in situ source for SO2 in the marine troposphere, namely, the oxidation of DMS to SO2 by reaction with OH by providing an alternate pathway (BrO+DMS) that reduces the yield of SO2 from DMS oxidation. Thus, the presence of bromine and chlorine in the troposphere lowers gas phase SO2 concentrations and thus the formation of new sulfate particles via the reaction sequence SO2+OH→H2SO4. (17K)Figure 1. Schematic depiction of the most important halogen-related processes in the troposphere. High mixing ratios of iodine oxide at a coastal site indicate a potentially significant role of iodine for the destruction of O3 and new particle embryo formation (Alicke et al., 1999; O'Dowd et al., 1998). Almost 20 years earlier, Chameides and Davis (1980) suggested that open ocean iodine chemistry would be initiated by the photolysis of CH3I. This was based on the measurements of Lovelock et al. (1973) and Singh et al. (1979), who found volume mixing ratios of CH3I of 1-5 pmol mol-1 over the ocean.The potentially strong involvement of halogens in tropospheric chemistry was first observed in the Arctic, where strong ozone depletion events were found to coincide with high levels of bromine (Barrie et al., 1988).The first mid-latitude demonstration of reactive halogen chemistry in the troposphere was made downwind of salt pans in the Dead Sea area, where the

  10. Mathematical problems for chemistry students

    CERN Document Server

    Pota, Gyorgy

    2011-01-01

    Mathematical Problems for Chemistry Students has been compiled and written (a) to help chemistrystudents in their mathematical studies by providing them with mathematical problems really occurring in chemistry (b) to help practising chemists to activate their applied mathematical skills and (c) to introduce students and specialistsof the chemistry-related fields (physicists, mathematicians, biologists, etc.) intothe world of the chemical applications.Some problems of the collection are mathematical reformulations of those in the standard textbooks of chemistry, others we

  11. Three-phase dynamic CT findings of liver abscess: related factors with multiple layering enhancement pattern

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Ju Bae; Kim, Yong Soo; Rhim, Hyun Chul; Koh, Byung Hee; Cho, On Koo; Kim, Bong Soo; Park, Dong Woo; Park, Choong Ki [Hanyang Univ. College of Medicine, Seoul (Korea, Republic of)

    2001-01-01

    To determine the number of multiple alternating layers of liver abscess, and changes in this number, as revealed by spiral CT, and to ascertain which factors are related to changes occurring during the three phase of this modality. Using three-phase sprial CT imagingewe studied 26 cases of liver abscess (pyogenic: amebi = 23:3). The number of layers comprising the abscess, as seen on postcontrast CT scans, was determined during the arterial (30sec), portal (70sec),and delayed (220sec) phase, and all cases were assigned to one of to groups according to changes in the number of layers observed during the three phases. With regard to underlying disease, the two groups were compared in terms of the presence of abscess and of diabetes mellitus, CT interval (time from oneset of symptoms to CT scanning), microbial agent (pyogenic vs. amebic), and the largest diameter of abscess as revealed by CT. Except in one case, three or four alternating layers (in 13(50%) and 7(27%) cases, respectively) were seen only during the arterial and portal phase. During each of the three phase and especially the delayed phase, where it was present in 25 of cases (96%)-two alternating layers (2:2:2) was the most common pattern, with a 3:3:3 pattern occurring in one case. All 12 cases (46%) in the unchanging-layer group showed one of three two patterns. All changing-layer group cases (14;54%) demonstrated three or four layers during the arterial and portal phase but only two during the delayed phase. The CT interval was the only significantly different factor between the two groups. During the first week, the number of cases in the unchanging-layer group was much higher than in the changing layergroup (86%, 14%), but during the second week this situation reversed (25%, 75%). Our study reveals that on three-phase dynamic CT images, a characteristic enhancement feature of liver abscess is three or four layers during the arterial and portal phases, with reduction to two layers during the delayed

  12. Determining phase relations of proxy data using the eccentricity-precession pattern

    Science.gov (United States)

    Zeeden, C.; Rivera, T. A.

    2012-04-01

    The phase relation between proxy data and orbital forcing is not always obvious; a link to both precession/insolation maxima or -minima can often be reasoned for. We present a novel approach to extract the phase relation using solely eccentricity-precession pattern from high quality proxy data. We determine the position of consecutive eccentricity maxima as precisely as possible from a stratigraphic record using both eccentricity filters and the amplitude modulation of precession. This way we obtain both the position of these eccentricity maxima as well as the sedimentation rate between successive maxima with error margins. Combining these results with the precession pattern in the geological record, we can determine whether precession-related patterns relate to precession (or insolation) minima or maxima. This approach relies on high quality geological data, the assumption of a direct eccentricity and precession response to orbital forcing, and a well defined orbital solution, but avoids the assumption of an instantaneous response to obliquity. For data with filtered components showing a good fit with the proxy data, this approach yields good results. Using high quality proxy data (color, magnetic susceptibility), we are able to determine the phase relation for equatorial Atlantic Miocene successions of ODP Leg 154. The research leading to these results has received funding from the [European Community's] Seventh Framework Programme ([FP7/2007-2013] under grant agreement n° [215458]. This research used data provided by IODP. Funding for this research was provided by NWO.

  13. Some issues in the simulation of two-phase flows: The relative velocity

    Science.gov (United States)

    Gräbel, J.; Hensel, S.; Ueberholz, P.; Zeidan, D.; Farber, P.

    2016-06-01

    In this paper we compare numerical approximations for solving the Riemann problem for a hyperbolic two-phase flow model in two-dimensional space. The model is based on mixture parameters of state where the relative velocity between the two-phase systems is taken into account. This relative velocity appears as a main discontinuous flow variable through the complete wave structure and cannot be recovered correctly by some numerical techniques when simulating the associated Riemann problem. Simulations are validated by comparing the results of the numerical calculation qualitatively with OpenFOAM software. Simulations also indicate that OpenFOAM is unable to resolve the relative velocity associated with the Riemann problem.

  14. MODELLING THE INTERACTION IN GAME SPORTS - RELATIVE PHASE AND MOVING CORRELATIONS

    Directory of Open Access Journals (Sweden)

    Martin Lames

    2006-12-01

    Full Text Available Model building in game sports should maintain the constitutive feature of this group of sports, the dynamic interaction process between the two parties. For single net/wall games relative phase is suggested to describe the positional interaction between the two players. 30 baseline rallies in tennis were examined and relative phase was calculated by Hilbert transform from the two time-series of lateral displacement and trajectory in the court respectively. Results showed that relative phase indicates some aspects of the tactical interaction in tennis. At a more abstract level the interaction between two teams in handball was studied by examining the relationship of the two scoring processes. Each process can be conceived as a random walk. Moving averages of the scoring probabilities indicate something like a momentary strength. A moving correlation (length = 20 ball possessions describes the momentary relationship between the teams' strength. Evidence was found that this correlation is heavily time-dependent, in almost every single game among the 40 examined ones we found phases with a significant positive as well as significant negative relationship. This underlines the importance of a dynamic view on the interaction in these games.

  15. Subsolidus Phase Relations in the ZnO-BaO-V2O5 System

    Institute of Scientific and Technical Information of China (English)

    ZHENG Meng; LV Pei-Wen; CHEN Da-Gui; YAN Feng-Bo; HUANG Feng

    2013-01-01

    The subsolidus phase relations of the ZnO-BaO-V2O5 ternary systems were investigated by means of X-ray diffraction analysis.There are three ternary compounds,nine binary compounds and sixteen 3-phase regions found in this system.The crystal structure of the ternary compound Ba2ZnV2O8 was refined by Rietveld profile fitting method and the powder diffraction pattern is given.A new ternary compound Ba3.4Zn0.8V4O14.2 has been found by the powder diffraction pattern.

  16. Direct measurements of the current-phase relation in graphene Josephson junctions

    Science.gov (United States)

    English, Christopher; Hamilton, David; van Harlingen, Dale; Mason, Nadya

    2013-03-01

    The current-phase relation (CPR) of a Josephson junction can provide key information about the microscopic processes and symmetries that control the supercurrent. In this talk, we present CPR measurements on Josephson junctions incorporating single-layer graphene as a weak link between Al superconducting electrodes with spacing supercurrent amplitude and phase as a function of temperature and electrostatic doping (gate voltage). As the critical current is varied, we observe a crossover from forward skewing in the CPR that arises from the low density of discrete electronic states in the junction to backward skewing induced by noise-rounding in the CPR measurement. We compare our results to theoretical models.

  17. Quantum State Reduction by Matter-Phase-Related Measurements in Optical Lattices

    CERN Document Server

    Kozlowski, Wojciech; Mekhov, Igor B

    2016-01-01

    A many-body atomic system coupled to quantized light is subject to weak measurement. Instead of coupling light to the on-site density, we consider the quantum backaction due to the measurement of matter-phase-related variables such as global phase coherence. We show how this unconventional approach opens up new opportunities to affect system evolution and demonstrate how this can lead to a new class of measurement projections, thus extending the measurement postulate for the case of strong competition with the system's own evolution.

  18. General Relativity in the radial gauge I. Reduced phase space and canonical structure

    CERN Document Server

    Bodendorfer, Norbert; Świeżewski, Jedrzej

    2015-01-01

    Firstly, we present a reformulation of the standard canonical approach to spherically symmetric systems in which the radial gauge is imposed. This is done via the gauge unfixing techniques, which serves as their exposition in the context of the radial gauge. Secondly, we apply the same techniques to the full theory, without assuming spherical symmetry, resulting in a reduced phase space description of General Relativity. The canonical structure of the theory is analysed. In a companion paper a quantization of the reduced phase space is presented. The construction is well suited for the treatment of spherically symmetric situations and allows for a quantum definition thereof.

  19. Phase relations near ternary eutectic point in the Ag-In-Sb system

    Directory of Open Access Journals (Sweden)

    Jendrzejczyk-Handzlik D.

    2007-01-01

    Full Text Available The results of the phase relations near ternary eutectic point in the Ag-In-Sb system are investigated in this paper. Phase equilibrium calculation was done using Thermocalc software and experimental DTA results for the chosen alloys in the isopleths with molar ration of In:Sb = 7:3; 9:1 and 1:1. The structural characteristics of these alloys have been investigated using light optic microscopy and scanning electron microscopy, while hardness measurements have also been done. Solidification path for three ternary alloys located on three different investigated isopleths was calculated using Pandat software.

  20. Mathematical Thinking in Chemistry

    Directory of Open Access Journals (Sweden)

    José L. Villaveces

    2012-05-01

    Full Text Available Mathematical chemistry is often thought to be a 20th-century subdiscipline of chemistry, but in this paper we discuss several early chemical ideas and some landmarks of chemistry as instances of the mathematical way of thinking; many of them before 1900. By the mathematical way of thinking, we follow Weyl's description of it in terms of functional thinking, i.e. setting up variables, symbolizing them, and seeking for functions relating them. The cases we discuss are Plato's triangles, Geoffroy's affinity table, Lavoisier's classification of substances and their relationships, Mendeleev's periodic table, Cayley's enumeration of alkanes, Sylvester's association of algebra and chemistry, and Wiener's relationship between molecular structure and boiling points. These examples show that mathematical chemistry has much more than a century of history.

  1. Social Chemistry

    OpenAIRE

    Lichtfouse, Eric; Schwarzbauer, Jan; Robert, Didier

    2012-01-01

    International audience This article is both an essay to propose social chemistry as a new scientific discipline, and a preface of the book Environmental Chemistry for a Sustainable World. Environmental chemistry is a fast emerging discipline aiming at the understanding the fate of pollutants in ecosystems and at designing novel processes that are safe for ecosystems. Past pollution should be cleaned, future pollution should be predicted and avoided (Lichtfouse et al., 2005a). Such advices ...

  2. Computational chemistry

    OpenAIRE

    Truhlar, Donald G.; McKoy, Vincent

    2000-01-01

    Computational chemistry has come of age. With significant strides in computer hardware and software over the last few decades, computational chemistry has achieved full partnership with theory and experiment as a tool for understanding and predicting the behavior of a broad range of chemical, physical, and biological phenomena. The Nobel Prize award to John Pople and Walter Kohn in 1998 highlighted the importance of these advances in computational chemistry. With massively parallel computers ...

  3. Bioinorganic Chemistry

    OpenAIRE

    Bertini, Ivano; Gray, Harry B.; Lippard, Stephen J.; Valentine, Joan Selverstone

    1994-01-01

    This book covers material that could be included in a one-quarter or one-semester course in bioinorganic chemistry for graduate students and advanced undergraduate students in chemistry or biochemistry. We believe that such a course should provide students with the background required to follow the research literature in the field. The topics were chosen to represent those areas of bioinorganic chemistry that are mature enough for textbook presentation. Although each chapter presents material...

  4. Microscopic Experimental Approaches to High Pressure Chemistry

    OpenAIRE

    Russell, T.; ALLEN, T.; Rice, J.; Gupta, Y.

    1995-01-01

    The experimental study of the chemistry related to the deflagration/detonation of energetic materials is extremely challenging due to the high pressure, high temperature, and time domain under which the chemical reactions occur. In addition, non equilibrium pressure and temperature conditions temporally effect the reaction pathways and rates during the reaction process. The multiple phases of material present (i.e. the heterogeneous nature of the problem), the multiple reaction pathways (both...

  5. Current-phase relation measurements of SFS π-Josephson junctions

    Science.gov (United States)

    Frolov, S. M.; van Harlingen, D. J.; Oboznov, V. A.; Ryazanov, V. V.

    2004-03-01

    We present measurements of the current-phase relation (CPR) of Superconductor-Ferromagnet-Superconductor (SFS) Josephson junctions as a function of temperature. The CPR is determined by incorporating the junction in an rf SQUID geometry coupled to a dc SQUID, allowing measurement of the junction phase difference. Junctions fabricated with a thin ( ˜25 nm) barrier of Cu_0.48Ni_0.52 sandwiched between Nb electrodes exhibit a re-entrant critical current with temperature, vanishing at T=T_π ˜2-4 K. We find a phase shift of π for T

  6. Ion irradiation-induced diffusion in bixbyite-fluorite related oxides: Dislocations and phase transformation

    Energy Technology Data Exchange (ETDEWEB)

    Rolly, Gaboriaud, E-mail: Rolly.gaboriaud@univ-poitiers.fr [Institut Pprime, CNRS-University of Poitiers, SP2MI-BP 30179, 86962 Chasseneuil-Futuroscope (France); Fabien, Paumier [Institut Pprime, CNRS-University of Poitiers, SP2MI-BP 30179, 86962 Chasseneuil-Futuroscope (France); Bertrand, Lacroix [CSIC – University of Sevilla, Avenida Américo Vespucio, 49, 41092 Sevilla (Spain)

    2014-05-01

    Ion-irradiation induced diffusion and the phase transformation of a bixbyite-fluorite related rare earth oxide thin films are studied. This work is focused on yttrium sesquioxide, Y{sub 2}O{sub 3}, thin films deposited on Si (1 0 0) substrates using the ion beam sputtering technique (IBS). As-deposited samples were annealed ant then irradiated at cryogenic temperature (80 K) with 260 keV Xe{sup 2+} at different fluences. The irradiated thin oxide films are characterized by X-ray diffraction. A cubic to monoclinic phase transformation was observed. Analysis of this phenomenon is done in terms of residual stresses. Stress measurements as a function of irradiation fluences were realised using the XRD-sin{sup 2}ψ method. Stress evolution and kinetic of the phase transformation are compared and leads to the role-played by the nucleation of point and extended defects.

  7. Technetium chemistry

    International Nuclear Information System (INIS)

    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)

  8. Observations and implications of liquid-liquid phase separation at high relative humidities in secondary organic material produced by α-pinene ozonolysis without inorganic salts

    Science.gov (United States)

    Renbaum-Wolff, Lindsay; Song, Mijung; Marcolli, Claudia; Zhang, Yue; Liu, Pengfei F.; Grayson, James W.; Geiger, Franz M.; Martin, Scot T.; Bertram, Allan K.

    2016-07-01

    Particles consisting of secondary organic material (SOM) are abundant in the atmosphere. To predict the role of these particles in climate, visibility and atmospheric chemistry, information on particle phase state (i.e., single liquid, two liquids and solid) is needed. This paper focuses on the phase state of SOM particles free of inorganic salts produced by the ozonolysis of α-pinene. Phase transitions were investigated in the laboratory using optical microscopy and theoretically using a thermodynamic model at 290 K and for relative humidities ranging from change. In the modeling studies, the SOM took up very little water and was a single organic-rich phase at low RH values. At high RH, the SOM underwent LLPS to form an organic-rich phase and a water-rich phase, consistent with the laboratory studies. The presence of LLPS at high RH values can have consequences for the cloud condensation nuclei (CCN) activity of SOM particles. In the simulated Köhler curves for SOM particles, two local maxima were observed. Depending on the composition of the SOM, the first or second maximum can determine the critical supersaturation for activation. Recently researchers have observed inconsistencies between measured CCN properties of SOM particles and hygroscopic growth measured below water saturation (i.e., hygroscopic parameters measured below water saturation were inconsistent with hygroscopic parameters measured above water saturation). The work presented here illustrates that such inconsistencies are expected for systems with LLPS when the water uptake at subsaturated conditions represents the hygroscopicity of an organic-rich phase while the barrier for CCN activation can be determined by the second maximum in the Köhler curve when the particles are water rich.

  9. Observations and implications of liquid-liquid phase separation at high relative humidities in secondary organic material produced by α-pinene ozonolysis without inorganic salts

    Science.gov (United States)

    Renbaum-Wolff, Lindsay; Song, Mijung; Marcolli, Claudia; Zhang, Yue; Liu, Pengfei F.; Grayson, James W.; Geiger, Franz M.; Martin, Scot T.; Bertram, Allan K.

    2016-07-01

    Particles consisting of secondary organic material (SOM) are abundant in the atmosphere. To predict the role of these particles in climate, visibility and atmospheric chemistry, information on particle phase state (i.e., single liquid, two liquids and solid) is needed. This paper focuses on the phase state of SOM particles free of inorganic salts produced by the ozonolysis of α-pinene. Phase transitions were investigated in the laboratory using optical microscopy and theoretically using a thermodynamic model at 290 K and for relative humidities ranging from curves for SOM particles, two local maxima were observed. Depending on the composition of the SOM, the first or second maximum can determine the critical supersaturation for activation. Recently researchers have observed inconsistencies between measured CCN properties of SOM particles and hygroscopic growth measured below water saturation (i.e., hygroscopic parameters measured below water saturation were inconsistent with hygroscopic parameters measured above water saturation). The work presented here illustrates that such inconsistencies are expected for systems with LLPS when the water uptake at subsaturated conditions represents the hygroscopicity of an organic-rich phase while the barrier for CCN activation can be determined by the second maximum in the Köhler curve when the particles are water rich.

  10. Menstrual cycle phase modulates reward-related neural function in women

    OpenAIRE

    Dreher, Jean-Claude; Schmidt, Peter J.; Kohn, Philip; Furman, Daniella; Rubinow, David; Berman, Karen Faith

    2007-01-01

    There is considerable evidence from animal studies that the mesolimbic and mesocortical dopamine systems are sensitive to circulating gonadal steroid hormones. Less is known about the influence of estrogen and progesterone on the human reward system. To investigate this directly, we used functional MRI and an event-related monetary reward paradigm to study women with a repeated-measures, counterbalanced design across the menstrual cycle. Here we show that during the midfollicular phase (days ...

  11. On Dual Phase-Space Relativity, the Machian Principle and Modified Newtonian Dynamics

    OpenAIRE

    De Castro C

    2005-01-01

    We investigate the consequences of the Mach’s principle of inertia within the context of the Dual Phase Space Relativity which is compatible with the Eddington-Dirac large numbers coincidences and may provide with a physical reason behind the observed anomalous Pioneer acceleration and a solution to the riddle of the cosmological constant problem. The cosmological implications of Non-Archimedean Geometry by assigning an upper impossible scale in Nature and the cosmologi...

  12. Nonlinear Time Domain Relation between Respiratory Phase and Timing of the First Heart Sound

    OpenAIRE

    Hong Tang; Yongwan Park; Chengjie Ruan

    2015-01-01

    The previous studies on respiratory physiology have indicated that inspiration and expiration have opposite effects on heart hemodynamics. The basic reason why these opposite hemodynamic changes cause regular timing variations in heart sounds is the heart sound generation mechanism that the acoustic vibration is triggered by heart hemodynamics. It is observed that the timing of the first heart sound has nonlinear relation with respiratory phase; that is, the timing delay with respect to the R...

  13. Computational quantum chemistry website

    International Nuclear Information System (INIS)

    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

  14. Good chemistry

    OpenAIRE

    Petsko, Gregory A

    2004-01-01

    The subject matter in chemistry courses reflects almost nothing of the issues that chemists are interested in. It is important to formulate a set of topics - and a Medical College Admissions Test reflecting them - that would leave chemistry departments no choice but to change their teaching.

  15. Soil radon pulses related to the initial phase of volcanic eruptions

    Energy Technology Data Exchange (ETDEWEB)

    Segovia, N. [Instituto Nacional de Investigaciones Nucleares, Mexico City (Mexico); Mena, M. [IGFUNAM, Mexico City (Mexico)

    1999-08-01

    Soil radon behaviour related to the initial phase of volcanic eruptions is analysed from reported values related to the explosiveness of four American stratovolcaneos: El Chicon (1982) and Popocatepetl (1994) in Mexico, Poas (1987-1990) in Costa Rica and Cerro Negro (1982) in Nicaragua. The measurements in the field were performed with solid-state nuclear track detectors and electrets. The ratio between the magnitudes of the radon in soil peaks generated when the eruptive period started and the average radon values corresponding to quiescence periods indicate a dependence on the volcanic eruptive index for each one of the eruptive periods.

  16. Soil radon pulses related to the initial phase of volcanic eruptions

    International Nuclear Information System (INIS)

    Soil radon behaviour related to the initial phase of volcanic eruptions is analysed from reported values related to the explosivity of four American stratovolcaneos: El Chicon (1982) and Popocatepetl (1994) in Mexico, Poas (1987-1990) in Costa Rica and Cerro Negro (1982) in Nicaragua. The measurements in the field were performed with solid-state nuclear track detectors and electrets. The ratio between the magnitudes of the radon in soil peaks generated when the eruptive period started and the average radon values corresponding to quiescence periods indicate a dependence on the volcanic eruptive index for each one of the eruptive periods

  17. Measurement of the atmospheric muon depth intensity relation with the NEMO Phase-2 tower

    CERN Document Server

    Aiello, S; Anghinolfi, M; Barbarino, G; Barbarito, E; Barbato, F; Beverini, N; Biagi, S; Bouhadef, B; Bozza, C; Cacopardo, G; Calamai, M; Calì, C; Capone, A; Caruso, F; Ceres, A; Chiarusi, T; Circella, M; Cocimano, R; Coniglione, R; Costa, M; Cuttone, G; D'Amato, C; D'Amico, A; De Bonis, G; De Luca, V; Deniskina, N; De Rosa, G; Di Capua, F; Distefano, C; Fermani, P; Fusco, L A; Garufi, F; Giordano, V; Gmerk, A; Grasso, R; Grella, G; Hugon, C; Imbesi, M; Kulikovskiy, V; Larosa, G; Lattuada, D; Leismueller, K P; Leonora, E; Litrico, P; Lonardo, A; Longhitano, F; Presti, D Lo; Maccioni, E; Margiotta, A; Martini, A; Masullo, R; Migliozzi, P; Migneco, E; Miraglia, A; Mollo, C M; Mongelli, M; Morganti, M; Musico, P; Musumeci, M; Nicolau, C A; Orlando, A; Papaleo, R; Pellegrino, C; Pellegriti, M G; Perrina, C; Piattelli, P; Pugliatti, C; Pulvirenti, S; Orselli, A; Raffaelli, F; Randazzo, N; Riccobene, G; Rovelli, A; Sanguineti, M; Sapienza, P; Sciacca, V; Sgura, I; Simeone, F; Sipala, V; Speziale, F; Spina, M; Spitaleri, A; Spurio, M; Stellacci, S M; Taiuti, M; Terreni, G; Trasatti, L; Trovato, A; Ventura, C; Vicini, P; Viola, S; Vivolo, D

    2014-01-01

    The results of the analysis of the data collected with the NEMO Phase-2 tower, deployed at 3500 m depth about 80 km off-shore Capo Passero (Italy), are presented. Cherenkov photons detected with the photomultipliers tubes were used to reconstruct the tracks of atmospheric muons. Their zenith-angle distribution was measured and the results compared with Monte Carlo simulations. An evaluation of the systematic effects due to uncertainties on environmental and detector parameters is also included. The associated depth intensity relation was evaluated and compared with previous measurements and theoretical predictions. With the present analysis, the muon depth intensity relation has been measured up to 13 km of water equivalent.

  18. Radiation chemistry of amino acids, peptides and proteins in relation to the radiation sterilization of high-protein foods

    International Nuclear Information System (INIS)

    An important source of information on the question of whether or not toxic or other deleterious substances are formed in the radiation sterilization of foods is the chemical study of reaction products and reaction mechanisms in the radiolysis of individual food components. The present evaluation of the radiation chemistry of amino acids, peptides and proteins outlines the various radiation-induced processes which lead to amino acid degradation and to the synthesis of amino acid derivatives of higher molecular weight. Among the latter are the α,α'-diamino dicarboxylic acids which are formed as major products in the radiolysis of peptides both in aqueous solution and in the solid state. The α,α'-diamino acids are of particular interest as irradiation products because they represent a class of compounds not normally encountered in plant and animal protein sources. Such compounds have, however, been isolated from certain types of bacteria and pathogenic toxins. All of the available data strongly suggest that the α,α'-diamino acids are produced in significant yield in the radiation sterilization of high protein foods. The importance of initiating extensive chemical and biological studies of initiating extensive chemical and biological studies of these and of other high molecular weight products in irradiated food is emphasized

  19. Radiation chemistry of amino acids, peptides and proteins in relation to the radiation sterilization of high-protein foods

    International Nuclear Information System (INIS)

    An important source of information on the question of whether or not toxic or other deleterious substances are formed in the radiation sterilization of foods is the chemical study of reaction products and reaction mechanisms in the radiolysis of individual food components. The present evaluation of the radiation chemistry of amino acids, peptides, and proteins outlines the various radiation-induced processes which lead to amino acid degradation and to the synthesis of amino acid derivatives of higher molecular weight. Among the latter are the α,α'-diamino dicarboxylic acids which are formed as major products in the radiolysis of peptides both in aqueous solution and in the solid state. The α,α'-diamino acids are of particular interest as irradiation products because they represent a class of compounds not normally encountered in plant and animal protein sources. Such compounds have, however, been isolated from certain types of bacteria and bacterial products. All of the available data strongly suggest that the α,α'-diamino acids are produced in significant yield in the radiation sterilization of high protein foods. The importance of initiating extensive chemical and biological studies of these and of other high molecular weight products in irradiated food is emphasized

  20. The radiation chemistry of amino acids, peptides and proteins in relation to the radiation sterilization of high-protein foods

    International Nuclear Information System (INIS)

    An important source of information on the question of whether or not toxic or other deleterious substances are formed in the radiation sterilization of foods is the chemical study of reaction products and reaction mechanisms in the radiolysis of individual food components. The present evaluation of the radiation chemistry of amino acids, peptides and proteins outlines the various radiation-induced processes which lead to amino acid degradation and to the synthesis of amino acid derivatives of higher molecular weight. Among the latter are the α,α'-diamino dicarboxylic acids which are formed as major products in the radiolysis of peptides both in aqueous solution and in the solid state. The α,α'-diamino acids are of particular interest as irradiation products because they represent a class of compounds not normally encountered in plant and animal protein sources. Such compounds have, however, been isolated from certain types of bacteria and bacterial products. All of the available data strongly suggest that the α,α'-diamino acids are produced in significant yield in the radiation sterilization of high protein foods. The importance of initiating extensive chemical and biological studies of these and of other high molecular weight products in irradiated food is emphasised. (author)

  1. Exploring Systematic Effects in the Relation Between Stellar Mass, Gas Phase Metallicity, and Star Formation Rate

    CERN Document Server

    Telford, O Grace; Skillman, Evan D; Conroy, Charlie

    2016-01-01

    There is evidence that the well-established mass-metallicity relation in galaxies is correlated with a third parameter: star formation rate (SFR). The strength of this correlation may be used to disentangle the relative importance of different physical processes (e.g., infall of pristine gas, metal-enriched outflows) in governing chemical evolution. However, all three parameters are susceptible to biases that might affect the observed strength of the relation between them. We analyze possible sources of systematic error, including sample bias, application of S/N cuts on emission lines, choice of metallicity calibration, uncertainty in stellar mass determination, aperture effects, and dust. We present the first analysis of the relation between stellar mass, gas phase metallicity, and SFR using strong line abundance diagnostics from Dopita et al. (2013) for ~130,000 star-forming galaxies in the Sloan Digital Sky Survey and provide a detailed comparison of these diagnostics in an appendix. Using these abundance ...

  2. Relative velocity measurement from the spectral phase of a match-filtered linear frequency modulated pulse.

    Science.gov (United States)

    Pinson, Samuel; Holland, Charles W

    2016-08-01

    Linear frequency modulated signals are commonly used to perform underwater acoustic measurements since they can achieve high signal-to-noise ratios with relatively low source levels. However, such signals present a drawback if the source or receiver or target is moving. The Doppler effect affects signal amplitude, delay, and resolution. To perform a correct match filtering that includes the Doppler shift requires prior knowledge of the relative velocity. In this paper, the relative velocity is extracted directly from the Doppler cross-power spectrum. More precisely, the quadratic coefficient of the Doppler cross-power-spectrum phase is proportional to the relative velocity. The proposed method achieves velocity estimates that compare favorably with Global Positioning System ground truth and the ambiguity method. PMID:27586779

  3. The Relation between Students' Math and Reading Ability and Their Mathematics, Physics, and Chemistry Examination Grades in Secondary Education

    Science.gov (United States)

    Korpershoek, Hanke; Kuyper, Hans; van der Werf, Greetje

    2015-01-01

    Word problems are math- or science-related problems presented in the context of a story or real-life scenario. Literature suggests that, to solve these problems, advanced reading skills are required, in addition to content-related skills in, for example, mathematics. In the present study, we investigated the relation between students' reading…

  4. Phase-oriented treatment of structural dissociation in complex traumatization: overcoming trauma-related phobias.

    Science.gov (United States)

    Steele, Kathy; van der Hart, Onno; Nijenhuis, Ellert R S

    2005-01-01

    The theory of structural dissociation of the personality proposes that patients with complex trauma-related disorders are characterized by a division of their personality into different prototypical parts, each with its own psychobiological underpinnings. As one or more apparently normal parts (ANPs), patients have a propensity toward engaging in evolutionary prepared action systems for adaptation to daily living to guide their actions. Two or more emotional parts (EPs) are fixated in traumatic experience. As EPs, patients predominantly engage action systems related to physical defense and attachment cry. ANP and EP are insufficiently integrated, but interact and share a number of dispositions of the personality (e.g., speaking). All parts are stuck in maladaptive action tendencies that maintain dissociation, including a range of phobias, which is a major focus of this article. Phase-oriented treatment helps patients gradually develop adaptive mental and behavioral actions, thus overcoming their phobias and structural dissociation. Phase 1, symptom reduction and stabilization, is geared toward overcoming phobias of mental contents, dissociative parts, and attachment and attachment loss with the therapist. Phase 2, treatment of traumatic memories, is directed toward overcoming the phobia of traumatic memories, and phobias related to insecure attachment to the perpetrator(s), particularly in EPs. In Phase 3, integration and rehabilitation, treatment is focused on overcoming phobias of normal life, healthy risk-taking and change, and intimacy. To the degree that the theory of structural dissociation serves as an integrative heuristic for treatment, it should be compatible with other theories that guide effective treatment of patients with complex dissociative disorders. PMID:16172081

  5. 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.

  6. Chemistry and nuclear technology

    International Nuclear Information System (INIS)

    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

  7. 3.6 AND 4.5 μm PHASE CURVES AND EVIDENCE FOR NON-EQUILIBRIUM CHEMISTRY IN THE ATMOSPHERE OF EXTRASOLAR PLANET HD 189733b

    International Nuclear Information System (INIS)

    this planet's dayside spectrum provide a reasonably accurate estimate of the amount of energy transported to the night side. Our 3.6 and 4.5 μm phase curves are generally in good agreement with the predictions of general circulation models for this planet from Showman et al., although we require either excess drag or slower rotation rates in order to match the locations of the measured maxima and minima in the 4.5, 8.0, and 24 μm bands. We find that HD 189733b's 4.5 μm nightside flux is 3.3σ smaller than predicted by these models, which assume that the chemistry is in local thermal equilibrium. We conclude that this discrepancy is best explained by vertical mixing, which should lead to an excess of CO and correspondingly enhanced 4.5 μm absorption in this region. This result is consistent with our constraints on the planet's transmission spectrum, which also suggest excess absorption in the 4.5 μm band at the day-night terminator.

  8. Direct measurements of the current-phase relation in long-range spin-triplet SFS Josephson junctions

    Science.gov (United States)

    Hamilton, David; van Harlingen, Dale; Wang, Yixing; Birge, Norman

    2015-03-01

    We present direct measurements of the current-phase relation (CPR) of Josephson junctions which use multiple ferromagnetic layers to generate long-range spin-triplet pair correlations. Using a phase-sensitive Josephson interferometry technique, we obtain the phase and temperature dependence of this spin-triplet supercurrent. We also demonstrate the use of an inductive shunt to enhance this technique at higher critical currents. Our data suggest that the current-phase relation of these junctions is harmonic in character. Further measurements are planned in order to determine the ground state phase shift of these junctions.

  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. Phase improvement via the Phantom Derivative technique: ancils that are related to the target structure.

    Science.gov (United States)

    Carrozzini, Benedetta; Cascarano, Giovanni Luca; Giacovazzo, Carmelo

    2016-04-01

    Density modification is a general standard technique which may be used to improve electron density derived from experimental phasing and also to refine densities obtained by ab initio approaches. Here, a novel method to expand density modification is presented, termed the Phantom derivative technique, which is based on non-existent structure factors and is of particular interest in molecular replacement. The Phantom derivative approach uses randomly generated ancil structures with the same unit cell as the target structure to create non-existent derivatives of the target structure, called phantom derivatives, which may be used for ab initio phasing or for refining the available target structure model. In this paper, it is supposed that a model electron density is available: it is shown that ancil structures related to the target obtained by shifting the target by origin-permissible translations may be employed to refine model phases. The method enlarges the concept of the ancil, is as efficient as the canonical approach using random ancils and significantly reduces the CPU refinement time. The results from many real test cases show that the proposed methods can substantially improve the quality of electron-density maps from molecular-replacement-based phases. PMID:27050134

  11. THE ADVANCED CHEMISTRY BASINS PROJECT

    Energy Technology Data Exchange (ETDEWEB)

    William Goddard; Peter Meulbroek; Yongchun Tang; Lawrence Cathles III

    2004-04-05

    In the next decades, oil exploration by majors and independents will increasingly be in remote, inaccessible areas, or in areas where there has been extensive shallow exploration but deeper exploration potential may remain; areas where the collection of data is expensive, difficult, or even impossible, and where the most efficient use of existing data can drive the economics of the target. The ability to read hydrocarbon chemistry in terms of subsurface migration processes by relating it to the evolution of the basin and fluid migration is perhaps the single technological capability that could most improve our ability to explore effectively because it would allow us to use a vast store of existing or easily collected chemical data to determine the major migration pathways in a basin and to determine if there is deep exploration potential. To this end a the DOE funded a joint effort between California Institute of Technology, Cornell University, and GeoGroup Inc. to assemble a representative set of maturity and maturation kinetic models and develop an advanced basin model able to predict the chemistry of hydrocarbons in a basin from this input data. The four year project is now completed and has produced set of public domain maturity indicator and maturation kinetic data set, an oil chemistry and flash calculation tool operable under Excel, and a user friendly, graphically intuitive basin model that uses this data and flash tool, operates on a PC, and simulates hydrocarbon generation and migration and the chemical changes that can occur during migration (such as phase separation and gas washing). The DOE Advanced Chemistry Basin Model includes a number of new methods that represent advances over current technology. The model is built around the concept of handling arbitrarily detailed chemical composition of fluids in a robust finite-element 2-D grid. There are three themes on which the model focuses: chemical kinetic and equilibrium reaction parameters, chemical

  12. Teacher Didactic Content Knowledge and its relation with the utilization of practical activities in chemistry classes: A study with expert teachers of the Angolan educational system

    Directory of Open Access Journals (Sweden)

    Laurinda Baca

    2014-03-01

    Full Text Available This study was developed within the Angolan educational system, with chemistry expert teachers who teach the 7th grade (12 years old. Aiming to characterize the didactic content knowledge and relate it with the quality of teaching and with the development of practical activities that ensure the active participation of students in the construction of knowledge, we observed and analyzed the classes of a group of expert teachers, specifically in the content of chemical reactions and chemical equations. In a quasi-experimental design methodology, the used technique was the observation from the capture of images in the classes. An element we paid particular attention in the analysis of the classes was the implementation of strategies that involve practical activities, since the didactic research has amply demonstrated that they are likely to generate active learning in science education, with particular emphasis in chemistry. The results revealed that the expert teachers often use practical activities in their classrooms, using group work procedures, work front and questions oral and written.

  13. 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,

  14. Ballistic and diffusive regimes in current-phase relations of graphene SNS heterojunctions

    Science.gov (United States)

    Kratz, Philip; Amet, Francois; Watson, Christopher; Moler, Kathryn; Ke, Chung; Borzenets, Ivan; Watanabe, Kenji; Taniguchi, Takashi; Deacon, Russell; Yamamoto, Michihisa; Bomze, Yuriy; Tarucha, Seigo; Finkelstein, Gleb

    Current-phase relations (CPRs) are an indirect measurement of the energy distribution of phase-coherent modes in Josephson junctions through the spectral supercurrent near equilibrium, probing low-energy excitations not accessible by transport. We report on planned experimental measurements of the CPRs of gated, high-mobility (105 cm2/Vs) single-layer graphene SNS heterojunctions in ring geometries with superconducting MoRe alloy contacts, inductively read out with a scanning superconducting quantum interference device (SQUID) magnetometer. The graphene layers are encapsulated on both sides with hexagonal-BN (h-BN). We will address the CPR dependence on experimentally tunable parameters (temperature, carrier density, and channel length), and possible crossovers between the ballistic and diffusive regimes.

  15. Soil-plant transfer factors for Pu in the field and laboratory in relation to desorption from the solid phase

    International Nuclear Information System (INIS)

    Laboratory hydroponics experiments using an environmentally contaminated sediment as source of Pu, were carried out to determine the soil-plant, soil solution-plant and root-plant transfer factors. Soil-plant transfer factors, calculated from field observations, varied according to the degree of animal usage and were more than two orders of magnitude larger than those from the laboratory experiments. The discrepancies between field and laboratory measurements are probably due to the complex sediment speciation and desorption chemistry of Pu. The transfer factors based on the solution or root activities are likely to provided a better estimate of the vegetation activity than those based on the solid phase activity. (author)

  16. Click chemistry-based synthesis of water-dispersible hydrophobic magnetic nanoparticles for use in solid phase extraction of non-steroidal anti-inflammatory drugs

    International Nuclear Information System (INIS)

    Magnetic nanoparticles (MNPs), prepared via thiol-ene click chemistry and containing both diol and octadecyl groups, are shown to possess both hydrophobic and hydrophilic functionalities. They display excellent dispersibility in water and also are capable of extracting non-steroidal anti-inflammatory drugs (NSAIDs) from water samples. The MNPs can be magnetically separated, and the NSAIDs eluted with acetonitrile-water (9:1, v:v) and submitted to high performance liquid chromatographic analysis. Extraction variables, such as the kind of ion-pairing reagents, amount of MNPs, pH of sample solution, extraction and desorption time, volume of desorption solvent and salt addition, were optimized. Under optimum conditions, the method has a wide analytical range (from 5 to 800 ng∙mL-1), good reproducibility with intra-day and inter-day relative standard deviations of <19.2 % (for n = 6), and low detection limits of 0.32 to 1.44 ng∙mL-1 for water samples. The results demonstrate that the material possesses good water compatibility, thus warranting ease of operation and good reproducibility. (author)

  17. Phase relations in the Fe-FeSi system at high pressures and temperatures

    Science.gov (United States)

    Fischer, Rebecca A.; Campbell, Andrew J.; Reaman, Daniel M.; Miller, Noah A.; Heinz, Dion L.; Dera, Przymyslaw; Prakapenka, Vitali B.

    2013-07-01

    The Earth's core is comprised mostly of iron and nickel, but it also contains several weight percent of one or more unknown light elements, which may include silicon. Therefore it is important to understand the high pressure, high temperature properties and behavior of alloys in the Fe-FeSi system, such as their phase diagrams. We determined melting temperatures and subsolidus phase relations of Fe-9 wt% Si and stoichiometric FeSi using synchrotron X-ray diffraction at high pressures and temperatures, up to ~200 GPa and ~145 GPa, respectively. Combining this data with that of previous studies, we generated phase diagrams in pressure-temperature, temperature-composition, and pressure-composition space. We find the B2 crystal structure in Fe-9Si where previous studies reported the less ordered bcc structure, and a shallower slope for the hcp+B2 to fcc+B2 boundary than previously reported. In stoichiometric FeSi, we report a wide B2+B20 two-phase field, with complete conversion to the B2 structure at ~42 GPa. The minimum temperature of an Fe-Si outer core is 4380 K, based on the eutectic melting point of Fe-9Si, and silicon is shown to be less efficient at depressing the melting point of iron at core conditions than oxygen or sulfur. At the highest pressures reached, only the hcp and B2 structures are seen in the Fe-FeSi system. We predict that alloys containing more than ~4-8 wt% silicon will convert to an hcp+B2 mixture and later to the hcp structure with increasing pressure, and that an iron-silicon alloy in the Earth's inner core would most likely be a mixture of hcp and B2 phases.

  18. Phase relations in the Fe-FeSi system at high pressures and temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, Rebecca A.; Campbell, Andrew J.; Reaman, Daniel M.; Miller, Noah A.; Heinz, Dion L.; Dera, Przymyslaw; Prakapenka, Vitali B. (UC); (Maryland)

    2016-07-29

    The Earth's core is comprised mostly of iron and nickel, but it also contains several weight percent of one or more unknown light elements, which may include silicon. Therefore it is important to understand the high pressure, high temperature properties and behavior of alloys in the Fe–FeSi system, such as their phase diagrams. We determined melting temperatures and subsolidus phase relations of Fe–9 wt% Si and stoichiometric FeSi using synchrotron X-ray diffraction at high pressures and temperatures, up to ~200 GPa and ~145 GPa, respectively. Combining this data with that of previous studies, we generated phase diagrams in pressure–temperature, temperature–composition, and pressure–composition space. We find the B2 crystal structure in Fe–9Si where previous studies reported the less ordered bcc structure, and a shallower slope for the hcp+B2 to fcc+B2 boundary than previously reported. In stoichiometric FeSi, we report a wide B2+B20 two-phase field, with complete conversion to the B2 structure at ~42 GPa. The minimum temperature of an Fe–Si outer core is 4380 K, based on the eutectic melting point of Fe–9Si, and silicon is shown to be less efficient at depressing the melting point of iron at core conditions than oxygen or sulfur. At the highest pressures reached, only the hcp and B2 structures are seen in the Fe–FeSi system. We predict that alloys containing more than ~4–8 wt% silicon will convert to an hcp+B2 mixture and later to the hcp structure with increasing pressure, and that an iron–silicon alloy in the Earth's inner core would most likely be a mixture of hcp and B2 phases.

  19. THE RELATION BETWEEN STUDENTS' MATH AND READING ABILITY AND THEIR MATHEMATICS, PHYSICS, AND CHEMISTRY EXAMINATION GRADES IN SECONDARY EDUCATION

    NARCIS (Netherlands)

    Korpershoek, Hanke; Kuyper, Hans; van der Werf, Greetje

    2015-01-01

    Word problems are math- or science-related problems presented in the context of a story or real-life scenario. Literature suggests that, to solve these problems, advanced reading skills are required, in addition to content-related skills in, for example, mathematics. In the present study, we investi

  20. Crystal chemistry and phase equilibrium studies of the BaO(BaCo3)-R2O3-CuO systems. 5

    International Nuclear Information System (INIS)

    This paper reports on the influence of the ionic size of the lanthanides R on melting relations of Ba2RCu3O6+x, where R = Y, Eu and Nd, studied and compared with that of a high-Tc superconductor mixed-lanthanide phase Ba2(Y.75Eu.125Nd.125)Cu3O6+x. These materials have been characterized by a variety of methods including differential thermogravimetric analysis (DTA), scanning electron microscopy (SEM) with energy dispersive x-ray spectroscopy (EDX) and x-ray powder diffraction. Single phase samples of Ba2(Y.75Eu.125Nd.125)Cu3O6+x were annealed at 1004, 1040, 1052, 1060, 1078, 1107 and 1160 degrees C and quenched into a helium gas container cooled by liquid nitrogen

  1. Investigation of the two- and three-phase relative permeability relation in carbon dioxide-oil-water systems for light and heavy oil reservoirs

    Science.gov (United States)

    Zarivnyy, Ostap

    CO2 flooding has gained increased interest in regard to both light and heavy oil reservoirs, as a means of combining improved oil recovery and geological storage of CO2 in partially depleted oil reservoirs. Distribution and movement of CO2 in oil reservoirs is a function of the relative permeability of three phases of water, oil, and CO2 in oil reservoirs. In general, three-phase relative permeability relations are required with respect to the design of CO2 field projects for accurate predictions via numerical reservoir simulation of CO 2 flood performance and to model production and injection problems. However, a two-phase relative permeability relation is used to generate the three-phase relative permeability relation for use in reservoir simulations. An overview of the available literature indicates few attempts have been made to experimentally determine the three-phase relative permeability relation for CO2-oil-water systems under practical reservoir conditions. This research attempts to investigate the two- and three-phase relative permeability relation of CO2-oil-water systems through a series of carefully designed laboratory experiments. Fourteen experiments in two-phase systems, and four experiments in three-phase systems with heavy and light oils, were conducted in order to study the effect of pressure, temperature, viscosity, and flow rate on the relative permeability relation. It was shown that relative permeability is temperature dependent and increases with an increase in temperature. Pressure and oil viscosity had similar effects, although higher pressure caused a decrease in relative permeability to water in water-oil and water-oil-gas systems. Investigating the effect of flow rate it was found that higher injection flow rate caused increase in relative permeability values. The effect of the injection flow rate on relative permeability behaviour can be explained by the formation of emulsion during the displacement process. A set of new correlations

  2. Melting phase relations in the system H2O - NH3 at high pressure

    Science.gov (United States)

    Sugimura, E.; Hirose, K.; Komabayashi, T.; Ohishi, Y.; Hirao, N.; Dubrovinsky, L. S.

    2012-12-01

    The density models of Uranus and Neptune constrained by their gravitational moments from Voyager mission suggest that mantles of these planets may be predominantly comprised of water (H2O), methane (CH4), and ammonia (NH3). The impurities in pure water would greatly influence the phase relations in the water-rich system expected in the icy mantle, which must be known to construct a plausible planetary model. One of important effects of the impurity is on the liquidus temperature (Tliq), since it decides the actual presence of solid phase within the icy mantle. In order to determine Tliq in H2O-rich region of the H2O - CH4 - NH3 ternary system, the melting phase relations in the H2O - CH4 and H2O - NH3 systems must be accurately known. However, previous melting experiments on each binary system were limited to several gigapascals, thus need to be explored to higher P-T conditions for application in interiors of Uranus and Neptune. We have investigated high-pressure (P) and -temperature (T) melting phase relations in the H2O - NH3 system based on a combination of visual observation and angle-dispersive x-ray diffraction (XRD) measurements at BL10XU, SPring-8. High-P-T conditions were generated in an externally-resistive heated diamond anvil cell (DAC). Starting material was 20wt% NH3 aqueous solution whose composition was checked via Tliq of the solution measured in a DAC at near atmospheric pressure. The aqueous solution was loaded into a gold-lined hole in a preindented rhenium gasket in order to insulate the sample from rhenium. Pressure was determined from the unit-cell volume of gold liner. Melting and freezing of the sample were detected by monitoring disappearance/appearance of diffraction peaks of solid and diffuse scattering of liquids, as well as observing melting/crystallization of crystal grains under microscope. Up to 20 GPa at room temperature, in addition to ice VII, diffraction peaks of bcc-like phase, which is most likely to be the reported phase VI

  3. 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...

  4. Introductory Chemistry

    OpenAIRE

    Baron, Mark; Gonzalez-Rodriguez, Jose; Stevens, Gary; Gray, Nathan; Atherton, Thomas; Winn, Joss

    2010-01-01

    Teaching and Learning resources for the 1st Year Introductory Chemistry course (Forensic Science). 30 credits. These are Open Educational Resources (OER), made available for re-use under a Creative Commons license.

  5. Analytical chemistry

    International Nuclear Information System (INIS)

    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.

  6. 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.

  7. Shape change as entropic phase transition: A study using Jarzynski relation

    Indian Academy of Sciences (India)

    Moupriya Das; Debasish Mondal; Deb Shankar Ray

    2012-01-01

    A Brownian particle in a confined space with varying cross-section, experiences an effective entropic potential in reduced dimension. We modulate the shape of the confinement and examine the nature of dynamical transition between two distinct thermalized entropic states corresponding to different shapes of the enclosure, using Jarzynski relation on the basis of work-distribution over non-equilibrium paths. Our analysis reveals that modulating the shape of the boundaries of the enclosure makes the resident Brownian particles feel an entropic phase transition.

  8. Manipulation role of the relative phase and incoherent pumping on a light pulse propagation

    Institute of Scientific and Technical Information of China (English)

    Ni Cui; Aiyun Li; Hui Ma; Hua Li; Xijun Fan

    2006-01-01

    @@ In an open A type system with the spontaneously generated coherence (SGC), when the probe and driving fields have different frequencies, the switching of the group velocity of the probe pulse from subluminal to superluminal is realized not only by adjusting values of the relative phase between the probe and driving fields but also by varying values of the incoherent pumping rate. For the subluminal propagation, the system always exhibits the probe absorption, however, the superluminal propagation is always companied with gain of the probe field.

  9. Bidirectional reflectance spectroscopy 7. The single particle phase function hockey stick relation

    Science.gov (United States)

    Hapke, Bruce

    2012-11-01

    The measured volume-average single particle angular scattering functions of a large number of types of particle of interest for planetary regoliths in the visible-near-IR wavelength region can be represented to a reasonable approximation by two-parameter, double Henyey-Greenstein functions. When the two parameters of this function are plotted against one another they are found to be inversely correlated and lie within a restricted zone shaped like a hockey stick within the parameter space. The centroid of the zone is a curve that can be represented by a simple empirical equation. The wide variety of types of particles used to construct the plot implies that this equation may represent most of the particles found in regoliths. This means that when modeling the bidirectional reflectance of a regolith it may be possible to reduce the number of parameters necessary to specify the reflectance, and also to characterize the entire single particle phase function from observations at phase angles less than 90°. Even if the hockey stick relation has a finite width, rather than being a line, it restricts the parameter space that must be searched when fitting data. The curve should also be useful for forward modeling particle phase functions.

  10. Phase relationship between the relative sunspot numbers and solar mean magnetic field

    Science.gov (United States)

    Yin, Zq; Han, YB

    2015-08-01

    Short-term variations of the solar mean magnetic field (SMMF) were investigated through re-analyzing the data from the Wilcox Solar Observatory during the last four solar activity cycles using continuous wavelet transforms. We demonstrated the time-variable characters of short-term periods of SMMF. Our results indicate that the SMMF has main periods of about 27 and 13.5 days not only in the minimum and maximum years of each activity cycle, but also in the increase and decrease of the solar cycle. The entire time span of SMMF was investigated and discussed further (DOI 10.1007/s11434-014-0594-x). Sunspot numbers (SSN) are caused by intense magnetic activity, and they are associated with strong magnetic fields in active region, while SMMF describe the large-scale manifestations of solar magnetism. The continuous wavelet, cross wavelet, and wavelet coherence analyses, are employed to clarify the phase relationship between the daily and smoothed monthly mean sunspot number and SMMF. Analysis shows that there is a region of high spectral power sitting across the Schwabe cycle belt, where the SSN lead the SMMF by about 10 months. However, analysis of the cross-wavelet transform and wavelet coherence unveils asynchronous behavior featured with phase mixing in the high-frequency components of SSN and SMMF, The time-variable characteristics of periods of SMMF and sunspots and their cross-relations are investigated and discussed during the different phase of solar cycles.

  11. The current-phase relation of graphene-based Josephson junctions

    Science.gov (United States)

    Chialvo, Cesar Eduardo

    The current-phase relation (CPR) of a Josephson junction reveals valuable information about the microscopic processes and symmetries that influence the supercurrent. For the work described in this thesis, we have studied the CPR of graphene-based Josephson junctions, inspired by previous theoretical predictions of a departure from the usual sinusoidal functionality, or skewness, of the CPR. The experimental data was obtained by incorporating the junction into an rf SQUID geometry coupled to a dc SQUID magnetometer, a technique usually referred to as phase-sensitive SQUID interferometry, which allows for the direct measurement of the phase difference across the junction. While some of the predictions from theory---like the departure of the CPR from sinusoidal behavior, its symmetry with carrier nature and the de-skewing with increasing temperature---were qualitatively observed, others were inconsistent with the experimental data. Perhaps the most important disparity was that of the functionality of the skewing, which we found to vary linearly with critical current (Ic), independent of the carrier density/temperature combination used to attain Ic. It is worth mentioning that our measurements have prompted renewed theoretical interest in this system, culminating in the modification of the original model to include the effects of temperature, and a recent publication venturing an explanation for the observed linearity of the CPR skewness with Ic.

  12. Current-phase relation of a ballistic asymmetric double superconductor-normal-metal-superconductor junction

    International Nuclear Information System (INIS)

    The zero-temperature current-phase (I-φ) relation (CPR) of a mesoscopic, ballistic, and asymmetrically stacked, double superconductor-normal-metal-superconduc tor (SNS) junction is studied. Here φ is the phase difference between the two superconducting end-electrodes. The lack of configuration symmetry in such asymmetric SNSNS junctions forbids a simple choice of values for the phase φ2 of the middle superconductor. We propose to determine the values of φ2 by equating the currents in the two normal regions. Two features in the CPR are found. First, the CPR of the asymmetric junction has a cutoff feature, whose origin is best demonstrated in the long middle superconductor (large L2) cases, when the critical current of the double SNS junction is bounded by the SNS junction that has the longer normal region. This cutoff feature is more pronounced for longer L2 and for higher degree of junction asymmetry. Second, in regions other than the cutoff region, the CPR of the asymmetric junction deviates only within a few percent from the CPR of the symmetric junction which has the same total length LTotal in the normal regions and the same L2. This is in contrast with the greater sensitivity the CPR has to the changes in LTotal or L2. (orig.)

  13. Phase relations and ionic transport behaviour in new mixed oxides of ceria–zirconia–gadolinia

    International Nuclear Information System (INIS)

    The present study investigates structure and the phase relations observed in complex oxide systems obtained by substituting Gd2O3 in the mixed oxide (Ce0.8Zr0.2)O2. The X-ray diffraction studies performed on this system revealed two single-phasic phase-fields; fluorite-type (F-type) and C-type. The transformation from F-type to C-type structure was observed at 60 mol% Gd3+ substitution. The Raman spectroscopic studies, however, reveal further fine structural insights wherein the F-type region was observed only up to 30 mol% of Gd3+ which was followed by the co-existence of C-type ordered region and F-type region. The single-phasic C-type phase-field was observed only beyond 80 mol% Gd3+-substitution. The AC impedance analysis revealed minimum in the activation energy and maximum in ionic conductivity values as a function of Gd3+-content. An antagonistic interplay of activation energy and pre-exponential factor is explained as the major factor behind this behaviour. The determination of migration and association energies supported the trend observed in the ionic conductivity values as a function of Gd3+-content. The activation energies for hopping are in good agreement with migration activation energies thus establishing that the conduction mechanism involved hopping of oxygen ions. - Highlights: • Presence of single-phasic F- and C-type phases was revealed by XRD studies. • Both, inter-anionic repulsions and ionic sizes governed the lattice parameters. • C-type micro domains in F-type region and vice versa observed by Raman spectra. • High conductivity of 30% Gd3+ doped sample agrees with low association energy. • Similar migration and hopping energies reveal the hopping mechanism for conduction

  14. Phase relations and ionic transport behaviour in new mixed oxides of ceria–zirconia–gadolinia

    Energy Technology Data Exchange (ETDEWEB)

    Anithakumari, P.; Grover, V., E-mail: vinita@barc.gov.in; Tyagi, A.K.

    2015-10-25

    The present study investigates structure and the phase relations observed in complex oxide systems obtained by substituting Gd{sub 2}O{sub 3} in the mixed oxide (Ce{sub 0.8}Zr{sub 0.2})O{sub 2}. The X-ray diffraction studies performed on this system revealed two single-phasic phase-fields; fluorite-type (F-type) and C-type. The transformation from F-type to C-type structure was observed at 60 mol% Gd{sup 3+} substitution. The Raman spectroscopic studies, however, reveal further fine structural insights wherein the F-type region was observed only up to 30 mol% of Gd{sup 3+} which was followed by the co-existence of C-type ordered region and F-type region. The single-phasic C-type phase-field was observed only beyond 80 mol% Gd{sup 3+}-substitution. The AC impedance analysis revealed minimum in the activation energy and maximum in ionic conductivity values as a function of Gd{sup 3+}-content. An antagonistic interplay of activation energy and pre-exponential factor is explained as the major factor behind this behaviour. The determination of migration and association energies supported the trend observed in the ionic conductivity values as a function of Gd{sup 3+}-content. The activation energies for hopping are in good agreement with migration activation energies thus establishing that the conduction mechanism involved hopping of oxygen ions. - Highlights: • Presence of single-phasic F- and C-type phases was revealed by XRD studies. • Both, inter-anionic repulsions and ionic sizes governed the lattice parameters. • C-type micro domains in F-type region and vice versa observed by Raman spectra. • High conductivity of 30% Gd{sup 3+} doped sample agrees with low association energy. • Similar migration and hopping energies reveal the hopping mechanism for conduction.

  15. Measurement of the atmospheric muon depth intensity relation with the NEMO Phase-2 tower

    Science.gov (United States)

    Aiello, S.; Ameli, F.; Anghinolfi, M.; Barbarino, G.; Barbarito, E.; Barbato, F.; Beverini, N.; Biagi, S.; Bouhadef, B.; Bozza, C.; Cacopardo, G.; Calamai, M.; Calí, C.; Capone, A.; Caruso, F.; Ceres, A.; Chiarusi, T.; Circella, M.; Cocimano, R.; Coniglione, R.; Costa, M.; Cuttone, G.; D'Amato, C.; D'Amico, A.; De Bonis, G.; De Luca, V.; Deniskina, N.; De Rosa, G.; Di Capua, F.; Distefano, C.; Fermani, P.; Flaminio, V.; Fusco, L. A.; Garufi, F.; Giordano, V.; Gmerk, A.; Grasso, R.; Grella, G.; Hugon, C.; Imbesi, M.; Kulikovskiy, V.; Larosa, G.; Lattuada, D.; Leismueller, K. P.; Leonora, E.; Litrico, P.; Lonardo, A.; Longhitano, F.; Lo Presti, D.; Maccioni, E.; Margiotta, A.; Martini, A.; Masullo, R.; Migliozzi, P.; Migneco, E.; Miraglia, A.; Mollo, C. M.; Mongelli, M.; Morganti, M.; Musico, P.; Musumeci, M.; Nicolau, C. A.; Orlando, A.; Papaleo, R.; Pellegrino, C.; Pellegriti, M. G.; Perrina, C.; Piattelli, P.; Pugliatti, C.; Pulvirenti, S.; Orselli, A.; Raffaelli, F.; Randazzo, N.; Riccobene, G.; Rovelli, A.; Sanguineti, M.; Sapienza, P.; Sciacca, V.; Sgura, I.; Simeone, F.; Sipala, V.; Speziale, F.; Spina, M.; Spitaleri, A.; Spurio, M.; Stellacci, S. M.; Taiuti, M.; Terreni, G.; Trasatti, L.; Trovato, A.; Ventura, C.; Vicini, P.; Viola, S.; Vivolo, D.

    2015-06-01

    The results of the analysis of the data collected with the NEMO Phase-2 tower, deployed at 3500 m depth about 80 km off-shore Capo Passero (Italy), are presented. Čerenkov photons detected with the photomultipliers tubes were used to reconstruct the tracks of atmospheric muons. Their zenith-angle distribution was measured and the results compared with Monte Carlo simulations. An evaluation of the systematic effects due to uncertainties on environmental and detector parameters is also included. The associated depth intensity relation was evaluated and compared with previous measurements and theoretical predictions. With the present analysis, the muon depth intensity relation has been measured up to 13 km of water equivalent.

  16. Two Phases of the Non-Commutative Quantum Mechanics with the Generalized Uncertainty Relations

    Science.gov (United States)

    Chung, Won Sang

    2016-04-01

    We consider the quantum mechanics on the noncommutative plane with the generalized uncertainty relations {Δ } x1 {Δ } x2 ge frac {θ }{2}, {Δ } p1 {Δ } p2 ge frac {bar {θ }}{2}, {Δ } xi {Δ } pi ge frac {hbar }{2}, {Δ } x1 {Δ } p2 ge frac {η }{2}. We show that the model has two essentially different phases which is determined by kappa = 1 + frac {1}{hbar 2 } (η 2 - θ bar {θ }). We construct a operator hat {π }i commuting with hat {x}j and discuss the harmonic oscillator model in two dimensional non-commutative space for three case κ > 0, κ = 0, κ < 0. Finally, we discuss the thermodynamics of a particle whose hamiltonian is related to the harmonic oscillator model in two dimensional non-commutative space.

  17. On Dual Phase-Space Relativity, the Machian Principle and Modified Newtonian Dynamics

    Directory of Open Access Journals (Sweden)

    Castro C.

    2005-04-01

    Full Text Available We investigate the consequences of the Mach’s principle of inertia within the context of the Dual Phase Space Relativity which is compatible with the Eddington-Dirac large numbers coincidences and may provide with a physical reason behind the observed anomalous Pioneer acceleration and a solution to the riddle of the cosmological constant problem. The cosmological implications of Non-Archimedean Geometry by assigning an upper impossible scale in Nature and the cosmological variations of the fundamental constants are also discussed. We study the corrections to Newtonian dynamics resulting from the Dual Phase Space Relativity by analyzing the behavior of a test particle in a modified Schwarzschild geometry (due to the the effects of the maximal acceleration that leads in the weak-field approximation to essential modifications of the Newtonian dynamics and to violations of the equivalence principle. Finally we follow another avenue and find modified Newtonian dynamics induced by the Yang’s Noncommutative Spacetime algebra involving a lower and upper scale in Nature.

  18. Tunable current-phase relation in double-dot Josephson junctions

    Science.gov (United States)

    Koch, Jens; Le Hur, Karyn

    2008-03-01

    The current-phase relation I() for a Josephson junction contains information about the microscopic nature of the Cooper pair transfer. In particular, junctions more complicated than the single tunnel junction exhibit characteristic non-sinusoidal forms. Here, we investigate the Josephson effect in a superconducting double dot device, similar to the devices studied experimentally by Y. A. Pashkin et al. [1] and E. Bibow et al. [2]. In the vicinity of a charge degeneracy line, the system reduces to a two-level system equivalent to a charge qubit. In this regime, we find that the interplay between sequential tunneling and cotunneling of Cooper pairs leads to a strongly non-sinusoidal current- phase relation, tunable via gate electrodes. We propose the measurement of I() in a SQUID configuration, analyze the implications of flux noise, and compare our results to different types of Josephson junctions such as single-dot systems and microbridges. [1] Y. A. Pashkin et al., Nature (London) 421 (2003), 823 [2] E. Bibow, P. Lafarge, L. L'evy, Phys. Rev. Lett. 88 (2002), 017003

  19. Electronic structure and crystal chemistry of TlBa sub 2 CuO sub 5 and related cuprate superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Mattheiss, L.F. (AT T Bell Laboratories, Murray Hill, New Jersey 07974 (USA))

    1990-12-01

    In contrast to the fixed Cu valence ({similar to}2+) in the Tl-bilayer cuprate superconductors, the average formal valence of Cu in the Tl-monolayer compounds TlBa{sub 2}Ca{sub {ital n}{minus}1}Cu{sub {ital n}}O{sub 2{ital n}+3} varies as (2+{ital n}{sup {minus}1})+. This characteristic is reflected in linear augmented-plane-wave band-structure results for the simplest {ital n}=1 member of this Tl-monolayer homologous series, TlBa{sub 2}CuO{sub 5}, where the filling ({similar to}0.16) of the planar Cu(3{ital d})-O(2{ital p}) {sigma}{sup *} band is reduced well below one-half. It is shown that the 50-50 Ba-La alloy is an appropriate parent'' compound for this {ital n}=1 phase since the half-filled-band condition is restored. For any member of this Tl-monolayer series, the optimal doping for high-temperature superconductivity should involve a combination of structural and chemical contributions.

  20. Dry chemistry and initiatory thermodynamics at the Metallurgical Laboratory

    International Nuclear Information System (INIS)

    The dry chemistry group Glenn T. Seaborg's direction in the New Chemistry site of the Metallurgical Laboratory was involved not only in the isolation of elementary plutonium but in the study of its phase behavior and chemistry and the physical properties of several metallic phases as well. In addition, the production of simple binary compounds (e.g., hydrides, nitrides, and silicides) was pursued. All of this was achieved on the microgram or milligram scale. When the pressure of metal production was less demanding, attention was turned (at the instigation of Wendell M. Latimer) to the thermochemistry of uranium and the transuranium elements. Other related thermodynamic problems, such as the volatilization of BeO, were subsequently subjects of concern. Anecdotal and historical aspects-as well as scientific matters-will be featured in this paper. More recent developments in still-crucial aspects of nuclear energy application will also be accommodated

  1. Fundamental studies of fuel chemistry as related to internal combustion engine phenomena. Technical progress report, July 1, 1988--June 30, 1989

    Energy Technology Data Exchange (ETDEWEB)

    Dryer, F.L.; Brezinsky, K.

    1989-07-01

    The present research effort was initiated with the intent of providing substantially improved insights (through homogeneous gas phase kinetic studies at different constant pressures) to the fuel chemistry issues important to autoignition in engines. The conditions of the proposed experiments were chosen to represent those similar to the engine parameters under knocking conditions: temperatures in the range of 700--1,100K, pressures from one to approximately 20 atmospheres and stoichiometries around one. A major part of the proposed research has been to design and construct a variable pressure flow reactor facility in which a range of reaction pressures, and in fact, lower reaction temperatures could be accessed. The reactor facility design and construction are nearly complete, and initial testing has begun to compare the overall experimental operating characteristics of the reactor with the design parameters. Experiments on Isobutene/oxygen mixtures have also been conducted in the existing atmospheric pressure flow reactor at about 1,150 K and in an equivalence ratio range of pyrolysis with about 100 ppm oxygen background to 0.42. A detailed kinetic model has been developed to interpret the pyrolysis and oxidation characteristics. 89 refs.

  2. Radiation Chemistry

    Science.gov (United States)

    Wojnárovits, L.

    Ionizing radiation causes chemical changes in the molecules of the interacting medium. The initial molecules change to new molecules, resulting in changes of the physical, chemical, and eventually biological properties of the material. For instance, water decomposes to its elements H2 and O2. In polymers, degradation and crosslinking take place. In biopolymers, e.g., DNS strand breaks and other alterations occur. Such changes are to be avoided in some cases (radiation protection), however, in other cases they are used for technological purposes (radiation processing). This chapter introduces radiation chemistry by discussing the sources of ionizing radiation (radionuclide sources, machine sources), absorption of radiation energy, techniques used in radiation chemistry research, and methods of absorbed energy (absorbed dose) measurements. Radiation chemistry of different classes of inorganic (water and aqueous solutions, inorganic solids, ionic liquids (ILs)) and organic substances (hydrocarbons, halogenated compounds, polymers, and biomolecules) is discussed in concise form together with theoretical and experimental backgrounds. An essential part of the chapter is the introduction of radiation processing technologies in the fields of polymer chemistry, food processing, and sterilization. The application of radiation chemistry to nuclear technology and to protection of environment (flue gas treatment, wastewater treatment) is also discussed.

  3. Diesel-related hydrocarbons can dominate gas phase reactive carbon in megacities

    Directory of Open Access Journals (Sweden)

    R. E. Dunmore

    2015-09-01

    Full Text Available Hydrocarbons are key precursors to two priority air pollutants, ozone and particulate matter. Those with two to seven carbons have historically been straightforward to observe and have been successfully reduced in many developed cities through air quality policy interventions. Longer chain hydrocarbons released from diesel vehicles are not considered explicitly as part of air quality strategies and there are few direct measurements of their gaseous abundance in the atmosphere. This study describes the chemically comprehensive and continuous measurements of organic compounds in a developed megacity (London, which demonstrate that on a seasonal median basis, diesel-related hydrocarbons represent only 20–30 % of the total hydrocarbon mixing ratio but comprise more than 50 % of the atmospheric hydrocarbon mass and are a dominant local source of secondary organic aerosols. This study shows for the first time that 60 % of the winter primary hydrocarbon hydroxyl radical reactivity is from diesel-related hydrocarbons and using the maximum incremental reactivity scale, we predict that they contribute up to 50 % of the ozone production potential in London. Comparing real-world urban composition with regulatory emissions inventories in the UK and US highlights a previously unaccounted for, but very significant, under-reporting of diesel-related hydrocarbons; an underestimation of a factor ~4 for C9 species rising to a factor of over 70 for C12 during winter. These observations show that hydrocarbons from diesel vehicles can dominate gas phase reactive carbon in cities with high diesel fleet fractions. Future control of urban particulate matter and ozone in such locations requires a shift in policy focus onto gas phase hydrocarbons released from diesels as this vehicle type continues to displace gasoline world-wide.

  4. Diesel-related hydrocarbons can dominate gas phase reactive carbon in megacities

    Directory of Open Access Journals (Sweden)

    R. E. Dunmore

    2015-03-01

    Full Text Available Hydrocarbons are key precursors to two priority air pollutants, ozone and particulate matter. Those with two to seven carbons have historically been straightforward to observe and have been successfully reduced in many developed cities through air quality policy interventions. Longer chain hydrocarbons released from diesel vehicles are not considered explicitly as part of air quality strategies and there are few direct measurements of their gaseous abundance in the atmosphere. This study describes the chemically comprehensive and continuous measurements of organic compounds in a developed megacity (London, which demonstrate that on a seasonal median basis, diesel-related hydrocarbons represent only 20–30% of the total hydrocarbon mixing ratio but comprise more than 50% of the atmospheric hydrocarbon mass and are a dominant local source of secondary organic aerosols. This study shows for the first time that, 60% of the winter primary hydrocarbon hydroxyl radical reactivity is from diesel-related hydrocarbons and using the maximum incremental reactivity scale, we predict that they contribute up to 50% of the ozone production potential in London. Comparing real-world urban composition with regulatory emissions inventories in the UK and US highlights a previously unaccounted for but, very significant under-reporting of diesel related hydrocarbons; an underestimation of a factor ~ 4 for C9 species rising to a factor of over 70 for C12 during winter. These observations show that hydrocarbons from diesel vehicles can dominate gas phase reactive carbon in cities with high diesel fleet fractions. Future control of urban particulate matter and ozone in such locations requires a shift in policy focus onto gas phase hydrocarbons released from diesels as this vehicle type continues to displace gasoline world-wide.

  5. Diesel-related hydrocarbons can dominate gas phase reactive carbon in megacities

    Science.gov (United States)

    Dunmore, R. E.; Hopkins, J. R.; Lidster, R. T.; Lee, J. D.; Evans, M. J.; Rickard, A. R.; Lewis, A. C.; Hamilton, J. F.

    2015-09-01

    Hydrocarbons are key precursors to two priority air pollutants, ozone and particulate matter. Those with two to seven carbons have historically been straightforward to observe and have been successfully reduced in many developed cities through air quality policy interventions. Longer chain hydrocarbons released from diesel vehicles are not considered explicitly as part of air quality strategies and there are few direct measurements of their gaseous abundance in the atmosphere. This study describes the chemically comprehensive and continuous measurements of organic compounds in a developed megacity (London), which demonstrate that on a seasonal median basis, diesel-related hydrocarbons represent only 20-30 % of the total hydrocarbon mixing ratio but comprise more than 50 % of the atmospheric hydrocarbon mass and are a dominant local source of secondary organic aerosols. This study shows for the first time that 60 % of the winter primary hydrocarbon hydroxyl radical reactivity is from diesel-related hydrocarbons and using the maximum incremental reactivity scale, we predict that they contribute up to 50 % of the ozone production potential in London. Comparing real-world urban composition with regulatory emissions inventories in the UK and US highlights a previously unaccounted for, but very significant, under-reporting of diesel-related hydrocarbons; an underestimation of a factor ~4 for C9 species rising to a factor of over 70 for C12 during winter. These observations show that hydrocarbons from diesel vehicles can dominate gas phase reactive carbon in cities with high diesel fleet fractions. Future control of urban particulate matter and ozone in such locations requires a shift in policy focus onto gas phase hydrocarbons released from diesels as this vehicle type continues to displace gasoline world-wide.

  6. Exploring Systematic Effects in the Relation Between Stellar Mass, Gas Phase Metallicity, and Star Formation Rate

    Science.gov (United States)

    Telford, O. Grace; Dalcanton, Julianne J.; Skillman, Evan D.; Conroy, Charlie

    2016-08-01

    There is evidence that the well-established mass–metallicity relation in galaxies is correlated with a third parameter: star formation rate (SFR). The strength of this correlation may be used to disentangle the relative importance of different physical processes (e.g., infall of pristine gas, metal-enriched outflows) in governing chemical evolution. However, all three parameters are susceptible to biases that might affect the observed strength of the relation between them. We analyze possible sources of systematic error, including sample bias, application of signal-to-noise ratio cuts on emission lines, choice of metallicity calibration, uncertainty in stellar mass determination, aperture effects, and dust. We present the first analysis of the relation between stellar mass, gas phase metallicity, and SFR using strong line abundance diagnostics from Dopita et al. for ∼130,000 star-forming galaxies in the Sloan Digital Sky Survey and provide a detailed comparison of these diagnostics in an appendix. Using these new abundance diagnostics yields a 30%–55% weaker anti-correlation between metallicity and SFR at fixed stellar mass than that reported by Mannucci et al. We find that, for all abundance diagnostics, the anti-correlation with SFR is stronger for the relatively few galaxies whose current SFRs are elevated above their past average SFRs. This is also true for the new abundance diagnostic of Dopita et al., which gives anti-correlation between Z and SFR only in the high specific star formation rate (sSFR) regime, in contrast to the recent results of Kashino et al. The poorly constrained strength of the relation between stellar mass, metallicity, and SFR must be carefully accounted for in theoretical studies of chemical evolution.

  7. Planetary nebulae: the universal mass-metallicity relation for Local Group dwarf galaxies and the chemistry of NGC 205

    CERN Document Server

    Gonçalves, D R; Teodorescu, Ana M; Carneiro, Carolina M

    2014-01-01

    Here we study 16 planetary nebulae (PNe) in the dwarf irregular galaxy NGC 205 by using GMOS@Gemini spectra to derive their physical and chemical parameters. The chemical patterns and evolutionary tracks for 14 of our PNe suggest that there are no type I PNe among them. These PNe have an average oxygen abundance of 12+log(O/H)=8.08$\\pm$0.28, progenitor masses of 2-2.5M$_{\\odot}$ and thus were born ~1.0-1.7Gyr ago. Our results are in good agreement with previous PN studies in NGC 205. The present 12+log(O/H) is combined with our previous works and with the literature to study the PN metallicity trends of the Local Group (LG) dwarf galaxies, in an effort to establish the PN luminosity- and mass-metallicity relations (LZR and MZR) for the LG dwarf irregulars (dIrrs) and dwarf spheroidals (dSphs). Previous attempts to obtain such relations failed to provide correct conclusions because were based on limited samples (Richer & McCall 1995; Gon\\c{c}calves et al. 2007). As far as we are able to compare stellar wit...

  8. From organic chemistry to fat and oil chemistry*

    OpenAIRE

    Deffense Etienne

    2009-01-01

    With his work on animal fat and identification of fatty acids, Chevreul was a pioneer in organic chemistry. As Chevreul, I had a passion for organic chemistry too. It was then, an honour and a pleasure to present in 2008 at EFL in Athens this presentation entitled “From organic chemistry to fat and oil chemistry” because my background in organic chemistry helped me all along my professional career to understand and implement new developments related to oil and fat technology and processing. A...

  9. Calculation of the relative chemical stabilities of proteins as a function of temperature and redox chemistry in a hot spring.

    Directory of Open Access Journals (Sweden)

    Jeffrey M Dick

    Full Text Available Uncovering the chemical and physical links between natural environments and microbial communities is becoming increasingly amenable owing to geochemical observations and metagenomic sequencing. At the hot spring known as Bison Pool in Yellowstone National Park, the cooling of the water in the outflow channel is associated with an increase in oxidation potential estimated from multiple field-based measurements. Representative groups of proteins whose sequences were derived from metagenomic data also exhibit an increase in average oxidation state of carbon in the protein molecules with distance from the hot-spring source. The energetic requirements of reactions to form selected proteins used in the model were computed using amino-acid group additivity for the standard molal thermodynamic properties of the proteins, and the relative chemical stabilities of the proteins were investigated by varying temperature, pH and oxidation state, expressed as activity of dissolved hydrogen. The relative stabilities of the proteins were found to track the locations of the sampling sites when the calculations included a function for hydrogen activity that increases with temperature and is higher, or more reducing, than values consistent with measurements of dissolved oxygen, sulfide and oxidation-reduction potential in the field. These findings imply that spatial patterns in the amino acid compositions of proteins can be linked, through energetics of overall chemical reactions representing the formation of the proteins, to the environmental conditions at this hot spring, even if microbial cells maintain considerably different internal conditions. Further applications of the thermodynamic calculations are possible for other natural microbial ecosystems.

  10. On the current-phase relation of diffusive superconductor/normal-conductor/superconductor Josephson contacts

    International Nuclear Information System (INIS)

    The aim of this thesis is to develop a measurement method based on micro-Hall probes, in order to measure the current-phase-relation (CPR) of mesoscopic diffusive SNS contacts. To achieve this the SNS junctions are built into superconducting loops, which are structured onto the 10 aem large active area of the Hall-probes by means of shadow evaporation. The Hall-probes are made of a GaAs/AlGaAs heterostructure, which develops a two-dimensional electron gas 200 nm below the surface. The phase gradient can then be controlled by applying an external magnetic flux to the loop. The response of the generated phase gradient is a circulating Josephson current in the loop, which also generates a magnetic flux. Through the detection of this flux by the Hall sensor the CPR can be measured. In this thesis the systems AlAu, AlAg, AlCu and NbAg are examined. In the high temperature regime of the Josephson effect a sinusoidal CPR is found as the theory states. At temperatures below 1 K a non-sinusoidal CPR containing higher harmonics is found. These higher harmonic contributions result from the high critical currents of the SNS contacts at low temperatures in combination with a inhomogenous spatial resolution of the Hall probes. These superimpose the intrinsic higher harmonics, which may exist. In conclusion, it was not possible to find any evidence of intrinsic higher harmonic contributions to the CPR, which result from MAR, within the accuracy range of the measurement. By reducing the maximum critical current of the SNS contacts, the influence of the inhomogeneous spatial resolution of the sensors could be reduced and the intrinsic higher harmonics could be detected unambiguously. This could be done by reducing the geometry of the normal metal in order to increase the normal resistance

  11. Quantum chemistry

    CERN Document Server

    Lowe, John P

    2006-01-01

    Lowe's new edition assumes little mathematical or physical sophistication and emphasizes an understanding of the techniques and results of quantum chemistry. It can serve as a primary text in quantum chemistry courses, and enables students and researchers to comprehend the current literature. This third edition has been thoroughly updated and includes numerous new exercises to facilitate self-study and solutions to selected exercises.* Assumes little initial mathematical or physical sophistication, developing insights and abilities in the context of actual problems* Provides thorough treatment

  12. Polymer Chemistry

    Science.gov (United States)

    Williams, Martha; Roberson, Luke; Caraccio, Anne

    2010-01-01

    This viewgraph presentation describes new technologies in polymer and material chemistry that benefits NASA programs and missions. The topics include: 1) What are Polymers?; 2) History of Polymer Chemistry; 3) Composites/Materials Development at KSC; 4) Why Wiring; 5) Next Generation Wiring Materials; 6) Wire System Materials and Integration; 7) Self-Healing Wire Repair; 8) Smart Wiring Summary; 9) Fire and Polymers; 10) Aerogel Technology; 11) Aerogel Composites; 12) Aerogels for Oil Remediation; 13) KSC's Solution; 14) Chemochromic Hydrogen Sensors; 15) STS-130 and 131 Operations; 16) HyperPigment; 17) Antimicrobial Materials; 18) Conductive Inks Formulations for Multiple Applications; and 19) Testing and Processing Equipment.

  13. Current ADC Linker Chemistry

    OpenAIRE

    Jain, Nareshkumar; Smith, Sean W.; Ghone, Sanjeevani; Tomczuk, Bruce

    2015-01-01

    The list of ADCs in the clinic continues to grow, bolstered by the success of first two marketed ADCs: ADCETRIS® and Kadcyla®. Currently, there are 40 ADCs in various phases of clinical development. However, only 34 of these have published their structures. Of the 34 disclosed structures, 24 of them use a linkage to the thiol of cysteines on the monoclonal antibody. The remaining 10 candidates utilize chemistry to surface lysines of the antibody. Due to the inherent heterogeneity of conjugati...

  14. Non-sinusoidal current-phase relations in SFS pi-Josephson junctions

    Science.gov (United States)

    van Harlingen, Dale J.

    2010-03-01

    We report the direct observation of a sin(2φ) component in the current-phase relation (CPR) of Superconductor-Ferromagnet-Superconductor (SFS) Josephson junctions. The deviation from a sinusoidal CPR is most evident near the crossover between the 0-junction to π-junction states reached by tuning the thickness of the ferromagnet barrier and the temperature. We measure the CPR in Nb-CuNi-Nb junctions using a phase-sensitive Josephson interferometer technique in which the junctions are incorporated into a superconducting loop coupled to a dc SQUID. We correlate the CPR data with measurements of subharmonic Shapiro steps and anomalous critical current diffraction patterns that have previously been cited as evidence for higher-order Josephson tunneling components. We will discuss possible origins and implications for the non-sinusoidal component. In collaboration with M.J.A. Stoutimore (University of Illinois at Urbana-Champaign) and A.Yu. Rusanov, V.A. Oboznov, V.V. Bolginov, A.N. Rossolenko, and V.V. Ryazanov (Institute of Solid State Physics, Russian Academy of Sciences, Chernogolovka, Russia).

  15. Relations between the kinetic equation and the Langevin models in two-phase flow modelling

    International Nuclear Information System (INIS)

    The purpose of this paper is to discuss PDF and stochastic models which are used in two-phase flow modelling. The aim of the present analysis is essentially to try to determine relations and consistency between different models. It is first recalled that different approaches actually correspond to PDF models written either in terms of the process trajectories or in terms of the PDF itself. The main difference lies in the choice of the independent variables which are retained. Two particular models are studied, the Kinetic Equation and the Langevin Equation model. The latter uses a Langevin equation to model the fluid velocities seen along particle trajectories. The Langevin model is more general since it contains an additional variable. It is shown that, in certain cases, this variable can be summed up exactly to retrieve the Kinetic Equation model as a marginal PDF. A joint fluid and solid particle PDF which includes the characteristics of both phases is proposed at the end of the paper. (author)

  16. Variation of solar acoustic emission and its relation to phase of the solar cycle

    Science.gov (United States)

    Chen, Ruizhu; Zhao, Junwei

    2016-05-01

    Solar acoustic emission is closely related to solar convection and photospheric magnetic field. Variation of acoustic emission and its relation to the phase of solar cycles are important to understand dynamics of solar cycles and excitation of acoustic waves. In this work we use 6 years of SDO/HMI Dopplergram data to study acoustic emissions of the whole sun and of the quiet-sun regions, respectively, in multiple acoustic frequency bands. We show the variation of acoustic emission from May 2010 to April 2016, covering half of the solar cycle 24, and analyze its correlation with the solar activity level indexed by daily sunspot number and total magnetic flux. Results show that the correlation between the whole-Sun acoustic emission and the solar activity level is strongly negative for low frequencies between 2.5 and 4.5 mHz, but strongly positive for high frequencies between 4.5 and 6.0 mHz. For high frequencies, the acoustic emission excess in sunspot halos overwhelms the emission deficiency in sunspot umbrae and penumbrae. The correlation between the acoustic emission in quiet regions and the solar activity level is negative for 2.5-4.0 mHz and positive for 4.0-5.5 mHz. This shows that the solar background acoustic power, with active regions excluded, also varies during a solar cycle, implying the excitation frequencies or depths are highly related to the solar magnetic field.

  17. Precortical Phase of Alzheimer's Disease (AD)-Related Tau Cytoskeletal Pathology.

    Science.gov (United States)

    Stratmann, Katharina; Heinsen, Helmut; Korf, Horst-Werner; Del Turco, Domenico; Ghebremedhin, Estifanos; Seidel, Kay; Bouzrou, Mohamed; Grinberg, Lea T; Bohl, Jürgen; Wharton, Stephen B; den Dunnen, Wilfred; Rüb, Udo

    2016-05-01

    Alzheimer's disease (AD) represents the most frequent progressive neuropsychiatric disorder worldwide leading to dementia. We systematically investigated the presence and extent of the AD-related cytoskeletal pathology in serial thick tissue sections through all subcortical brain nuclei that send efferent projections to the transentorhinal and entorhinal regions in three individuals with Braak and Braak AD stage 0 cortical cytoskeletal pathology and fourteen individuals with Braak and Braak AD stage I cortical cytoskeletal pathology by means of immunostainings with the anti-tau antibody AT8. These investigations revealed consistent AT8 immunoreactive tau cytoskeletal pathology in a subset of these subcortical nuclei in the Braak and Braak AD stage 0 individuals and in all of these subcortical nuclei in the Braak and Braak AD stage I individuals. The widespread affection of the subcortical nuclei in Braak and Braak AD stage I shows that the extent of the early subcortical tau cytoskeletal pathology has been considerably underestimated previously. In addition, our novel findings support the concept that subcortical nuclei become already affected during an early 'pre-cortical' evolutional phase before the first AD-related cytoskeletal changes occur in the mediobasal temporal lobe (i.e. allocortical transentorhinal and entorhinal regions). The very early involved subcortical brain regions may represent the origin of the AD-related tau cytoskeletal pathology, from where the neuronal cytoskeletal pathology takes an ascending course toward the secondarily affected allocortex and spreads transneuronally along anatomical pathways in predictable sequences. PMID:26193084

  18. Cardiovascular-related proteins identified in human plasma by the HUPO Plasma Proteome Project pilot phase.

    Science.gov (United States)

    Berhane, Beniam T; Zong, Chenggong; Liem, David A; Huang, Aaron; Le, Steven; Edmondson, Ricky D; Jones, Richard C; Qiao, Xin; Whitelegge, Julian P; Ping, Peipei; Vondriska, Thomas M

    2005-08-01

    Proteomic profiling of accessible bodily fluids, such as plasma, has the potential to accelerate biomarker/biosignature development for human diseases. The HUPO Plasma Proteome Project pilot phase examined human plasma with distinct proteomic approaches across multiple laboratories worldwide. Through this effort, we confidently identified 3020 proteins, each requiring a minimum of two high-scoring MS/MS spectra. A critical step subsequent to protein identification is functional annotation, in particular with regard to organ systems and disease. Performing exhaustive literature searches, we have manually annotated a subset of these 3020 proteins that have cardiovascular-related functions on the basis of an existing body of published information. These cardiovascular-related proteins can be organized into eight groups: markers of inflammation and/or cardiovascular disease, vascular and coagulation, signaling, growth and differentiation, cytoskeletal, transcription factors, channels/receptors and heart failure and remodeling. In addition, analysis of the peptide per protein ratio for MS/MS identification reveals group-specific trends. These findings serve as a resource to interrogate the functions of plasma proteins, and moreover, the list of cardiovascular-related proteins in plasma constitutes a baseline proteomic blueprint for the future development of biosignatures for diseases such as myocardial ischemia and atherosclerosis. PMID:16052623

  19. Deflection of polarised radiation - Relative phase delay technique. [photon geodesic motion variations

    Science.gov (United States)

    Dennison, B.; Melnick, G.; Harwit, M.; Sato, T.; Stelzried, C. T.; Jauncey, D.

    1978-01-01

    The article discusses the geodesic motion of photons, considering particularly whether oppositely polarized photons fall at the same rate. It is assumed that orthogonally polarized photons would be equally deflected by the gravitational field of a nonrotating mass. Upon the introduction of rotation, the angular momentum of the deflecting source couples to the photon spin through gravitational field action. Thus there arise separate trajectories for orthogonal polarizations. Searching for changes in polarization in a deflected beam is accomplished by a relative phase delay technique. If the beam is split into orthogonal linear polarization, final polarization is elliptical. Experiments have been performed on searching for ellipticity developments in the linearly polarized carrier waves from Helios 1 and 2, and the results are presented.

  20. Solving dispersion relation integrals with phase space of two different particles

    International Nuclear Information System (INIS)

    The theoretical determination of approximate low energy kaon-pion scattering amplitude from Chiral Perturbation Theory (ChPT) follows from the calculation of graphs using well established rules. The complexity of the calculation increases with the order of the approximation. Another method consists in solving dispersion relation integrals, however the computational difficulties take place again, because the integrals become more and more involved for higher orders in perturbative unitarity. In this work, we present a method to obtain the analytical solution of many integrals involving the phase space factor for two different masses. These integrals are needed for kaon and pion vector and scalar form factor calculations, for instance. This is a first step towards the construction of a kaon-pion scattering amplitude, equivalent to a ChPT two-loop corrected one, which is not available in the literature up to the present moment. (author)

  1. A recent accretion burst in the low-mass protostar IRAS 15398-3359: ALMA imaging of its related chemistry

    CERN Document Server

    Jorgensen, Jes K; Sakai, Nami; Bergin, Edwin A; Brinch, Christian; Harsono, Daniel; Lindberg, Johan E; van Dishoeck, Ewine F; Yamamoto, Satoshi; Bisschop, Suzanne E; Persson, Magnus V

    2013-01-01

    Low-mass protostars have been suggested to show highly variable accretion rates through-out their evolution. Such changes in accretion, and related heating of their ambient envelopes, may trigger significant chemical variations on different spatial scales and from source-to-source. We present images of emission from C17O, H13CO+, CH3OH, C34S and C2H toward the low-mass protostar IRAS 15398-3359 on 0.5" (75 AU diameter) scales with the Atacama Large Millimeter/submillimeter Array (ALMA) at 340 GHz. The resolved images show that the emission from H13CO+ is only present in a ring-like structure with a radius of about 1-1.5" (150-200 AU) whereas the CO and other high dipole moment molecules are centrally condensed toward the location of the central protostar. We propose that HCO+ is destroyed by water vapor present on small scales. The origin of this water vapor is likely an accretion burst during the last 100-1000 years increasing the luminosity of IRAS 15398-3359 by a factor of 100 above its current luminosity....

  2. Chemistry, photophysics, and ultrafast kinetics of two structurally related Schiff bases containing the naphthalene or quinoline ring

    Science.gov (United States)

    Fita, P.; Luzina, E.; Dziembowska, T.; Radzewicz, Cz.; Grabowska, A.

    2006-11-01

    The two structurally related Schiff bases, 2-hydroxynaphthylidene-(8-aminoquinoline) (HNAQ) and 2-hydroxynaphthylidene-1'-naphthylamine (HNAN), were studied by means of steady-state and time resolved optical spectroscopies as well as time-dependent density functional theory (TDDFT) calculations. The first one, HNAQ, is stable as a keto tautomer in the ground state and in the excited state in solutions, therefore it was used as a model of a keto tautomer of HNAN which exists mainly in its enol form in the ground state at room temperature. Excited state intramolecular proton transfer in the HNAN molecule leads to a very weak (quantum yield of the order of 10-4) strongly Stokes-shifted fluorescence. The characteristic time of the proton transfer (about 30fs) was estimated from femtosecond transient absorption data supported by global analysis and deconvolution techniques. Approximately 35% of excited molecules create a photochromic form whose lifetime was beyond the time window of the experiment (2ns). The remaining ones reach the relaxed S1 state (of a lifetime of approximately 4ps), whose emission is present in the decay associated difference spectra. Some evidence for the back proton transfer from the ground state of the keto form with the characteristic time of approximately 13ps was also found. The energies and orbital characteristics of main electronic transitions in both molecules calculated by TDDFT method are also discussed.

  3. Storytelling with Chemistry and Related Hands-on Activities: Informal Learning Experiences to Prevent "Chemophobia" and Promote Young Children's Scientific Literacy

    Science.gov (United States)

    Morais, Carla

    2015-01-01

    The dissemination of chemistry has been experienced as a difficult task, largely because of the negative image that the public has of this science, but also because of its inherent complexity and its own semantics and symbolism. Science centers, as informal learning environments, can contribute to a more effective dissemination of chemistry to an…

  4. Climate-related Changes in Tropical-fruit Flowering Phases in Songkhla Province, Southern Thailand

    Directory of Open Access Journals (Sweden)

    Supakracha Apiratikorn

    2014-04-01

    Full Text Available Changes in the timing of plant phenological phases in response to anomalous climate variability and the ongoing anthropogenic climate change have recently been studied in southern Thailand. In this study, we showed the evidence of climate-related changes in flowering phases of 2 tropical-fruit species: mangosteen (Garcinia mangostana and longkong (Lansium domesticum Corr. during 2003-2012. The flowering dates of these tropical fruits recorded at Hat Yai district, Songkhla province and daily climate data were used to assess phenophase response to variations in rainfall and evaporation. With the observed changes in local climate conditions which are defining factors for phenological development of tropical fruits particularly in southern Thailand, the flowering dates of both tropical fruits during 2003-2012 have significantly delayed comparing with the regular pattern in the past. Paradoxically, below-than-normal rainfall was also found in the El Niño years, while La Niña years were found in opposite. In summary, rainfall variations in Hat Yai district, Songkhla province are associated with ENSO. It was evident that the flowering period of tropical fruits tended to shift to the second-half of the year instead of the first-half of the year as usual. The results revealed that, during 33 years (1980-2012, annual rainfall totals, the annual number of rainy days, relative humidity, maximum and minimum temperatures from the Thai Meteorological Department significantly increased by 29.5 mm/year, 0.83 day/year, 0.116 %/year, 0.033 and 0.035C/year, respectively. These findings suggest that anthropogenically warm climate and its associated inter-annual variations in local weather patterns may to the great extent influence on tropical-fruit phenology and their responses to recent climate change seem to be complex and nonlinear. Therefore, further study is needed to shed more light on such causal-effect linkages and plausible underlying mechanisms.

  5. Water quality in the vicinity of Mosquito Creek Lake, Trumbull County, Ohio, in relation of the chemistry of locally occurring oil, natural gas, and brine

    International Nuclear Information System (INIS)

    The purpose of this report is to describe current water quality and the chemistry of oil, natural gas, and brine in the Mosquito Creek Lake area. Additionally, these data are used to characterize water quality in the Mosquito Creek Lake area in relation to past oil and natural gas well drilling and production. To meet the overall objective, several goals for this investigation were established. These include (1) collect water-quality and subsurface-gas data from shallow sediments and rock that can be used for future evaluation of possible effects of oil and natural gas well drilling and production on water supplies, (2) characterize current surface-water and ground-water quality as it relates to the natural occurrence and (or) release of oil, gas, and brine (3) sample and chemically characterize the oil in the shallow Mecca Oil Pool, gas from the Berea and Cussewago Sandstone aquifers, and the oil, gas, and brine from the Clinton sandstone, and (4) identify areas where aquifers are vulnerable to contamination from surface spills at oil and natural gas drilling and production sites

  6. Water quality in the vicinity of Mosquito Creek Lake, Trumbull County, Ohio, in relation of the chemistry of locally occurring oil, natural gas, and brine

    Energy Technology Data Exchange (ETDEWEB)

    Barton, G.J.; Burruss, R.C.; Ryder, R.T.

    1998-12-31

    The purpose of this report is to describe current water quality and the chemistry of oil, natural gas, and brine in the Mosquito Creek Lake area. Additionally, these data are used to characterize water quality in the Mosquito Creek Lake area in relation to past oil and natural gas well drilling and production. To meet the overall objective, several goals for this investigation were established. These include (1) collect water-quality and subsurface-gas data from shallow sediments and rock that can be used for future evaluation of possible effects of oil and natural gas well drilling and production on water supplies, (2) characterize current surface-water and ground-water quality as it relates to the natural occurrence and (or) release of oil, gas, and brine (3) sample and chemically characterize the oil in the shallow Mecca Oil Pool, gas from the Berea and Cussewago Sandstone aquifers, and the oil, gas, and brine from the Clinton sandstone, and (4) identify areas where aquifers are vulnerable to contamination from surface spills at oil and natural gas drilling and production sites.

  7. Organic chemistry

    International Nuclear Information System (INIS)

    The activities of the mycotoxin research group are discussed. This includes the isolation and structure determination of mycotoxins, plant products, the biosyntheris of mycotoxins, the synthesis and characteristics of steroids, the synthesis and mechanistic aspects of heterocyclic chemistry and the functionality of steroids over long distances. Nmr spectra and mass spectroscopy are some of the techniques used

  8. 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.

  9. 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…

  10. News from Online: Green Chemistry

    Science.gov (United States)

    Uffelman, Erich S.

    2004-01-01

    Green chemistry closely relates to energy and environmental problems, and includes the promotion of environmental friendly products and systems within the framework of renewable resources. Various websites on green chemistry are reviewed, one of which lists the 12 commandments of this particular subject.

  11. On the relative stability of the α-, β- and ω-phases in some Zr-based alloys

    International Nuclear Information System (INIS)

    The dependence of the thermodynamic stability of the h.c.p.-α-phase of Zr alloys on the content of different solutes has acquired great technological importance on the nuclear industry. In what follows, some aspects of the relative stability of h.c.p. α-and hexagonal ω-phases in equiatomic ZrTi will be discussed and the influence of two interstitial solutes, O and N, will be considered. It is well known that in dilute solutions of O and N in pure Zr and Ti, the h.c.p. ''alpha-phase is stabilized with respect to the b.c.c. β-phase. However, in equiatomic ZrTi the influence of these interstitial solutes is reversed, the β-phase being stabilized with respect to α, as well shall demonstrate here by experimental results obtained using electrical resistivity, optical and electronic metallography, and X-rays. Moreover, upon cooling from the β-ZrTi single-phase region, these interstitial solutes also induce the precipitation of metastable ω in the β-matrix. Our discussion of the influence of interstitial O and N on the relative stability of α and ω-phases leads us to reconsider some recent experimental results suggesting that the ω-phase is stable in pure Zr ar atmospheric pressure below room temperature. We conclude that this suggested stability must be related to contamination by interstitials. (author)

  12. Bayesian Modeling of the Dynamics of Phase Modulations and their Application to Auditory Event Related Potentials at Different Loudness Scales.

    Science.gov (United States)

    Mortezapouraghdam, Zeinab; Wilson, Robert C; Schwabe, Lars; Strauss, Daniel J

    2016-01-01

    We study the effect of long-term habituation signatures of auditory selective attention reflected in the instantaneous phase information of the auditory event-related potentials (ERPs) at four distinct stimuli levels of 60, 70, 80, and 90 dB SPL. The analysis is based on the single-trial level. The effect of habituation can be observed in terms of the changes (jitter) in the instantaneous phase information of ERPs. In particular, the absence of habituation is correlated with a consistently high phase synchronization over ERP trials. We estimate the changes in phase concentration over trials using a Bayesian approach, in which the phase is modeled as being drawn from a von Mises distribution with a concentration parameter which varies smoothly over trials. The smoothness assumption reflects the fact that habituation is a gradual process. We differentiate between different stimuli based on the relative changes and absolute values of the estimated concentration parameter using the proposed Bayesian model. PMID:26858631

  13. Advances in electron transfer chemistry

    CERN Document Server

    Mariano, Patrick S

    1993-01-01

    Advances in Electron Transfer Chemistry, Volume 3 presents studies that discuss findings in the various aspects of electron chemistry. The book is comprised of four chapters; each chapter reviews a work that tackles an issue in electron transfer chemistry. Chapter 1 discusses the photoinduced electron transfer in flexible biaryl donor-acceptor molecules. Chapter 2 tackles light-induced electron transfer in inorganic systems in homogeneous and heterogeneous phases. The book also covers internal geometry relaxation effects on electron transfer rates of amino-centered systems. The sequential elec

  14. Chemistry in Protoplanetary Disks

    OpenAIRE

    Henning, Thomas; Semenov, Dmitry

    2013-01-01

    This comprehensive review summarizes our current understanding of the evolution of gas, solids and molecular ices in protoplanetary disks. Key findings related to disk physics and chemistry, both observationally and theoretically, are highlighted. We discuss which molecular probes are used to derive gas temperature, density, ionization state, kinematics, deuterium fractionation, and study organic matter in protoplanetary disks.

  15. Progress in physical chemistry

    CERN Document Server

    Hempelmann, Rolf

    2008-01-01

    Progress in Physical Chemistry is a collection of recent ""Review Articles"" published in the ""Zeitschrift für Physikalische Chemie"". The second volume of Progress in Physical Chemistry is a collection of thematically closely related minireview articles written by the members of the Collaborative Research Centre (SFB) 277 of the German Research Foundation (DFG). These articles are based on twelve years of intense coordinated research efforts. Central topics are the synthesis and the characterization of interface-dominated, i.e. nanostructured materials, mainly in the solid state but also as

  16. A new titanium-bearing calcium aluminosilicate phase. 2: Crystallography and crystal chemistry of grains formed in slowly cooled melts with bulk compositions of calcium-aluminium-rich inclusions

    Science.gov (United States)

    Barber, David J.; Beckett, John R.; Paque, Julie M.; Stolper, Edward

    1994-01-01

    The crystallography and crystal chemistry of a new calcium- titanium-aluminosilicate mineral (UNK) observed in synthetic analogs to calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrites was studied by electron diffraction techniques. The unit cell is primitive hexagonal or trigonal, with a = 0.790 +/- 0.02 nm and c = 0.492 +/- 0.002 nm, similar to the lattice parameters of melilite and consistent with cell dimensions for crystals in a mixer furnace slag described by Barber and Agrell (1994). The phase frequently displays an epitactic relationship in which melilite acts as the host, with (0001)(sub UNK) parallel (001)(sub mel) and zone axis group 1 0 -1 0(sub UNK) parallel zone axis group 1 0 0(sub mel). If one of the two space groups determined by Barber and Agrell (1994) for their sample of UNK is applicable (P3m1 or P31m), then the structure is probably characterized by puckered sheets of octahedra and tetrahedra perpendicular to the c-axis with successive sheets coordinated by planar arrays of Ca. In this likely structure, each unit cell contains three Ca sites located in mirror planes, one octahedrally coordinated cation located along a three-fold axis and five tetrahedrally coordinated cations, three in mirrors and two along triads. The octahedron contains Ti but, because there are 1.3-1.9 cations of Ti/formula unit, some of the Ti must also be in tetrahedral coordination, an unusual but not unprecedented situation for a silicate. Tetrahedral sites in mirror planes would contain mostly Si, with lesser amounts of Al while those along the triads correspondingly contain mostly Al with subordinate Ti. The structural formula, therefore, can be expressed as Ca(sub 3)(sup VIII)(Ti,Al)(sup VI)(Al,Ti,Si)(sub 2)(sup IV)(Si,Al)(sub 3)(sup IV)O14 with Si + Ti = 4. Compositions of meteoritic and synthetic Ti-bearing samples of the phase can be described in terms of a binary solid solution between the end-members Ca3TiAl2Si3O14 and Ca3Ti(AlTi)(AlSi2)O14. A Ti

  17. Revitalizing chemistry laboratory instruction

    Science.gov (United States)

    McBride, Phil Blake

    This dissertation involves research in three major domains of chemical education as partial fulfillment of the requirements for the Ph.D. program in chemistry at Miami University with a major emphasis on chemical education, and concurrent study in organic chemistry. Unit I, Development and Assessment of a Column Chromatography Laboratory Activity, addresses the domain of Instructional Materials Development and Testing. This unit outlines the process of developing a publishable laboratory activity, testing and revising that activity, and subsequently sharing that activity with the chemical education community. A laboratory activity focusing on the separation of methylene blue and sodium fluorescein was developed to demonstrate the effects of both the stationary and mobile phase in conducting a separation. Unit II, Bringing Industry to the Laboratory, addresses the domain of Curriculum Development and Testing. This unit outlines the development of the Chemistry of Copper Mining module, which is intended for use in high school or undergraduate college chemistry. The module uses the learning cycle approach to present the chemistry of the industrial processes of mining copper to the students. The module includes thirteen investigations (three of which are web-based and ten which are laboratory experiments) and an accompanying interactive CD-ROM, which provides an explanation of the chemistry used in copper mining with a virtual tour of an operational copper mine. Unit III, An Alternative Method of Teaching Chemistry. Integrating Lecture and the Laboratory, is a project that addresses the domain of Research in Student Learning. Fundamental Chemistry was taught at Eastern Arizona College as an integrated lecture/laboratory course that met in two-hour blocks on Monday, Wednesday, and Friday. The students taking this integrated course were compared with students taking the traditional 1-hour lectures held on Monday, Wednesday, and Friday, with accompanying 3-hour lab on

  18. Phase relations in the lanthanum nitrate (copper nitrate) - poly(vinylpyrrolidone) - water systems

    International Nuclear Information System (INIS)

    Room-temperature isothermal sections of the phase diagrams of lanthanum nitrate-poly(vinylpyrrolidone)-water and copper nitrate-poly(vinylpyrrolidone)-water systems were studied. The following features were found: a wide region of homogeneous water-polymer solutions, liquid-liquid phase separation field, and a three-phase region in which two liquids coexist with salt crystals. In the lanthanum nitrate system, liquid-liquid phase separation has a lower critical solution point (polythermal sections were studied); in the copper nitrate system, it has an upper critical solution point. The type of diagram for unstudied systems is predicted based on the analysis of polymer-salt phase diagrams

  19. Emission and chemistry of organic carbon in the gas and aerosol phase at a sub-urban site near Mexico City in March 2006 during the MILAGRO study

    Directory of Open Access Journals (Sweden)

    J. A. de Gouw

    2009-05-01

    Full Text Available Volatile organic compounds (VOCs and carbonaceous aerosol were measured at a sub-urban site near Mexico City in March of 2006 during the MILAGRO study (Megacity Initiative: Local and Global Research Objectives. Diurnal variations of hydrocarbons, elemental carbon (EC and hydrocarbon-like organic aerosol (HOA were dominated by a high peak in the early morning when local emissions accumulated in a shallow boundary layer, and a minimum in the afternoon when the emissions were diluted in a significantly expanded boundary layer and, in case of the reactive gases, removed by OH. In comparison, diurnal variations of species with secondary sources such as the aldehydes, ketones, oxygenated organic aerosol (OOA and water-soluble organic carbon (WSOC stayed relatively high in the afternoon indicating strong photochemical formation. Emission ratios of many hydrocarbon species relative to CO were higher in Mexico City than in the U.S., but we found similar emission ratios for most oxygenated VOCs and organic aerosol. Secondary formation of acetone may be more efficient in Mexico City than in the U.S., due to higher emissions of alkane precursors from the use of liquefied petroleum gas. Secondary formation of organic aerosol was similar between Mexico City and the U.S. Combining the data for all measured gas and aerosol species, we describe the budget of total observed organic carbon (TOOC, and find that the enhancement ratio of TOOC relative to CO is conserved between the early morning and mid afternoon despite large compositional changes. Finally, the influence of biomass burning is investigated using the measurements of acetonitrile, which was found to correlate with levoglucosan in the particle phase. Diurnal variations of acetonitrile indicate a contribution from local burning sources. Scatter plots of acetonitrile versus CO suggest that the contribution of biomass burning to the enhancement of most gas and aerosol species was not dominant and perhaps

  20. Emission and chemistry of organic carbon in the gas and aerosol phase at a sub-urban site near Mexico City in March 2006 during the MILAGRO study

    Directory of Open Access Journals (Sweden)

    J. A. de Gouw

    2008-12-01

    Full Text Available Volatile organic compounds (VOCs and carbonaceous aerosol were measured at a sub-urban site near Mexico City in March of 2006 during the MILAGRO study (Megacity Initiative: Local and Global Research Objectives. Diurnal variations of hydrocarbons, elemental carbon (EC and hydrocarbon-like organic aerosol (HOA were dominated by a high peak in the early morning when local emissions accumulated in a shallow boundary layer, and a minimum in the afternoon when the emissions were diluted in a significantly expanded boundary layer and, in case of the reactive gases, removed by OH. In comparison, diurnal variations of species with secondary sources such as the aldehydes, ketones, oxygenated organic aerosol (OOA and water-soluble organic carbon (WSOC stayed relatively high in the afternoon indicating strong photochemical formation. Emission ratios of many hydrocarbon species relative to CO were higher in Mexico City than in the US, but we found similar emission ratios for most oxygenated VOCs and organic aerosol. Secondary formation of acetone may be more efficient in Mexico City than in the US, due to higher emissions of alkane precursors from the use of liquefied petroleum gas. Secondary formation of organic aerosol was similar between Mexico City and the US. Combining the data for all measured gas and aerosol species, we describe the budget of total observed organic carbon (TOOC, and find that the enhancement ratio of TOOC relative to CO is conserved between the early morning and mid afternoon despite large compositional changes. Finally, the influence of biomass burning is investigated using the measurements of acetonitrile, which was found to correlate with levoglucosan in the particle phase. Diurnal variations of acetonitrile indicate a contribution from local burning sources. Scatter plots of acetonitrile versus CO suggest that the contribution of biomass burning to the enhancement of most gas and aerosol species was not dominant and perhaps not

  1. A handbook of nuclear water chemistry

    International Nuclear Information System (INIS)

    This contents is divided three parts. The first part deals with chemistry which is related water nuclear energy. So it explains the role of water in atomic reactor including the basic properties of water, the oxide chemistry electricity chemistry, radiochemistry and measuring techniques of the quality of water in nuclear plant and radiation. The second part introduces technique of nuclear water chemistry, which explains purpose, definition and speciality of water chemistry in light-water reactor. The third part indicates application technology of water chemistry in nuclear energy including putting zinc in light-water reactor and technology of surveillance of leakage in steam generator.

  2. GEM-AQ, an on-line global multiscale chemical weather system: model description and evaluation of gas phase chemistry processes

    OpenAIRE

    Kaminski, J.W.; L. Neary; Struzewska, J.; Mcconnell, J. C.; A. Lupu; J. Jarosz; K. Toyota; Gong, S. L.; Côté, J; Liu, X; Chance, K.; Richter, A

    2007-01-01

    Tropospheric chemistry and air quality processes were implemented on-line in the Global Environmental Multiscale model. The integrated model, GEM-AQ, has been developed as a platform to investigate chemical weather at scales from global to urban. The model was exercised for five years (2001–2005) to evaluate its ability to simulate seasonal variations and regional distributions of trace gases such as ozone, nitrogen dioxide and carbon monoxide on the global scale. The model results ...

  3. Fine chemistry

    International Nuclear Information System (INIS)

    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

  4. Investigation of Attitudes of Students in The Programs of Class Teaching, and Science Teaching Towards Chemistry Lesson, and The Relation Between Their Multiple Intelligence Fields and Their Success in Chemistry and Language Lessons

    OpenAIRE

    Hasan ÖZYILDIRIM; Hüsnüye DURMAZ

    2005-01-01

    The basis of Multiple Intelligence Theory contains development and learning during life time. According to this theory all human have different intelligences which are verbal-linguistic, logical-mathematical, visual-spatial, bodily-kinesthetic, musical, interpersonal, intrapersonal and naturalist intelligences in varying amounts.In this study, the attitude toward Chemistry Lesson, the Multiple Intelligence Fields of the 1st class students in the program of Class Teaching and Science Teaching ...

  5. Organometallic chemistry

    OpenAIRE

    Bashkin, James K.; M.L.H. Green; Dr. M. L. H. Green

    1982-01-01

    Transition metal organometallic chemistry is a rapidly expanding field, which has an important relationship to industrial problems of petrochemical catalysis. This thesis describes studies of fundamental organometallic reaction processes, such as C-H and C-C bond formation and cleavage, and investigations of the structure and bonding of organometallic compounds. A number of techniques were used to pursue these studies, including synthesis, X-ray crystallography, and semi-em...

  6. Disk Chemistry*

    OpenAIRE

    Thi Wing-Fai

    2015-01-01

    The chemical species in protoplanetary disks react with each other. The chemical species control part of the thermal balance in those disks. How the chemistry proceeds in the varied conditions encountered in disks relies on detailed microscopic understanding of the reactions through experiments or theoretical studies. This chapter strives to summarize and explain in simple terms the different types of chemical reactions that can lead to complex species. The first part of the chapter deals wit...

  7. Interstellar chemistry

    OpenAIRE

    Klemperer, William

    2006-01-01

    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 o...

  8. Analytical chemistry

    International Nuclear Information System (INIS)

    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

  9. Green chemistry

    International Nuclear Information System (INIS)

    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'

  10. Green chemistry

    International Nuclear Information System (INIS)

    The depletion of world fossil fuel reserves and the involvement of greenhouse gases in the global warming has led to change the industrial and energy policies of most developed countries. The goal is now to reserve petroleum to the uses where it cannot be substituted, to implement renewable raw materials obtained from plants cultivation, and to consider the biodegradability of molecules and of manufactured objects by integrating the lifetime concept in their expected cycle of use. The green chemistry includes the design, development and elaboration of chemical products and processes with the aim of reducing or eliminating the use and generation of harmful compounds for the health and the environment, by adapting the present day operation modes of the chemical industry to the larger framework of the sustainable development. In addition to biofuels, this book reviews the applications of green chemistry in the different industrial processes in concern. Part 1 presents the diversity of the molecules coming from renewable carbon, in particular lignocellulose and the biotechnological processes. Part 2 is devoted to materials and treats of the overall available technological solutions. Part 3 focusses on functional molecules and chemical intermediates, in particular in sugar- and fats-chemistry. Part 4 treats of biofuels under the aspects of their production and use in today's technologies. The last part deals with the global approaches at the environmental and agricultural levels. (J.S.)

  11. Chemistry of superheavy elements

    Energy Technology Data Exchange (ETDEWEB)

    Schaedel, M. [Japan Atomic Energy Agency, Tokai, Ibaraki (Japan). Advanced Science Research Center; GSI Helmholtz Center for Heavy Ion Research, Darmstadt (Germany)

    2012-07-01

    The chemistry of superheavy elements - or transactinides from their position in the Periodic Table - is summarized. After giving an overview over historical developments, nuclear aspects about synthesis of neutron-rich isotopes of these elements, produced in hot-fusion reactions, and their nuclear decay properties are briefly mentioned. Specific requirements to cope with the one-atom-at-a-time situation in automated chemical separations and recent developments in aqueous-phase and gas-phase chemistry are presented. Exciting, current developments, first applications, and future prospects of chemical separations behind physical recoil separators ('pre-separator') are discussed in detail. The status of our current knowledge about the chemistry of rutherfordium (Rf, element 104), dubnium (Db, element 105), seaborgium (Sg, element 106), bohrium (Bh, element 107), hassium (Hs, element 108), copernicium (Cn, element 112), and element 114 is discussed from an experimental point of view. Recent results are emphasized and compared with empirical extrapolations and with fully-relativistic theoretical calculations, especially also under the aspect of the architecture of the Periodic Table. (orig.)

  12. Chemistry of superheavy elements

    International Nuclear Information System (INIS)

    The chemistry of superheavy elements - or transactinides from their position in the Periodic Table - is summarized. After giving an overview over historical developments, nuclear aspects about synthesis of neutron-rich isotopes of these elements, produced in hot-fusion reactions, and their nuclear decay properties are briefly mentioned. Specific requirements to cope with the one-atom-at-a-time situation in automated chemical separations and recent developments in aqueous-phase and gas-phase chemistry are presented. Exciting, current developments, first applications, and future prospects of chemical separations behind physical recoil separators ('pre-separator') are discussed in detail. The status of our current knowledge about the chemistry of rutherfordium (Rf, element 104), dubnium (Db, element 105), seaborgium (Sg, element 106), bohrium (Bh, element 107), hassium (Hs, element 108), copernicium (Cn, element 112), and element 114 is discussed from an experimental point of view. Recent results are emphasized and compared with empirical extrapolations and with fully-relativistic theoretical calculations, especially also under the aspect of the architecture of the Periodic Table. (orig.)

  13. ANSID: a Solid-Phase Proteomic Approach for Identification and Relative Quantification of Aromatic Nitration Sites

    Science.gov (United States)

    Nuriel, Tal; Whitehouse, Julia; Ma, Yuliang; Mercer, Emily; Brown, Neil; Gross, Steven

    2015-12-01

    Nitration of tyrosine and other aromatic amino acid residues in proteins occurs in the setting of inflammatory, neurodegenerative and cardiovascular diseases – importantly, this modification has been implicated in the pathogenesis of diverse diseases and the physiological process of tissue aging. To understand the biological consequences of aromatic nitration in both health and disease, it is critical to molecularly identify the proteins that undergo nitration, specify their cognate modification sites and quantify their extent of nitration. To date, unbiased identification of nitrated proteins has painstakingly employed 2D-gel electrophoresis followed by Western Blotting with an anti-nitrotyrosine antibody for detection. Apart from being relatively slow and laborious, this method suffers from limited coverage, the potential for false-positive identifications and failure to reveal specific amino acid modification sites. To overcome these shortcomings, we have developed a solid-phase, chemical-capture approach for unbiased and high-throughput discovery of nitrotyrosine and nitrotryptophan sites in proteins. Utilizing this method, we have successfully identified several endogenously nitrated proteins in rat brain and a total of 244 nitrated peptides from 145 proteins following in vitro exposure of rat brain homogenates to the nitrating agent peroxynitrite (1 mM). As expected, Tyr residues constituted the great majority of peroxynitrite-mediated protein nitration sites; however, we were surprised to discover several brain proteins that contain nitrated Trp residues. By incorporating a stable-isotope labeling step, this new Aromatic Nitrtion Site IDentification (ANSID) method was also adapted for relative quantification of nitration site abundances in proteins. Application of the quantitative ANSID method offers great potential to advance our understanding of the role of protein nitration in disease pathogenesis and normal physiology.

  14. Expression patterns of microRNAs associated with CML phases and their disease related targets

    Directory of Open Access Journals (Sweden)

    Trněný Marek

    2011-04-01

    Full Text Available Abstract Background MicroRNAs are important regulators of transcription in hematopoiesis. Their expression deregulations were described in association with pathogenesis of some hematological malignancies. This study provides integrated microRNA expression profiling at different phases of chronic myeloid leukemia (CML with the aim to identify microRNAs associated with CML pathogenesis. The functions of in silico filtered targets are in this report annotated and discussed in relation to CML pathogenesis. Results Using microarrays we identified differential expression profiles of 49 miRNAs in CML patients at diagnosis, in hematological relapse, therapy failure, blast crisis and major molecular response. The expression deregulation of miR-150, miR-20a, miR-17, miR-19a, miR-103, miR-144, miR-155, miR-181a, miR-221 and miR-222 in CML was confirmed by real-time quantitative PCR. In silico analyses identified targeted genes of these miRNAs encoding proteins that are involved in cell cycle and growth regulation as well as several key signaling pathways such as of mitogen activated kinase-like protein (MAPK, epidermal growth factor receptor (EGFR, ERBB, transforming growth factor beta (TGFB1 and tumor protein p53 that are all related to CML. Decreased levels of miR-150 were detected in patients at diagnosis, in blast crisis and 67% of hematological relapses and showed significant negative correlation with miR-150 proved target MYB and with BCR-ABL transcript level. Conclusions This study uncovers microRNAs that are potentially involved in CML and the annotated functions of in silico filtered targets of selected miRNAs outline mechanisms whereby microRNAs may be involved in CML pathogenesis.

  15. Composition, structure, and chemistry of interstellar dust

    Science.gov (United States)

    Tielens, A. G. G. M.; Allamandola, L. J.

    1987-01-01

    Different dust components present in the interstellar medium (IM) such as amorphous carbon, polycyclic aromatic hydrocarbons, and those IM components which are organic refractory grains and icy grain mantles are discussed as well as their relative importance. The physical properties of grain surface chemistry are discussed with attention given to the surface structure of materials, the adsorption energy and residence time of species on a grain surface, and the sticking probability. Consideration is also given to the contribution of grains to the gas-phase composition of molecular clouds.

  16. Chemistry and fluxes of magmatic gases powering the explosive trachyandesitic phase of Eyjafjallajokull 2010 eruption: constraints on degassing magma volumes and processes

    Science.gov (United States)

    Allard, P.; Burton, M. R.; Oskarsson, N.; Michel, A.; Polacci, M.

    2010-12-01

    The 2010 Eyjafjallajökull eruption developed in two distinct phases, with initial lateral effusion of alkali basalt since March 20, followed by highly explosive extrusion of a quite homogenous and crystal-poor trachyandesitic magma [1] through the central volcano ice cap between April 14 and May 24. As usual, magmatic volatiles played a key role in the eruption dynamics. Here we report on the chemical composition and the mass output of magmatic gases powering intense explosive activity during the second eruptive phase in early May. On May 8 we could measure the composition of magmatic gases directly issuing from the eruptive vents, by using OP-FTIR spectroscopy from the crater rim (~900 m distance) and molten lava blocks as IR radiation source. FTIR spectra reveal a variable mixture between two gas components equally rich in H2O (91.3 mol%) and CO2 (8%) but differing in their SO2/HCl ratio (up to 3.5 for the main one and 0.5 for the Cl-richer second one). Analysis of S-Cl-F in ash leachates and in ash and lava bomb samples (pyrohydrolysis) show that this second component was generated by greater chlorine loss during extensive magma fragmentation into fine ash. S/Cl and Cl/F ratios from both these analyses and solar occultation FTIR plume sensing indicate a modest fluorine content in emitted gas and its preferential adsorption onto solid particles during plume transport. DOAS traverses under the volcanic plume (4-6 km height), though hampered by dense ash load, gave most reliable SO2 fluxes of 4500-6600 tons d-1 on May 9, consistent with OMI satellite data [2]. These imply the daily co-emission of 7.2x105 tons of H2O, 1.5x105 tons of CO2, 2000 tons of HCl and ≤200 tons of HF. Eyjafjallajökull thus produced more hydrous and relatively CO2-poorer gas, in much greater quantities, during that stage than during its first basaltic phase [3]. Linear variations of dissolved S with TiO2/FeO ratio in nearby Katla alkali magmas [4] suggest possible pre-eruptive S contents

  17. Buried iron archaeological artefacts: Corrosion mechanisms related to the presence of Cl-containing phases

    International Nuclear Information System (INIS)

    Deterioration after excavation of archaeological iron artefacts buried in soil is often associated with the presence of Cl-containing phases in corrosion products, leading to serious problems for conservation of metallic objects of cultural heritage. Thus, in order to better understand the corrosion process related to the presence of chlorine, some high-resolution techniques of materials characterisation are implemented. Particularly this paper shows the great utility of the combination of micro-X-ray diffraction, micro-Raman spectroscopy and micro-X-ray absorption spectroscopy. The analyses are realised on the cross sections of iron corroded objects excavated on archaeological sites dated from the 12th to the 16th century AD. In addition to the common oxyhydroxide containing chloride, akaganeite (β-FeOOH) often mentioned in the literature, a ferrous hydroxychloride β-Fe2(OH)3Cl was also found in the corrosion layers. In order to explain the corrosion system formed during burial, a corrosion mechanism including the presence of chlorine, is proposed

  18. A trans-phase granular continuum relation and its use in simulation

    Science.gov (United States)

    Kamrin, Ken; Dunatunga, Sachith; Askari, Hesam

    The ability to model a large granular system as a continuum would offer tremendous benefits in computation time compared to discrete particle methods. However, two infamous problems arise in the pursuit of this vision: (i) the constitutive relation for granular materials is still unclear and hotly debated, and (ii) a model and corresponding numerical method must wear ``many hats'' as, in general circumstances, it must be able to capture and accurately represent the material as it crosses through its collisional, dense-flowing, and solid-like states. Here we present a minimal trans-phase model, merging an elastic response beneath a fictional yield criterion, a mu(I) rheology for liquid-like flow above the static yield criterion, and a disconnection rule to model separation of the grains into a low-temperature gas. We simulate our model with a meshless method (in high strain/mixing cases) and the finite-element method. It is able to match experimental data in many geometries, including collapsing columns, impact on granular beds, draining silos, and granular drag problems.

  19. A refractive phase relation in light composite particle-nucleus elastic and inelastic scattering at intermediate energies

    International Nuclear Information System (INIS)

    We separate the angular distributions of light composite particle-nucleus elastic and inelastic scattering at intermediate energies, into ''positive'' and ''negative'' angle components. We show that if oscillations in the ''negative'' angle component of elastic scattering are due to refractive interference effects, there will be corresponding oscillations in the ''negative'' angle component of inelastic scattering which are in phase with those in the elastic scattering. This phase relation is independent of the multipolarity of the excitation

  20. Relating field-induced shift in transition temperature to the kinetics of coexisting phases in magnetic shape memory alloys

    OpenAIRE

    Banerjee, A.; Dash, S.; Lakhani, Archana; Chaddah, P.; Chen, X; Ramanujan, R. V.

    2011-01-01

    In a magnetic shape memory alloy system, we vary composition following phenomenological arguments to tune macroscopic properties. We achieve significantly higher shift in austenite to martensitic phase transition temperature with magnetic field. This enhancement is accompanied by significant broadening of the transition and by field-induced arrest of kinetics, both of which are related to the dynamics of the coexisting phases. This reveals hitherto unknown interrelationship between different ...

  1. Phase relations in the hydrous CMAS pyrolite in presence of KCl at 2 GPa

    Science.gov (United States)

    Safonov, O.

    2012-04-01

    In the upper mantle, chlorides are constituents of concentrated aqueous solutions (brines), as well as chloride-carbonate and carbonatite melts. Mineral assemblages coming from diverse depth levels show that mobile (K, Na)Cl-bearing fluids are able to provoke intensive metasomatism of the peridotitic mantle accompanied by melting. Scarce experimental studies on influence of brines on mineral equilibria in the peridotitic mantle (Stalder et al., 2008; Chu et al., 2011) indicate that influence of chlorides on water activity in a fluid equilibrated with forsterite enstatite at pressures above 2 GPa is very similar to their effect at lower "crustal" pressures (e.g. Aranovich, Newton, 1997): decrease of the H2O activity with an increase of the salt content results in an increase of the melting temperature of silicates. Nevertheless, these experiments were performed in the Al-free systems. Presence of Al would provoke an active interaction of alkali chlorides, namely KCl, with silicates with formation of new K-Al-bearing phases, such as phlogopite (in presence of H2O), which would influence on the melting of complex assemblages. In order to investigate an effect of KCl on phase relations in the Al2O3, CaO, Na2O-rich hydrous peridotite and on stability of garnet, pyroxenes, and amphiboles, in particular, experiments on interaction of the model CMAS pyrolite Fo57En17Prp14Di12 (+0.3 wt. % of Na2O) with the H2O-KCl fluid were performed at 2 GPa in the temperature interval 900-1200. Mixtures of synthetic forsterite, diopside, enstatite and pyrope in the above weight ratio were mixed with 14 wt. % of Mg(OH)2 corresponding to 4.4 wt. % of H2O in the system. 2.4, 3.7, 5 and 10 wt. % of KCl were added to silicate-H2O mixture. Experiments were performed using a piston-cylinder apparatus with ½-inch talc high-pressure cells calibrated via brucite = periclase + H2O and albite = jadeite + quartz equilibria curves. Temperature was controlled with accuracy ?1 with the W95Re5/W80Re20

  2. A Riemann solver for single-phase and two-phase shallow flow models based on relaxation. Relations with Roe and VFRoe solvers

    International Nuclear Information System (INIS)

    We present a Riemann solver derived by a relaxation technique for classical single-phase shallow flow equations and for a two-phase shallow flow model describing a mixture of solid granular material and fluid. Our primary interest is the numerical approximation of this two-phase solid/fluid model, whose complexity poses numerical difficulties that cannot be efficiently addressed by existing solvers. In particular, we are concerned with ensuring a robust treatment of dry bed states. The relaxation system used by the proposed solver is formulated by introducing auxiliary variables that replace the momenta in the spatial gradients of the original model systems. The resulting relaxation solver is related to Roe solver in that its Riemann solution for the flow height and relaxation variables is formally computed as Roe's Riemann solution. The relaxation solver has the advantage of a certain degree of freedom in the specification of the wave structure through the choice of the relaxation parameters. This flexibility can be exploited to handle robustly vacuum states, which is a well known difficulty of standard Roe's method, while maintaining Roe's low diffusivity. For the single-phase model positivity of flow height is rigorously preserved. For the two-phase model positivity of volume fractions in general is not ensured, and a suitable restriction on the CFL number might be needed. Nonetheless, numerical experiments suggest that the proposed two-phase flow solver efficiently models wet/dry fronts and vacuum formation for a large range of flow conditions. As a corollary of our study, we show that for single-phase shallow flow equations the relaxation solver is formally equivalent to the VFRoe solver with conservative variables of Gallouet and Masella [T. Gallouet, J.-M. Masella, Un schema de Godunov approche C.R. Acad. Sci. Paris, Serie I, 323 (1996) 77-84]. The relaxation interpretation allows establishing positivity conditions for this VFRoe method.

  3. A Riemann solver for single-phase and two-phase shallow flow models based on relaxation. Relations with Roe and VFRoe solvers

    Science.gov (United States)

    Pelanti, Marica; Bouchut, François; Mangeney, Anne

    2011-02-01

    We present a Riemann solver derived by a relaxation technique for classical single-phase shallow flow equations and for a two-phase shallow flow model describing a mixture of solid granular material and fluid. Our primary interest is the numerical approximation of this two-phase solid/fluid model, whose complexity poses numerical difficulties that cannot be efficiently addressed by existing solvers. In particular, we are concerned with ensuring a robust treatment of dry bed states. The relaxation system used by the proposed solver is formulated by introducing auxiliary variables that replace the momenta in the spatial gradients of the original model systems. The resulting relaxation solver is related to Roe solver in that its Riemann solution for the flow height and relaxation variables is formally computed as Roe's Riemann solution. The relaxation solver has the advantage of a certain degree of freedom in the specification of the wave structure through the choice of the relaxation parameters. This flexibility can be exploited to handle robustly vacuum states, which is a well known difficulty of standard Roe's method, while maintaining Roe's low diffusivity. For the single-phase model positivity of flow height is rigorously preserved. For the two-phase model positivity of volume fractions in general is not ensured, and a suitable restriction on the CFL number might be needed. Nonetheless, numerical experiments suggest that the proposed two-phase flow solver efficiently models wet/dry fronts and vacuum formation for a large range of flow conditions. As a corollary of our study, we show that for single-phase shallow flow equations the relaxation solver is formally equivalent to the VFRoe solver with conservative variables of Gallouët and Masella [T. Gallouët, J.-M. Masella, Un schéma de Godunov approché C.R. Acad. Sci. Paris, Série I, 323 (1996) 77-84]. The relaxation interpretation allows establishing positivity conditions for this VFRoe method.

  4. Precise relative positioning of multiple moving platforms using GPS carrier phase observables

    Science.gov (United States)

    Luo, Ning

    Precise relative positioning of multiple moving platforms using GPS carrier phase observables has numerous applications. The essential point for this research is the fast and reliable OTF carrier phase ambiguity resolution. Algorithms for single baseline resolution cannot provide optimal performance for this application because it does not make use of the redundancy available in the configuration of multiple moving platforms. In this thesis, a novel method called MultiKin is proposed for OTF ambiguity resolution for multiple moving platforms. First, MultiKin applies Delaunay triangulation to select necessary baselines and to build an optimal structure of ambiguity constraints. Second, it improves the reliability of the OTF ambiguity resolution of single-baselines by optimizing the ambiguity monitoring algorithm. Finally, the resolved ambiguities from each baseline are processed using the multiple triangular constraints, which can speed up fixing ambiguity and detecting wrong fixes. To fully evaluate the performance of MultiKin, a sophisticated GPS software simulator is developed. Its significance lies in a GPS error simulator. New GPS error models are built based on the investigation of the existing models. The spatial correlation and temporal variation of errors are highlighted in the new models; thus, these models are proper for error simulation in both single-point and differential GPS systems. In addition, all the models have adjustable parameters that allow users to generate a wide range of testing conditions. The results of extensive simulation tests and field tests with MultiKin indicate that MultiKin is effective in speeding up ambiguity resolution. The time required to fix ambiguities can be reduced by up to 67% over the single-baseline method time. Also, MultiKin increases the limit on the distance by two to three kilometres over which ambiguity resolution can be performed. An increased magnitude of the GPS errors and weaker satellite visibility can

  5. Plasticity-induced characteristic changes of pattern dynamics and the related phase transitions in small-world neuronal networks

    International Nuclear Information System (INIS)

    Phase transitions widely exist in nature and occur when some control parameters are changed. In neural systems, their macroscopic states are represented by the activity states of neuron populations, and phase transitions between different activity states are closely related to corresponding functions in the brain. In particular, phase transitions to some rhythmic synchronous firing states play significant roles on diverse brain functions and disfunctions, such as encoding rhythmical external stimuli, epileptic seizure, etc. However, in previous studies, phase transitions in neuronal networks are almost driven by network parameters (e.g., external stimuli), and there has been no investigation about the transitions between typical activity states of neuronal networks in a self-organized way by applying plastic connection weights. In this paper, we discuss phase transitions in electrically coupled and lattice-based small-world neuronal networks (LBSW networks) under spike-timing-dependent plasticity (STDP). By applying STDP on all electrical synapses, various known and novel phase transitions could emerge in LBSW networks, particularly, the phenomenon of self-organized phase transitions (SOPTs): repeated transitions between synchronous and asynchronous firing states. We further explore the mechanics generating SOPTs on the basis of synaptic weight dynamics. (interdisciplinary physics and related areas of science and technology)

  6. Theme-Based Bidisciplinary Chemistry Laboratory Modules

    Science.gov (United States)

    Leber, Phyllis A.; Szczerbicki, Sandra K.

    1996-12-01

    A thematic approach to each of the two introductory chemistry laboratory sequences, general and organic chemistry, not only provides an element of cohesion but also stresses the role that chemistry plays as the "central science" and emphasizes the intimate link between chemistry and other science disciplines. Thus, in general chemistry the rubric "Environmental Chemistry" affords connections to the geosciences, whereas experiments on the topic of "Plant Assays" bridge organic chemistry and biology. By establishing links with other science departments, the theme-based laboratory experiments will satisfy the following multidisciplinary criteria: (i) to demonstrate the general applicability of core methodologies to the sciences, (ii) to help students relate concepts to a broader multidisciplinary context, (iii) to foster an attitude of both independence and cooperation that can transcend the teaching laboratory to the research arena, and (iv) to promote greater cooperation and interaction between the science departments. Fundamentally, this approach has the potential to impact the chemistry curriculum significantly by including student decision-making in the experimental process. Furthermore, the incorporation of GC-MS, a powerful tool for separation and identification as well as a state-of-the-art analytical technique, in the modules will enhance the introductory general and organic chemistry laboratory sequences by making them more instrument-intensive and by providing a reliable and reproducible means of obtaining quantitative analyses. Each multifaceted module has been designed to meet the following criteria: (i) a synthetic protocol including full spectral characterization of products, (ii) quantitative and statistical analyses of data, and (iii) construction of a database of results. The database will provide several concrete functions. It will foster the idea that science is a continuous incremental process building on the results of earlier experimentalists

  7. Phase diagram and dispersion relation of the non-commutative λφ4 model in d=3

    International Nuclear Information System (INIS)

    We present a non-perturbative study of the λφ4 model in a three dimensional Euclidean space, where the two spatial coordinates are non-commutative. Our results are obtained from numerical simulations of the lattice model, after its mapping onto a dimensionally reduced, twisted Hermitian matrix model. In this way we first reveal the explicit phase diagram of the non-commutative λφ4 lattice model. We observe that the ordered regime splits into a phase of uniform order and a phase of two stripes of opposite sign, and more complicated patterns. Next we discuss the behavior of the spatial and temporal correlators. From the latter we extract the dispersion relation, which allows us to introduce a dimensionful lattice spacing. To extrapolate to zero lattice spacing and infinite volume we perform a double scaling limit, which keeps the non-commutativity tensor constant. The dispersion relation in the disordered phase stabilizes in this limit, which represents a non-perturbative renormalization. In particular this confirms the existence of a striped phase in the continuum limit, in accordance with a conjecture by Gubser and Sondhi. The extrapolated dispersion relation also exhibits UV/IR mixing as a non-perturbative effect. % an IR divergence in the infinite volume. Finally we add some observations about a Nambu-Goldstone mode in the striped phase, and about the corresponding model in d = 2. (author)

  8. Phase diagram and dispersion relation of the non-commutative {lambda}{phi}{sup 4} model in d=3

    Energy Technology Data Exchange (ETDEWEB)

    Bietenholz, Wolfgang E-mail: bietenho@physik.hu-berlin.de; Hofheinz, Frank; Nishimura, Jun

    2004-06-01

    We present a non-perturbative study of the {lambda}{phi}{sup 4} model in a three dimensional Euclidean space, where the two spatial coordinates are non-commutative. Our results are obtained from numerical simulations of the lattice model, after its mapping onto a dimensionally reduced, twisted Hermitian matrix model. In this way we first reveal the explicit phase diagram of the non-commutative {lambda}{phi}{sup 4} lattice model. We observe that the ordered regime splits into a phase of uniform order and a phase of two stripes of opposite sign, and more complicated patterns. Next we discuss the behavior of the spatial and temporal correlators. From the latter we extract the dispersion relation, which allows us to introduce a dimensionful lattice spacing. To extrapolate to zero lattice spacing and infinite volume we perform a double scaling limit, which keeps the non-commutativity tensor constant. The dispersion relation in the disordered phase stabilizes in this limit, which represents a non-perturbative renormalization. In particular this confirms the existence of a striped phase in the continuum limit, in accordance with a conjecture by Gubser and Sondhi. The extrapolated dispersion relation also exhibits UV/IR mixing as a non-perturbative effect. % an IR divergence in the infinite volume. Finally we add some observations about a Nambu-Goldstone mode in the striped phase, and about the corresponding model in d = 2. (author)

  9. Possible existence of two amorphous phases of D-mannitol related by a first-order transition

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Men; Yu, Lian, E-mail: lian.yu@wisc.edu [Department of Chemistry and School of Pharmacy, University of Wisconsin-Madison, Madison, Wisconsin 53705 (United States); Wang, Jun-Qiang; Perepezko, John H. [Department of Materials Science and Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States)

    2015-06-28

    We report that the common polyalcohol D-mannitol may have two amorphous phases related by a first-order transition. Slightly above its glass transition temperature T{sub g} (284 K), the supercooled liquid (SCL) of D-mannitol transforms to a low-energy, apparently amorphous phase with stronger hydrogen bonds. The enthalpy of this so-called Phase X is approximately halfway between those of the known amorphous and crystalline phases, a position low for glass aging and high for crystal polymorphs. Similar to the SCL, Phase X is transparent with broad X-ray diffraction and Raman scattering; upon temperature cycling, it exhibits a glass-transition-like change of heat capacity. On fast heating, Phase X transforms back to the SCL near T{sub g} + 50 K, enabling a determination of their equilibrium temperature. The presence of D-sorbitol as a plasticizer enables observation of a first-order transition from the SCL to Phase X entirely in the liquid state (liquid-liquid transition). The transition from D-mannitol’s SCL to Phase X has intriguing similarities with the formation of the glacial phase of triphenyl phosphite (TPP) and the conversion from high-density to low-density amorphous ice, both studied intensely in the context of polyamorphism. All three processes occur near T{sub g} with substantial enthalpy decrease toward the crystalline phases; the processes in water and D-mannitol both strengthen the hydrogen bonds. In contrast to TPP, D-mannitol’s Phase X forms more rapidly and can transform back to the SCL. These features make D-mannitol a valuable new model for understanding polyamorphism.

  10. Possible existence of two amorphous phases of D-mannitol related by a first-order transition

    International Nuclear Information System (INIS)

    We report that the common polyalcohol D-mannitol may have two amorphous phases related by a first-order transition. Slightly above its glass transition temperature Tg (284 K), the supercooled liquid (SCL) of D-mannitol transforms to a low-energy, apparently amorphous phase with stronger hydrogen bonds. The enthalpy of this so-called Phase X is approximately halfway between those of the known amorphous and crystalline phases, a position low for glass aging and high for crystal polymorphs. Similar to the SCL, Phase X is transparent with broad X-ray diffraction and Raman scattering; upon temperature cycling, it exhibits a glass-transition-like change of heat capacity. On fast heating, Phase X transforms back to the SCL near Tg + 50 K, enabling a determination of their equilibrium temperature. The presence of D-sorbitol as a plasticizer enables observation of a first-order transition from the SCL to Phase X entirely in the liquid state (liquid-liquid transition). The transition from D-mannitol’s SCL to Phase X has intriguing similarities with the formation of the glacial phase of triphenyl phosphite (TPP) and the conversion from high-density to low-density amorphous ice, both studied intensely in the context of polyamorphism. All three processes occur near Tg with substantial enthalpy decrease toward the crystalline phases; the processes in water and D-mannitol both strengthen the hydrogen bonds. In contrast to TPP, D-mannitol’s Phase X forms more rapidly and can transform back to the SCL. These features make D-mannitol a valuable new model for understanding polyamorphism

  11. Possible existence of two amorphous phases of d-mannitol related by a first-order transition

    Science.gov (United States)

    Zhu, Men; Wang, Jun-Qiang; Perepezko, John H.; Yu, Lian

    2015-06-01

    We report that the common polyalcohol d-mannitol may have two amorphous phases related by a first-order transition. Slightly above its glass transition temperature Tg (284 K), the supercooled liquid (SCL) of d-mannitol transforms to a low-energy, apparently amorphous phase with stronger hydrogen bonds. The enthalpy of this so-called Phase X is approximately halfway between those of the known amorphous and crystalline phases, a position low for glass aging and high for crystal polymorphs. Similar to the SCL, Phase X is transparent with broad X-ray diffraction and Raman scattering; upon temperature cycling, it exhibits a glass-transition-like change of heat capacity. On fast heating, Phase X transforms back to the SCL near Tg + 50 K, enabling a determination of their equilibrium temperature. The presence of d-sorbitol as a plasticizer enables observation of a first-order transition from the SCL to Phase X entirely in the liquid state (liquid-liquid transition). The transition from d-mannitol's SCL to Phase X has intriguing similarities with the formation of the glacial phase of triphenyl phosphite (TPP) and the conversion from high-density to low-density amorphous ice, both studied intensely in the context of polyamorphism. All three processes occur near Tg with substantial enthalpy decrease toward the crystalline phases; the processes in water and d-mannitol both strengthen the hydrogen bonds. In contrast to TPP, d-mannitol's Phase X forms more rapidly and can transform back to the SCL. These features make d-mannitol a valuable new model for understanding polyamorphism.

  12. Common oscillatory modes in geomagnetic activity and climate variability and their phase relations

    International Nuclear Information System (INIS)

    Complete text of publication follows. Oscillatory modes with period of approximately 8 years were detected in monthly time series of geomagnetic activity aa-index, North Atlantic Oscillation index and near-surface air temperature from several mid-latitude European locations. Instantaneous phases of the modes underwent synchronization analysis and their statistically significant phase coherence, beginning from 1950's, has been observed.

  13. Binary and ternary carbides and nitrides of the transition metals and their phase relations

    International Nuclear Information System (INIS)

    The occurrance and the structure of the binary and ternary transition metal carbides and nitrides are described. Phase diagrams are assessed for most of the binary and ternary systems. Many ternary phase diagrams are published in this report for the first time. (orig.)

  14. GEM-AQ, an on-line global multiscale chemical weather system: model description and evaluation of gas phase chemistry processes

    Directory of Open Access Journals (Sweden)

    J. W. Kaminski

    2007-10-01

    Full Text Available Tropospheric chemistry and air quality processes were implemented on-line in the Global Environmental Multiscale model. The integrated model, GEM-AQ, has been developed as a platform to investigate chemical weather at scales from global to urban. The model was exercised for five years (2001–2005 to evaluate its ability to simulate seasonal variations and regional distributions of trace gases such as ozone, nitrogen dioxide and carbon monoxide on the global scale. The model results presented are compared with observations from satellites, aircraft measurement campaigns and balloon sondes.

  15. Determination of Plant Volatiles Using Solid Phase Microextraction GC-MS

    Science.gov (United States)

    Van Bramer, Scott; Goodrich, Katherine R.

    2015-01-01

    This experiment combines analytical techniques of solid phase microextraction and gas chromatography-mass spectrometry with easily relatable and accessible plant volatile chemistry (floral and vegetative scents of local/available plants). The biosynthesis and structure of these chemicals are of interest in the areas of organic chemistry,…

  16. Relative permeability and the microscopic distribution of wetting and nonwetting phases in the pore space of Berea sandstone

    Energy Technology Data Exchange (ETDEWEB)

    Schlueter, E.M.; Cook, N.G.W. [Lawrence Berkeley Lab., CA (United States)]|[California Univ., Berkeley, CA (United States). Dept. of Materials Science and Mineral Engineering; Witherspoon, P.A.; Myer, L.R. [Lawrence Berkeley Lab., CA (United States)

    1994-04-01

    Experiments to study relative permeabilities of a partially saturated rock have been carried out in Berea sandstone using fluids that can be solidified in place. The effective permeability of the spaces not occupied by the wetting fluid (paraffin wax) or the nonwetting fluid (Wood`s metal), have been measured at various saturations after solidifying each of the phases. The tests were conducted on Berea sandstone samples that had an absolute permeability of about 600 md. The shape of the laboratory-derived relative permeability vs. saturation curves measured with the other phase solidified conforms well with typical curves obtained using conventional experimental methods. The corresponding wetting and nonwetting fluid distributions at different saturations are presented and analyzed in light of the role of the pore structure in the invasion process, and their impact on relative permeability and capillary pressure. Irreducible wetting and nonwetting phase fluid distributions are studied. The effect of clay minerals on permeability is also assessed.

  17. Surface chemistry

    CERN Document Server

    Desai, KR

    2008-01-01

    The surface Chemistry of a material as a whole is crucially dependent upon the Nature and type of surfaces exposed on crystallites. It is therefore vitally important to independently Study different, well - defined surfaces through surface analytical techniques. In addition to composition and structure of surface, the subject also provides information on dynamic light scattering, micro emulsions, colloid Stability control and nanostructures. The present book endeavour to bring before the reader that the understanding and exploitation of Solid state phenomena depended largely on the ability to

  18. Hypercarbon chemistry

    International Nuclear Information System (INIS)

    This text points out the emerging significance of higher-valent carbon compounds. It describes the compounds of carbon with coordination numbers greater than four and explores the delocalized bonds of π aromatic molecules as a basis for rational description of orbitals; localized multicentered orbitals; the interactions of metallic ions with other atoms and molecules; the skeletal electron counts as a guide for synthesis; and the isolobal concept. Illustrated are the ways in which these subjects bring together structure and reactivity in the great diversity of novel carbon chemistry and its relationship to that of boron, lithium, hydrogen, the metals, and others

  19. 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

  20. Workgroup Report: Indoor Chemistry and Health

    OpenAIRE

    Weschler, Charles J.; Wells, J R; Poppendieck, Dustin; Hubbard, Heidi; Pearce, Terri A.

    2005-01-01

    Chemicals present in indoor air can react with one another, either in the gas phase or on surfaces, altering the concentrations of both reactants and products. Such chemistry is often the major source of free radicals and other short-lived reactive species in indoor environments. To what extent do the products of indoor chemistry affect human health? To address this question, the National Institute for Occupational Safety and Health sponsored a workshop titled “Indoor Chemistry and Health” on...

  1. On relation between Berry phase and one-dimensional models with long-range 1/r2-interaction

    International Nuclear Information System (INIS)

    It is shown, that the effective action of Berry phase type is connected with some one-dimensional models with long-range 1/r2-interaction. In particular, the Caldeira-Leggett action for Josephson junction with dissipation and classical spin systems are related with local effective action of holomorphic Berry phase type through the Hilbert reduction. Some consequences of this relation are discussed, including conformal symmetry of Caldeira-Leggett action and a possibility of exact solution of these models. (author). 19 refs

  2. Collaborative Physical Chemistry Projects Involving Computational Chemistry

    Science.gov (United States)

    Whisnant, David M.; Howe, Jerry J.; Lever, Lisa S.

    2000-02-01

    The physical chemistry classes from three colleges have collaborated on two computational chemistry projects using Quantum CAChe 3.0 and Gaussian 94W running on Pentium II PCs. Online communication by email and the World Wide Web was an important part of the collaboration. In the first project, students used molecular modeling to predict benzene derivatives that might be possible hair dyes. They used PM3 and ZINDO calculations to predict the electronic spectra of the molecules and tested the predicted spectra by comparing some with experimental measurements. They also did literature searches for real hair dyes and possible health effects. In the final phase of the project they proposed a synthetic pathway for one compound. In the second project the students were asked to predict which isomer of a small carbon cluster (C3, C4, or C5) was responsible for a series of IR lines observed in the spectrum of a carbon star. After preliminary PM3 calculations, they used ab initio calculations at the HF/6-31G(d) and MP2/6-31G(d) level to model the molecules and predict their vibrational frequencies and rotational constants. A comparison of the predictions with the experimental spectra suggested that the linear isomer of the C5 molecule was responsible for the lines.

  3. Correlation functions and fluctuation-dissipation relation in driven phase ordering systems: an exactly solvable model

    International Nuclear Information System (INIS)

    The dynamics of a phase ordering system with non-conserved order parameter under a plain shear flow with rate γ is solved analytically in the large-N limit. A phase transition is observed at a critical temperature Tc(γ). After a quench from a high temperature equilibrium state to a lower temperature T a non-equilibrium stationary state is entered when T > Tc(γ), while aging dynamics characterizes the phases with T ≤ Tc(γ). Two-time quantities are computed and the off-equilibrium generalization of the fluctuation-dissipation theorem is provided

  4. Synthesis of a stationary phase based on silica modified with branched octadecyl groups by Michael addition and photoinduced thiol-yne click chemistry for the separation of basic compounds.

    Science.gov (United States)

    Huang, Guang; Ou, Junjie; Wang, Hongwei; Ji, Yongsheng; Wan, Hao; Zhang, Zhang; Peng, Xiaojun; Zou, Hanfa

    2016-04-01

    A novel silica-based stationary phase with branched octadecyl groups was prepared by the sequential employment of the Michael addition reaction and photoinduced thiol-yne click chemistry with 3-aminopropyl-functionalized silica microspheres as the initial material. The resulting stationary phase denoted as SiO2 -N(C18)4 was characterized by elemental analysis, FTIR spectroscopy and Raman spectroscopy, demonstrating the existence of branched octadecyl groups in silica microspheres. The separations of benzene homologous compounds, acid compounds and amine analogues were conducted, demonstrating mixed-mode separation mechanism on SiO2 -N(C18)4 . Baseline separation of basic drugs mixture was acquired with the mobile phase of acetonitrile/H2 O (5%, v/v). SiO2 -N(C18)4 was further applied to separate Corydalis yanhusuo Wang water extracts, and more baseline separation peaks were obtained for SiO2 -N(C18)4 than those on Atlantis dC18 column. It can be expected that this new silica-based stationary phase will exhibit great potential in the analysis of basic compounds. PMID:26910263

  5. The clonic phase of seizures in patients treated with electroconvulsive therapy is related to age and stimulus intensity

    Directory of Open Access Journals (Sweden)

    Chih-ChiehTseng

    2013-12-01

    Full Text Available Background: Electroconvulsive therapy (ECT is effective in the treatment of major depressive disorder and schizophrenia in patients who are drug-naïve or less-receptive to antipsychotic drugs. Several studies have discussed the correlation between patient characteristics, input current volume and seizure duration. According to the present principle of ECT guidelines, the therapeutic effect of ECT mostly correlates with seizure duration. As the tonic phase is different from the clonic phase with respect to brain function and activity, it is informative to analyse both the tonic and clonic phases. Thus, this study sought to clarify the relationship between the features of the two phases, and to re-examine and refine guidelines regarding ECT treatment. Method: ECT-course data from 44 schizophrenia patients were recollected, including the number of treatments that they had received, their gender, age, and the association of these characteristics with motor seizure duration was analysed. A two-factor correlation was employed to test the relationship between each of the two factors. Result: The meta-analysis results indicate that seizure duration and age are significantly correlated. Older patients had relatively short seizure durations after ECT-treatment. Notably, a negative correlation was only found between age and the clonic phase of the seizure, not between age and the tonic phase. Furthermore, this study also found an inverse relationship between ECT-intensity and the clonic phase, but not between ECT-intensity and the tonic phase. Conclusion: This study demonstrated that age and ECT-intensity are negatively correlated with seizure duration, particularly in the clonic phase. The present observations are not fully consistent with the basic guidelines of the APA-ECT practical manual. Accordingly, the predictions regarding the therapeutic effect of ECT can be based on both the seizure duration and the clonic phase.

  6. The influence of the relative phase between the driving voltages on electron heating in asymmetric dual frequency capacitive discharges

    International Nuclear Information System (INIS)

    The influence of the relative phase between the driving voltages on electron heating in asymmetric phase-locked dual frequency capacitively coupled radio frequency plasmas operated at 2 and 14 MHz is investigated. The basis of the analysis is a nonlinear global model with the option to implement a relative phase between the two driving voltages. In recent publications it has been reported that nonlinear electron resonance heating can drastically enhance the power dissipation to electrons at moments of sheath collapse due to the self-excitation of nonlinear plasma series resonance (PSR) oscillations of the radio frequency current. This work shows that depending on the relative phase of the driving voltages, the total number and exact moments of sheath collapse can be influenced. In the case of two consecutive sheath collapses a substantial increase in dissipated power compared with the known increase due to a single PSR excitation event per period is observed. Phase resolved optical emission spectroscopy (PROES) provides access to the excitation dynamics in front of the driven electrode. Via PROES the propagation of beam-like energetic electrons immediately after the sheath collapse is observed. In this work we demonstrate that there is a close relation between moments of sheath collapse, and thus excitation of the PSR, and beam-like electron propagation. A comparison of simulation results to experiments in a single and dual frequency discharge shows good agreement. In particular the observed influence of the relative phase on the dynamics of a dual frequency discharge is described by means of the presented model. Additionally, the analysis demonstrates that the observed gain in dissipation is not accompanied by an increase in the electrode's dc-bias voltage which directly addresses the issue of separate control of ion flux and ion energy in dual frequency capacitively coupled radio frequency plasmas.

  7. Growth Performance, Carcass Characteristics and Plasma Mineral Chemistry as Affected by Dietary Chloride and Chloride Salts Fed to Broiler Chickens Reared under Phase Feeding System

    OpenAIRE

    Mushtaq, M. M. H.; Pasha, T.N.; M. Akram; Mushtaq, T.; R Parvin; Choi, H. C.; Hwangbo, J.; Kim, J. H.

    2013-01-01

    Requirements of dietary chloride (dCl) and chloride salts were determined by using 4×2 factorial arrangement under four phase feeding program. Four levels (0.31, 0.45, 0.59 and 0.73%) and two sources (NH4Cl and CaCl2) of the dCl were allocated to 1,472 chicks in eight dietary treatments in which each treatment was replicated four times with 46 birds per replicate. The four phase feeding program was comprised of four dietary phases: Prestarter (d 1 to 10), Starter (d 11 to 20), Grower (d 21 to...

  8. Phase shifts of synchronized oscillators and the systolic/diastolic blood pressure relation

    CERN Document Server

    Angelini, L; Maestri, R; Marinazzo, D; Nardulli, Giuseppe; Nitti, L; Pellicoro, M; Pinna, G D; Stramaglia, S

    2004-01-01

    We study the phase-synchronization properties of systolic and diastolic arterial pressure in healthy subjects. We find that delays in the oscillatory components of the time series depend on the frequency bands that are considered, in particular we find a change of sign in the phase shift going from the Very Low Frequency band to the High Frequency band. This behavior should reflect a collective behavior of a system of nonlinear interacting elementary oscillators. We prove that some models describing such systems, e.g. the Winfree and the Kuramoto models offer a clue to this phenomenon. For these theoretical models there is a linear relationship between phase shifts and the difference of natural frequencies of oscillators and a change of sign in the phase shift naturally emerges.

  9. Phase and structural transformations in annealed copper coatings in relation to oxide whisker growth

    Energy Technology Data Exchange (ETDEWEB)

    Dorogov, M.V.; Priezzheva, A.N. [Togliatti State University, Belorusskaya 14, 445667 Togliatti (Russian Federation); Vlassov, S., E-mail: vlassovs@ut.ee [Institute of Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga (Latvia); Kink, I.; Shulga, E. [Institute of Physics, University of Tartu, Ravila 14c, 50411 Tartu (Estonia); Dorogin, L.M. [Togliatti State University, Belorusskaya 14, 445667 Togliatti (Russian Federation); Institute of Physics, University of Tartu, Ravila 14c, 50411 Tartu (Estonia); ITMO University, Kronverkskiy 49, 197101 Saint Petersburg (Russian Federation); Lõhmus, R. [Institute of Physics, University of Tartu, Ravila 14c, 50411 Tartu (Estonia); Tyurkov, M.N.; Vikarchuk, A.A. [Togliatti State University, Belorusskaya 14, 445667 Togliatti (Russian Federation); Romanov, A.E. [Togliatti State University, Belorusskaya 14, 445667 Togliatti (Russian Federation); Institute of Physics, University of Tartu, Ravila 14c, 50411 Tartu (Estonia); ITMO University, Kronverkskiy 49, 197101 Saint Petersburg (Russian Federation); Ioffe Physical Technical Institute, RAS, Polytechnicheskaya 26, 194021 Saint Petersburg (Russian Federation)

    2015-08-15

    Highlights: • Coatings prepared by Cu microparticle electrodeposition. • Structural and phase transformation in Cu coatings annealed at 400 °C. • Annealing is accompanied by intensive growth of CuO whiskers. • Layered oxide phases (Cu{sub 2}O and CuO) in the coating are characterized. • Formation of volumetric defects in the coating is demonstrated. - Abstract: We describe structural and phase transformation in copper coatings made of microparticles during heating and annealing in air in the temperature range up to 400 °C. Such thermal treatment is accompanied by intensive CuO nanowhisker growth on the coating surface and the formation of the layered oxide phases (Cu{sub 2}O and CuO) in the coating interior. X-ray diffraction and focused ion beam (FIB) are employed to characterize the multilayer structure of annealed copper coatings. Formation of volumetric defects such as voids and cracks in the coating is demonstrated.

  10. Chemistry and Heritage

    Science.gov (United States)

    Vittoria Barbarulo, Maria

    2014-05-01

    Chemistry is the central science, as it touches every aspect of the society we live in and it is intertwined with many aspects of our culture; in particular, the strong link between Chemistry and Archaeology and Art History is being explored, offering a penetrating insight into an area of growing interest from an educational point of view. A series of vital and vibrant examples (i.e., ancient bronzes composition, colour changes due to natural pigment decomposition, marble degradation) has been proposed, on one hand, to improve student understanding of the relationship between cultural and scientific issues arising from the examination, the conservation, and the maintenance of cultural Heritage, on the other, to illustrate the role of the underlying Chemistry. In some case studies, a survey of the most relevant atmospheric factors, which are involved in the deterioration mechanisms, has also been presented to the students. First-hand laboratory experiences have been providing an invaluable means of discovering the full and varied world of Chemistry. Furthermore, the promotion of an interdisciplinary investigation of a famous painting or fresco, involving the study of its nature and significance, the definition of its historical context, any related literature, the chemical knowledge of the materials used, may be an excellent occasion to experiment the Content and Language Integrated Learning (CLIL). The aim of this approach is to convey the important message that everyone has the responsibility to care for and preserve Heritage for the benefit of present and future generations.

  11. Investigation of NOx emissions and NOx-related chemistry in East Asia using CMAQ-predicted and GOME-derived NO2 columns

    Directory of Open Access Journals (Sweden)

    J. Y. Kim

    2009-02-01

    Full Text Available In this study, NO2 columns from the US EPA Models-3/CMAQ model simulations carried out using the 2001 ACE-ASIA (Asia Pacific Regional Aerosol Characterization Experiment emission inventory over East Asia were compared with the GOME-derived NO2 columns. There were large discrepancies between the CMAQ-predicted and GOME-derived NO2 columns in the fall and winter seasons. In particular, while the CMAQ-predicted NO2 columns produced larger values than the GOME-derived NO2 columns over South Korea for all four seasons, the CMAQ-predicted NO2 columns produced smaller values than the GOME-derived NO2 columns over North China for all seasons with the exception of summer (summer anomaly. It is believed that there might be some error in the NOx emission estimates as well as uncertainty in the NOx chemical loss rates over North China and South Korea. Regarding the latter, this study further focused on the biogenic VOC (BVOC emissions that were strongly coupled with NOx chemistry during summer in East Asia. This study also investigated whether the CMAQ-modeled NO2/NOx ratios with the possibly overestimated isoprene emissions were higher than those with reduced isoprene emissions. Although changes in both the NOx chemical loss rates and NO2/NOx ratios from CMAQ-modeling with the different isoprene emissions affected the CMAQ-modeled NO2 levels, the effects were found to be limited, mainly due to the low absolute levels of NO2 in summer. Seasonal variations of the NOx emission fluxes over East Asia were further investigated by a set of sensitivity runs of the CMAQ model. Although the results still exhibited the summer anomaly possibly due to the uncertainties in both NOx-related chemistry in the CMAQ model and the GOME measurements, it is believed that consideration of both the seasonal variations in NOx emissions and the correct BVOC emissions in East Asia are critical. Overall, it is estimated that the NOx emissions are underestimated by ~57.3% in North

  12. Phase relation of CaSO4 at high pressure and temperature up to 90 GPa and 2300 K

    Science.gov (United States)

    Fujii, Taku; Ohfuji, Hiroaki; Inoue, Toru

    2016-05-01

    Calcium sulfate (CaSO4), one of the major sulfate minerals in the Earth's crust, is expected to play a major role in sulfur recycling into the deep mantle. Here, we investigated the crystal structure and phase relation of CaSO4 up to ~90 GPa and 2300 K through a series of high-pressure experiments combined with in situ X-ray diffraction. CaSO4 forms three thermodynamically stable polymorphs: anhydrite (stable below 3 GPa), monazite-type phase (stable between 3 and ~13 GPa) and barite-type phase (stable up to at least 93 GPa). Anhydrite to monazite-type phase transition is induced by pressure even at room temperature, while monazite- to barite-type transition requires heating at least to 1500 K at ~20 GPa. The barite-type phase cannot always be quenched from high temperature and is distorted to metastable AgMnO4-type structure or another modified barite structure depending on pressure. We obtained the pressure-volume data and density of anhydrite, monazite- and barite-type phases and found that their densities are lower than those calculated from the PREM model in the studied P-T conditions. This suggests that CaSO4 is gravitationally unstable in the mantle and fluid/melt phase into which sulfur dissolves and/or sulfate-sulfide speciation may play a major role in the sulfur recycling into the deep Earth.

  13. 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.

  14. Plug Pulled on Chemistry Computer Center.

    Science.gov (United States)

    Robinson, Arthur L.

    1980-01-01

    Discusses the controversy surrounding the initial decision to establish, and the current decision to phase out, the National Resource for Computation in Chemistry (NRCC), a computational chemistry center jointly sponsored by the National Science Foundation and the Department of Energy. (CS)

  15. Systems chemistry: All in a spin

    Science.gov (United States)

    Clark, Lucy; Lightfoot, Philip

    2016-05-01

    A fundamental challenge in systems chemistry is to engineer the emergence of complex behaviour. The collective structures of metal cyanide chains have now been interpreted in the same manner as the myriad of magnetic phases displayed by frustrated spin systems, highlighting a symbiotic approach between systems chemistry and magnetism.

  16. Can we recognize magmatic fluid inclusions in fossil sytems based on room-temperature phase relations and microthermometric bahavior

    Energy Technology Data Exchange (ETDEWEB)

    Bodnar, R. (Virginia Polytechnic Institute and State University, VA (USA))

    1992-08-31

    If the density and composition of magmatic fluid and how these properties vary as the system evolves are known, the room temperature phase relations and microthermometric behavior of fluid inclusions which have trapped these magmatic fluids are considered to be predictable. Using available experimental and theoretical data for the model system albite-H2O-NaCl, the salinity of the aqueous phase exsolving from melts crystallizing at various depths (pressures) in the crust were calculated. Consequently, the results of the analysis of the characteristics of fluid inclusions trapped during crystallization of a silicic melt indicated that great care should be exercised in the selection of fluid inclusions to investigate magmatic fluids. Furthermore, late hydrothermal inclusions and similar magmatic inclusions are considered to be distinguishable from one another based on mode of occurrence, presence of tiny opaque daughter phases in magmatic inclusions, and relative ages. 5 figs.

  17. Art and Chemistry

    OpenAIRE

    Walter, Philippe

    2015-01-01

    Philippe Walter’s teaching, which he delivered as holder of the Liliane Bettencourt Annual Chair of Technological Innovation, was completed with two lectures on “practical work” to deal with a real case. The conditions and challenges of interdisciplinary research combining analytical chemistry, art history and archaeology were thus discussed in relation to specific works. The Holy Family, Constantin Abraham (1785-1855) by Raphaël (aka), Sanzio Raffaello (1483-1520), hard porcelain, Sèvres, C...

  18. 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).

  19. Proposed Mechanism for HII Phase Induction by Gramicidin in Model Membranes and Its Relation to Channel Formation

    OpenAIRE

    Killian, J. Antoinette; de Kruijff, Ben

    1988-01-01

    A model is proposed for the molecular mechanism of HII phase induction by gramicidin in model membranes. The model describes the sequence of events that occurs upon hydration of a mixed lipid/gramicidin film, relating them to gramicidin channel formation and to relevant literature on gramicidin and lipid structure.

  20. The Re-Mo-S system: New data on phase relations between 400 and 1200 °C

    Czech Academy of Sciences Publication Activity Database

    Drábek, M.; Rieder, M.; Böhmová, Vlasta

    2010-01-01

    Roč. 22, č. 4 (2010), s. 479-484. ISSN 0935-1221 Institutional research plan: CEZ:AV0Z30130516 Keywords : phase relations * Re–Mo–S system, * molybdenite * rheniite * Re * Mo * S Subject RIV: DB - Geology ; Mineralogy Impact factor: 1.469, year: 2010

  1. Chemistry of the transactinide elements

    International Nuclear Information System (INIS)

    The synthesis and decay of the elements 104, 105 and 106 are described as well as the chemistry of the elements in the gaseous and liquid phase. The electron configurations of the ground state of the elements 105 and higher are described, as well as further chemical properties. (SR)

  2. Energy and Environment as Related to Chemistry Teaching. Proceeding of the UNESCO International Workshop/Symposium (Berkeley, California, December 1-8, 1989).

    Science.gov (United States)

    California Univ., Berkeley. Board of Regents.

    The proceedings of a program on teaching chemistry through energy and the environment that included plenary lectures, country and commission reports, introductions to new programs and materials, and an experimental approach to curriculum development across national boundaries via the production of an instruction unit are provided. The workshop…

  3. Phase Relations in the Uranium-Uranium Dioxide System at High Temperatures

    International Nuclear Information System (INIS)

    Data from the literature plus extensive new work reported from this laboratory permit the delineation of a substantial portion of the temperature-composition phase diagram for the uranium-uranium dioxide system. Of particular interest to the many current investigations of the thermodynamic and transport properties of urania as a function of its stoichiometry is the compositional existence range of hypostoichiometric uranium dioxide. The essential features of the phase diagram presented are: (1) A wide liquid miscibility gas exists at temperatures above 2470 ± 25°C; which is the monotectic temperature in the system. (2) At the monotectic temperature, the compositions in O/U atom ratio units of the three condensed phases in mutual equilibrium are: liquid uranium, 0.05 ± 0.01; monotectic liquid, 1.30 ± 0.10; and solid hypostoichiometric uranium dioxide solid, 1.60 ± 0.02. (3) The hypostoichiometric phase boundary in the range 1600 to 2470°C can be expressed by the equation: LogXU = 1.404 - 5769/T, in which XU is the mole fraction of uranium dissolved in a stoichiometric uranium dioxide, and T is in degrees Kelvin. From this equation, the heat of solution of uranium in uranium dioxide is 26.5 kcal/mole. (4) No evidence was observed for the existence of stable phases intermediate to the liquid uranium and solid hypostoichiometric uranium compositions. (author)

  4. Experimental investigation and thermodynamic calculation of phase relations in the Mg-Nd-Y ternary system

    International Nuclear Information System (INIS)

    Mg-Nd-Y alloys ingots were cast and annealed at 753 K, and then analyzed with scanning electron microscopy (SEM), X-ray diffraction (XRD) and electron-probe microanalysis (EPMA) to determine phase equilibria in the Mg-rich part of the Mg-Nd-Y system. Existence of the ternary compound β with Mg5Gd-type structure was verified, which is in the equilibrium with hcpA3 (Mg). Furthermore, thermodynamic description of the Mg-Nd-Y system was carried out on the basis of the present experimental results. The thermodynamic parameters of the boundary Mg-Nd and Nd-Y binary systems were directly cited from literatures, while most of the parameters for the Mg-Y binary system were taken from the latest literature with an exception of a minor revision for the bccB2 phase in this paper. The ordered bccB2 and disordered bccA2 phases were described with a sublattice model (Mg,Nd,Y)0.5(Mg,Nd,Y)0.5 and their Gibbs energies were expressed with same function. Most of the binary intermetallic phases, except for Mg3Nd, were assumed to have no ternary solubility. The Mg3Nd and ternary compound β were treated as semistoichiometric compounds with mutual substitution between Nd and Y. Reasonable agreement of the phase equilibria in the Mg-Nd-Y ternary system between thermodynamic extrapolation and experiments was achieved

  5. Gas-phase chemistry of the yttrium-imido cation YNH{sup +} with alkenes: {Beta}-hydrogen activation by a d{sup 0} system via a multicentered transition state

    Energy Technology Data Exchange (ETDEWEB)

    Ranatunga, D.R.A.; Hill, Y.D.; Freiser, B.S. [Purdue Univ., West Lafayette, IN (United States)

    1996-02-20

    The gas-phase chemistry of the yttrium-imido carbon cations with alkenes was studied by using Fourier transform mass spectrometry to explore the chemistry of transition metal ion complexes with low-valence metal centers. The YNH{sup +} species was synthesized by reacting Y{sup +}, generated by laser desorption, with ammonia. The dehydrogenation reaction is exothermic, yielding a lower limit for the imido bond energy of D{degree}(Y{sup +}-NH) > 101 kcal/mol. Due to the electron deficiency of the metal center upon binding to NH, the further reactivity of YNH{sup +} can only be explained by a reaction mechanism involving a multicentered transition state. YNH{sup +} reacts with ethene predominantly by dehydrogenation to produce YC{sub 2}H{sub 3}N{sup +}. Thus, instead of the metathesis reaction involving the cleavage of the 2-aza-1-metallacyclobutane intermediate, a {beta}-hydrogen transfers to the metal center and is then eliminated with a hydrogen from the remaining CH{sub 2} group to complete the reaction. All three linear butenes, 1-butene, cis-2-butene, and trans-2-butene, react very similarly with YNH{sup +}, yielding a variety of product ions with the predominant loss of NH{sub 3} resulting in the formation of YCH{sub 4}H{sub 6}{sup +}. Structural studies on this ion suggest that it is bent metallacyclopent-3-ene, not the butadiene isomer. 34 refs., 1 fig.

  6. A computer model for one-dimensional mass and energy transport in and around chemically reacting particles, including complex gas-phase chemistry, multicomponent molecular diffusion, surface evaporation, and heterogeneous reaction

    Science.gov (United States)

    Cho, S. Y.; Yetter, R. A.; Dryer, F. L.

    1992-01-01

    Various chemically reacting flow problems highlighting chemical and physical fundamentals rather than flow geometry are presently investigated by means of a comprehensive mathematical model that incorporates multicomponent molecular diffusion, complex chemistry, and heterogeneous processes, in the interest of obtaining sensitivity-related information. The sensitivity equations were decoupled from those of the model, and then integrated one time-step behind the integration of the model equations, and analytical Jacobian matrices were applied to improve the accuracy of sensitivity coefficients that are calculated together with model solutions.

  7. Remarks on nonlinear relation among phases and frequencies in modulational instabilities of parallel propagating Alfvén waves

    Directory of Open Access Journals (Sweden)

    Y. Nariyuki

    2006-01-01

    Full Text Available Nonlinear relations among frequencies and phases in modulational instability of circularly polarized Alfvén waves are discussed, within the context of one dimensional, dissipation-less, unforced fluid system. We show that generation of phase coherence is a natural consequence of the modulational instability of Alfvén waves. Furthermore, we quantitatively evaluate intensity of wave-wave interaction by using bi-coherence, and also by computing energy flow among wave modes, and demonstrate that the energy flow is directly related to the phase coherence generation. We first discuss the modulational instability within the derivative nonlinear Schrödinger (DNLS equation, which is a subset of the Hall-MHD system including the right- and left-hand polarized, nearly degenerate quasi-parallel Alfvén waves. The dominant nonlinear process within this model is the four wave interaction, in which a quartet of waves in resonance can exchange energy. By numerically time integrating the DNLS equation with periodic boundary conditions, and by evaluating relative phase among the quartet of waves, we show that the phase coherence is generated when the waves exchange energy among the quartet of waves. As a result, coherent structures (solitons appear in the real space, while in the phase space of the wave frequency and the wave number, the wave power is seen to be distributed around a straight line. The slope of the line corresponds to the propagation speed of the coherent structures. Numerical time integration of the Hall-MHD system with periodic boundary conditions reveals that, wave power of transverse modes and that of longitudinal modes are aligned with a single straight line in the dispersion relation phase space, suggesting that efficient exchange of energy among transverse and longitudinal wave modes is realized in the Hall-MHD. Generation of the longitudinal wave modes violates the assumptions employed in deriving the DNLS such as the quasi

  8. Anomalous subduction related seismic phase from Cascadia slab earthquakes - observations and possible interpretations

    Science.gov (United States)

    Medema, G. F.; Crosson, R. S.; Creager, K. C.

    2001-12-01

    Over the time period 1980 - 2001 we have identified 15-20 Cascadia slab earthquakes in western Washington and southern British Columbia which clearly exhibit anomalous phase arrivals between the primary P and S phases. This phase is observed from slab origin earthquakes only (not crustal earthquakes) in the depth range 45-55 km, with a characteristic apparent velocity between 5.6 and 6.2 km/s. Furthermore, the phase is only observed on stations located on the Olympic Peninsula over a restricted range of azimuths from the source region, and has amplitude typically larger than direct P (often as large as S). A common feature of the stations that record this phase is that they lie in a region where the Crescent formation, a basalt-rich unit that forms the basement of the Puget basin, is absent. Most of the observed events generating this phase lie between 122W and 123W extending from the southeastern tip of Vancouver Island to the Washington-Oregon border. There are a few events directly north and west of the Olympics that also show secondary arrivals, but it is not clear if these are due to the same phenomenon. The phase is not observed from slab earthquakes which lie directly beneath the Olympics and near the eastern margin of the Olympics. Although we are uncertain of the origin of this anomalous phase, two possible models are actively under consideration: S-to-P conversion and a low velocity waveguide origin. S-to-P conversion may be consistent with the energetic nature of the phase, and preliminary travel time analysis suggests that it is difficult to rule out this origin based on travel time alone. Depth dependence of the S-to-P phase may help to test this model; however, the azimuthal dependence of the phase is clearly not consistent with S-P conversion. A waveguide model may more readily explain the observations. Waveguides have been proposed to explain anomalous late arrivals in the Aleutians [Helffrich and Abers, 1997] and southwestern Japan [Hori et al

  9. Global OZone Chemistry And Related Datasets for the Stratosphere (GOZCARDS): methodology and sample results with a focus on HCl, H2O, and O3

    OpenAIRE

    L. Froidevaux; Anderson, J.; H.-J. Wang; Fuller, R. A.; M. J. Schwartz; Santee, M. L.; Livesey, N.J.; Pumphrey, H. C.; Bernath, P. F.; J. M. Russell III; M. P. McCormick

    2015-01-01

    We describe the publicly available dataset from the Global OZone Chemistry And Related Datasets for the Stratosphere (GOZCARDS) project, and provide some results, with a~focus on hydrogen chloride (HCl), water vapor (H2O), and ozone (O3). This dataset is a global long-term stratospheric Earth System Data Record (ESDR), consisting of monthly zonal mean time series starting as early as 1979. The data records are based on high quality measurements from several ...

  10. Optimization of molecular and crystalline forms of drugs, agrochemicals, pesticides in relation to activity, bioavailability, patentability and to the fabrication of polymorphs, solvates, co-crystals with green chemistry methods

    OpenAIRE

    Nanna, Saverio

    2015-01-01

    This doctorate was funded by the Regione Emilia Romagna, within a Spinner PhD project coordinated by the University of Parma, and involving the universities of Bologna, Ferrara and Modena. The aim of the project was: - Production of polymorphs, solvates, hydrates and co-crystals of active pharmaceutical ingredients (APIs) and agrochemicals with green chemistry methods; - Optimization of molecular and crystalline forms of APIs and pesticides in relation to activity, bioavailability an...

  11. Organoactinide chemistry: synthesis, structure, and solution dynamics

    International Nuclear Information System (INIS)

    This thesis considers three aspects of organoactinide chemistry. In chapter one, a bidentate phosphine ligand was used to kinetically stabilize complexes of the type Cp2MX2. Ligand redistribution processes are present throughout the synthetic work, as has often been observed in uranium cyclopentadienyl chemistry. The effects of covalent M-L bonding on the solution and solid state properties of U(III) coordination complexes are considered. In particular, the nature of the more subtle interaction between the metal and the neutral ligand are examined. Using relative basicity data obtained in solution, and solid state structural data (and supplemented by gas phase photoelectron measurements), it is demonstrated that the more electron rich U(III) centers engage in significant U → L π-donation. Trivalent uranium is shown to be capable of acting either as a one- or two-electron reducing agent toward a wide variety of unsaturated organic and inorganic molecules, generating molecular classes unobtainable via traditional synthetic approaches, as well as offering an alternative synthetic approach to molecules accessible via metathesis reactions. Ligand redistribution processes are again observed, but given the information concerning ligand lability, this reactivity pattern is applied to the synthesis of pure materials inaccessible from redox chemistry. 214 refs., 33 figs., 10 tabs

  12. Liquid-Gas Phase Transition of Supernova Matter and Its Relation to Nucleosynthesis

    OpenAIRE

    Ishizuka, C.; Ohnishi, A; Sumiyoshi, K.

    2002-01-01

    We investigate the liquid-gas phase transition of dense matter in supernova explosion by the relativistic mean field approach and fragment based statistical model. The boiling temperature is found to be high (T_{boil} >= 0.7 MeV for rho_B >= 10^{-7} fm^{-3}), and adiabatic paths are shown to go across the boundary of coexisting region even with high entropy. This suggests that materials experienced phase transition can be ejected to outside. We calculated fragment mass and isotope distributio...

  13. Columnar phases exhibited by some polycatenar ligands and a few related metal complexes

    Indian Academy of Sciences (India)

    B K Sadashiva; V A Raghunathan

    2003-08-01

    The synthesis and characterization of some polycatenar ligands which exhibit hexagonal columnar and cubic phases are reported. A pentacatenar with only four phenyl rings in the core and exhibiting a mesophase is also reported. A few copper (II) and palladium (II) complexes have been synthesized using these ligands and the mesomorphic properties exhibited by them are described. The hexagonal columnar phase exhibited by some of the complexes can be cooled down to room temperature. The mesophases have been characterized using a combination of polarized light microscopy, differential scanning calorimetry and X-ray diffraction methods.

  14. On the use of functional calculus for phase-type and related distributions

    DEFF Research Database (Denmark)

    Bladt, Mogens; Campillo Navarro, Azucena; Nielsen, Bo Friis

    matrices. Functional calculus, which is a branch of operator theory frequently associated with complex analysis, can be applied to phase-type and matrix-exponential distributions in a rather straightforward way. In this paper we provide a number of examples on how to execute the formal arguments.......The area of phase-type distributions is renowned for its ability to obtain closed form formulas or algorithmically exact solutions to many complex stochastic models. The method of functional calculus will provide an additional tool along these lines for establishing results in terms of functions of...

  15. On the use of functional calculus for phase-type and related distributions

    DEFF Research Database (Denmark)

    Bladt, Mogens; Navarro, Azucena Campillo; Nielsen, Bo Friis

    2016-01-01

    matrices. Functional calculus, which is a branch of operator theory frequently associated with complex analysis, can be applied to phase-type and matrix-exponential distributions in a rather straightforward way. In this article we provide a number of examples of how to execute the formal arguments.......The area of phase-type distributions is renowned for its ability to obtain closed form formulas or algorithmically exact solutions to many complex stochastic models. The method of functional calculus will provide an additional tool along these lines for establishing results in terms of functions of...

  16. PWR secondary water chemistry guidelines: Revision 3

    International Nuclear Information System (INIS)

    An effective, state-of-the art secondary water chemistry control program is essential to maximize the availability and operating life of major PWR components. Furthermore, the costs related to maintaining secondary water chemistry will likely be less than the repair or replacement of steam generators or large turbine rotors, with resulting outages taken into account. The revised PWR secondary water chemistry guidelines in this report represent the latest field and laboratory data on steam generator corrosion phenomena. This document supersedes Interim PWR Secondary Water Chemistry Recommendations for IGA/SCC Control (EPRI report TR-101230) as well as PWR Secondary Water Chemistry Guidelines--Revision 2 (NP-6239)

  17. Evaluation of two-phase relative permeability and capillary pressure relations for unstable displacements in a pore network

    Energy Technology Data Exchange (ETDEWEB)

    Dehoff, Karl J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Oostrom, Martinus [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Zhang, Changyong [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Grate, Jay W. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2012-10-29

    A series of displacement experiments was conducted using five wetting-nonwetting immiscible fluid pairs in a homogenous and uniform pore network. The micromodel was initially saturated with either polyethylene glycol 200 (PEG) or water as a wetting fluid, which was subsequently displaced by a nonwetting fluid (dodecane, hexadecane, or mineral oil) at different flow rates. The experiments were designed to allow determinations of nonwetting fluid relative permeabilities ( ), fluid saturations ( ), and capillary pressure heads ( ). In the displacements, nonwetting fluid saturations increased with increasing flow rates for all five fluid pairs, and viscous fingering, capillary fingering, and stable displacement were observed. Viscous fingering occurred when PEG was displaced by either dodecane or hexadecane. For the water displacements, capillary fingers were observed at low capillary numbers. Due to unstable fingering phenomena, values for the PEG displacements were smaller than for the water displacements. A fitting exercise using the Brooks-Corey (1964) relationship showed that the fitted entry pressure heads are reasonably close to the computed entry pressure head. The fitted pore geometry factor, Sn values for the displacements are considerably lower than what is expected for displacements in homogeneous, highly uniform, porous systems, demonstrating the impact of unstable displacement on the apparent value of Sn. It was shown that a continuum-based multiphase model could be used to predict the average behavior for wetting fluid drainage in a pore network as long as independently fitted - and - relations are used. The use of a coupled approach through the Brooks-Corey pore geometry factor underpredicts observed values.

  18. Science Update: Inorganic Chemistry

    Science.gov (United States)

    Rawls, Rebecca

    1978-01-01

    This first in a series of articles describing the state of the art of various branches of chemistry reviews inorganic chemistry, including bioinorganic, photochemistry, organometallic, and solid state chemistries. (SL)

  19. 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)

  20. Crystal chemistry and phase equilibrium studies of the BaO(BaCO[sub 3])-[1/2]R[sub 2]O[sub 3]-CuO[sub x] systems in air; 6: R = neodymium

    Energy Technology Data Exchange (ETDEWEB)

    Wong-Ng, W.; Cook, L.P.; Paretzkin, B.; Hill, M.D.; Stalick, J.K. (National Inst. of Standards and Technology, Gaithersburg, MD (United States). Materials Science and Engineering Lab.)

    1994-09-01

    Crystal chemistry and subsolidus phase equilibrium studies of the Ba-Nd-Cu-O system near the CuO and Nd[sub 2]O[sub 3] corners have been carried out at 950 C in air. Two solid-solution series have been identified in the Ba-Nd-Cu-O system. The first series involves the high-[Tc] superconductor phase, and has the formula Ba[sub 2[minus]x]Nd[sub 1+x]Cu[sub 3]O[sub 6+z], where x < [approx] 0.7. At the ideal compound stoichiometry of Ba[sub 2]NdCu[sub 3]O[sub 6+z], the transformation from the high-[Tc] orthorhombic to tetragonal phase occurs at 550--575 C in air. This temperature varies as a function of composition, and at x [approx] 0.2 to 0.3 it occurs at 950 C. The second solid solution is the non-superconducting brown phase'' represented by Ba[sub 2+2x]Nd[sub 4[minus]2x]Cu[sub 2[minus]x]O[sub 10[minus]2z], 0 [<=] x [<=] 0.1. Preliminary phase diagrams of the BaO-Nd[sub 2]O[sub 3] and Nd[sub 2]O[sub 3]-CuO[sub x] systems are also presented. Standard X-ray diffraction patterns of BaNd[sub 2]CuO[sub 5] and (Nd[sub 1.9]Ca[sub 0.1])CuO[sub 4[minus]z] are provided.