Photodegradation studies on C. I. reactive red 158

Dye-containing wastewater generated from textile industries is a major source of environmental pollution. Azo dyes, which are the largest group of coloring agents, are widely used in industry. Advanced Oxidative Processes are very promising for effluent treatment mainly due to their high efficiency and simplicity of operation. Our group became interested on photocatalytic methods (included in the AOP’s), using TiO2, for degradation of dyes, started with simpler structures and continued with commercial dyes. Titanium dioxide (TiO2) has proven to be the most effective and suitable catalyst for photocatalytic reaction due to its low cost economical, chemical stability, and insolubility. In this paper, the effects of UV light irradiation in the presence of TiO2 particles at various pH’s (3, 6, 8 and 10) on the photodegradation of an azo dye, Reactive Red 158, were investigated. The photocatalytic degradation was carried out either in aqueous solutions or in a synthetically prepared dyebath effluent, under UV irradiation, in the presence of Degussa P25 TiO2 as the catalyst. Reactive dyes of the pyrimidinyl type partly hydrolyse during dyeing in basic medium; RR 158 was hydrolysed and this solution was also irradiated. The fastest degradation was obtained with an acid solution (14 minutes, 95.53% loss of colour), but the hydrolysed dye took longer to be decolourised

Scope for Credit Risk Diversification

This paper considers a simple model of credit risk and derives the limit distribution of losses under different assumptions regarding the structure of systematic risk and the nature of exposure or firm heterogeneity. We derive fat-tailed correlated loss distributions arising from Gaussian risk factors and explore the potential for risk diversification. Where possible the results are generalised to non-Gaussian distributions. The theoretical results indicate that if the firm parameters are heterogeneous but come from a common distribution, for sufficiently large portfolios there is no scope for further risk reduction through active portfolio management. However, if the firm parameters come from different distributions, then further risk reduction is possible by changing the portfolio weights. In either case, neglecting parameter heterogeneity can lead to underestimation of expected losses. But, once expected losses are controlled for, neglecting parameter heterogeneity can lead to overestimation of risk, whether measured by unexpected loss or value-at-risk

Structure, dielectric relaxation and electrical conductivity of 2,3,7,8-Tetramethoxychalcogenanthrene-2,3-dichloro-5,6-dicyano-1,4-benzoquinone 1:1 charger-transfer complexes

[EN] 2,3,7,8-Tetramethoxychalcogenanthrenes (5,10-chalcogena-cyclo-diveratrylenes, 'Vn(2)E(2)', E = S, Se) form isotypical 1:1 charge-transfer (CT) complexes with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). X-ray analysis of Vn(2)S(2) . DDQ shows the compound to have a columnar structure with segregated stacks of donors and acceptors. The donors are virtually planar in accordance with a formulation of [Vn(2)E(2)](+)[DDQ](-). Donor cations and acceptor anions are equidistant in their respective stacks, but in each case they inclined to the stacking axis, nevertheless guaranteeing an optimum overlap of the half-filled frontier orbitals which are of pi-type character according to MNDO calculations. Dielectric ac measurements of permittivity epsilon' and loss factor E '' clearly reveal two processes, a dielectric one at low temperatures and a conductive one at high temperatures. The dielectric process can be described by the Havriliak-Negami (HN) and the Kohlrausch-Williams-Watts (KWW) model, and the conductive process by a Debye-type plot. Using these methods, the relevant parameters are evaluated. The de conductivities of polycrystalline samples moulded at 10(8) Pa show a temperature dependence in the plots of ln sigma vs. T-1, which is typical of semiconductors. Two slopes are found; that in the low-temperature region (<285 K) is explained by an easy-path model (intragrain conductivity with low activation energies), whereas in the high-temperature region conduction across the grain boundaries (with higher activation energies) is becoming predominant. The activation energies for the intrinsic conductivities obtained by the ac and de measurements are similar. Despite the columnar structure with segregated stacks, due to stoichiometric oxidation states of the components, the absolute values of conductivity are low ten. 10(-6) S cm(-1) at 293 K), though higher (by a factor of ca. 10(3)) than those of compounds like Vn(2)E(2) . TCNQ with stacks in which donor and acceptor molecules alternate.Behrens, U.; Díaz Calleja, R.; Dötze, M.; Franke, U.; Gunsser, W.; Klar, G.; Kudnig, J.... (1996). Structure, dielectric relaxation and electrical conductivity of 2,3,7,8-Tetramethoxychalcogenanthrene-2,3-dichloro-5,6-dicyano-1,4-benzoquinone 1:1 charger-transfer complexes. Journal of Materials Chemistry. 6(4):547-553. https://doi.org/10.1039/JM9960600547S54755364Behrens, J., Hinrichs, W., Link, T., Schiffling, C., & Klar, G. (1995). SELFSTACKING SYSTEMS, PART 6.1HOST LATTICE FUNCTION OF 2,3,8,9-TETRAMETHOXYDIBENZO[c,e][1,2]-DICHALCOGENINS IN THEIR ELECTRICALLY CONDUCTING IODINE COMPLEXES. Phosphorus, Sulfur, and Silicon and the Related Elements, 101(1-4), 235-244. doi:10.1080/10426509508042522Berges, P., Kudnig, J., Klar, G., Martínez, E. S., & Calleja, R. D. (1989). Elementorganische Verbindungen mit o-Phenylenresten, XVI . 2:1-Komplexe von 2,3,7,8-Tetramethoxychalcogenanthrenen mit Tetracyanethen / Organometallic Compounds with o-Phenylene Substituents, Part XVI 2:1-Complexes of 2,3,7,8-Tetramethoxychalcogenanthrenes with Tetracyanoethene. Zeitschrift für Naturforschung B, 44(2), 211-219. doi:10.1515/znb-1989-0219Hinrichs, W., Berges, P., Klar, G., Sánchez-Martínez, E., & Gunsser, W. (1987). Structure and electrical conductivity of TCNQ-2,3,7,8-tetramethoxychalcogenanthrene complexes. Synthetic Metals, 20(3), 357-364. doi:10.1016/0379-6779(87)90832-0Sánchez Martínez, E., Díaz Calleja, R., Gunsser, W., Berges, P., & Klar, G. (1989). Structure and dielectric relaxation of 2,3,7,8-tetramethoxychalcogenanthrene-TCNQ complexes. Synthetic Metals, 30(1), 67-78. doi:10.1016/0379-6779(89)90642-5Gunßer, W., Henning, J. H., Klar, G., & Martínez, E. S. (1989). Spin Density and Magnetic Susceptibility of Charge-Transfer Complexes with Chalkogenanthrene Donors. Berichte der Bunsengesellschaft für physikalische Chemie, 93(11), 1370-1373. doi:10.1002/bbpc.19890931148G. M. Sheldrick , SHELXTL-PLUS, Release 4.21/0, Siemens Analytical X-Ray Instruments, 1990.Bock, H., Rauschenbach, A., Näther, C., Havlas, Z., Gavezzotti, A., & Filippini, G. (1995). Orthorhombisches und monoklines 2,3,7,8-Tetramethoxythianthren: kleiner Strukturunterschied – große Gitteränderung. Angewandte Chemie, 107(1), 120-122. doi:10.1002/ange.19951070132Bock, H., Rauschenbach, A., Näther, C., Havlas, Z., Gavezzotti, A., & Filippini, G. (1995). Orthorhombic and Monoclinic 2,3,7,8-Tetramethoxythianthrene: Small Structural Difference–Large Lattice Change. Angewandte Chemie International Edition in English, 34(1), 76-78. doi:10.1002/anie.199500761Hinrichs, W., Berges, P., & Klar, G. (1987). Selbststapelnde Systeme, IV 2,3,7,8-Tetramethoxythianthreniumsalze/Selfstacking Systems, Part IV 2.3.7.8-Tetramethoxythianthrenium Salts. Zeitschrift für Naturforschung B, 42(2), 169-176. doi:10.1515/znb-1987-0209Peover, M. E. (1962). 879. A polarographic investigation into the redox behaviour of quinones: the roles of electron affinity and solvent. Journal of the Chemical Society (Resumed), 4540. doi:10.1039/jr9620004540Wheland, R. C., & Gillson, J. L. (1976). Synthesis of electrically conductive organic solids. Journal of the American Chemical Society, 98(13), 3916-3925. doi:10.1021/ja00429a030Zanotti, G., Del Pra, A., & Bozio, R. (1982). Structure of tetraethylammonium–2,3-dichloro-5,6-dicyano-p-benzoquinone. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, 38(4), 1225-1229. doi:10.1107/s0567740882005330Zanotti, G., Bardi, R., & Del Pra, A. (1980). Structure of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ). Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, 36(1), 168-171. doi:10.1107/s0567740880002750Handbook of Chemistry and Physics, ed. R. C. Weast, CRC Press, Cleveland, OH, 1977–1978, 58th edn., p. D–178.Sánchez Martínez, E., Díaz Calleja, R., Berges, P., Kudnig, J., & Klar, G. (1989). Structure, electrical conductivity and dielectric relaxation of a 1,2-dimethoxybenzene-tetracyanoethene 1:1 complex. Synthetic Metals, 32(1), 79-89. doi:10.1016/0379-6779(89)90831-xÅsbrink, L., Fridh, C., & Lindholm, E. (1977). HAM/3, a semi-empirical MO theory. I. The SCF method. Chemical Physics Letters, 52(1), 63-68. doi:10.1016/0009-2614(77)85121-xÅsbrink, L., Fridh, C., & Lindholm, E. (1977). HAM/3, a semi-empirical MO theory. III. Unoccupied orbitals. Chemical Physics Letters, 52(1), 72-75. doi:10.1016/0009-2614(77)85123-3Dewar, M. J. S., & Thiel, W. (1977). Ground states of molecules. 38. The MNDO method. Approximations and parameters. Journal of the American Chemical Society, 99(15), 4899-4907. doi:10.1021/ja00457a004Dewar, M. J. S., & Thiel, W. (1977). Ground states of molecules. 39. MNDO results for molecules containing hydrogen, carbon, nitrogen, and oxygen. Journal of the American Chemical Society, 99(15), 4907-4917. doi:10.1021/ja00457a005Åsbrink, L., Fridh, C., & Lindholm, E. (1978). Valence excitation of linear molecules.I. Excitation and UV spectra of N2, Co, acetylene and HCN. Chemical Physics, 27(2), 159-168. doi:10.1016/0301-0104(78)88001-xFridh, C., Åsbrink, L., & Lindholm, E. (1978). Valence excitation of linear molecules. II. Excitation and UV spectra of C2N2, CO2 and N2O. Chemical Physics, 27(2), 169-181. doi:10.1016/0301-0104(78)88002-1Lindholm, E., Bieri, G., Åsbrink, L., & Fridh, C. (1978). Interpretation of electron spectra. III. Spectra of formamide, studied withHAM/3. International Journal of Quantum Chemistry, 14(6), 737-740. doi:10.1002/qua.560140605Starkweather, H. W. (1981). Simple and complex relaxations. Macromolecules, 14(5), 1277-1281. doi:10.1021/ma50006a025Starkweather, H. W. (1990). Distribution of activation enthalpies in viscoelastic relaxations. Macromolecules, 23(1), 328-332. doi:10.1021/ma00203a056Havriliak, S., & Negami, S. (1967). A complex plane representation of dielectric and mechanical relaxation processes in some polymers. Polymer, 8, 161-210. doi:10.1016/0032-3861(67)90021-3J. Ross McDonald , Complex Nonlinear Least Squares Immitance Fitting Program, LEVM6, 1993;Impedance Spectroscopy, Wiley-Interscience, New York, 1987.Williams, G. (1978). Time-correlation functions and molecular motion. Chemical Society Reviews, 7(1), 89. doi:10.1039/cs9780700089Williams, G., & Watts, D. C. (1970). Non-symmetrical dielectric relaxation behaviour arising from a simple empirical decay function. Transactions of the Faraday Society, 66, 80. doi:10.1039/tf9706600080A. R. West , Solid State Chemistry and its Applications, Wiley, Chichester, 1984, ch. 13.Sánchez Martínez, E., Díaz Calleja, R., & Klar, G. (1990). Self-stacking systems 5. Electrical and dielectric properties of 5,5-dibromo-2,3,7,8-tetramethoxyselenanthrene. Synthetic Metals, 38(1), 93-98. doi:10.1016/0379-6779(90)90071-

Naphthotriazole derivatives : synthesis and fluorescence properties

Eight fluorescent compounds containing a naphthotriazole moiety substituted at position 2 by a (vinylsulfonyl)aryl group or its precursors, containing hydroxyl or sulphonic groups or N-methylglycine, were prepared and characterized. The products were recovered in moderate yields after column chromatography or recrystallization and identified by proton and carbon nuclear magnetic resonance spectroscopy. Double resonance, heteronuclear multiple quantum coherence and heteronuclear multiple bond correlation experiments were carried out for complete assignment of proton and carbon signals. Absorption and emission spectra were obtained, in acetonitrile, for all the compounds and the fluorescence quantum yields determined. All compounds are promising fluorescent probes due to their high fluorescence quantum yields.Research grant VZ MSMT-0021627501, Czech RepublicFundação para a Ciência e a Tecnologia (FCT) - REEQ/ 630/QUI/2005; REDE/1517/RMN/2005FEDER - REEQ/ 630/QUI/2005; REDE/1517/RMN/200

Astrochemistry in an Ion Storage Ring

Storage ring studies of low energy electron collisions with molecular ions have been carried out for dissociative recombination (DR) of fluorine-bearing molecules. Here we report on work aiming to improve the understanding of astrochemistry involving HF, a possible spectroscopic tracer of interstellar H2. For CF+ the rate coefficient was obtained for temperatures down to 10 K. For D2F+ the DR fragmentation branching ratios were determined to be 66(3)%, 24(2)%, and 10(2)% for the F+D+D, DF+D, and D2+F channels, respectively. The molecular DR products of this reaction, DF and D2, display an unusually high level of internal excitation, close to their dissociation limit

Dissociative recombination measurements of NH+ using an ion storage ring

We have investigated dissociative recombination (DR) of NH+ with electrons using a merged beams configuration at the TSR heavy-ion storage ring located at the Max Planck Institute for Nuclear Physics in Heidelberg, Germany. We present our measured absolute merged-beams recombination rate coefficient for collision energies from 0 to 12 eV. From these data, we have extracted a cross section, which we have transformed to a plasma rate coefficient for the collisional plasma temperature range from T pl = 10 to 18,000 K. We show that the NH+ DR rate coefficient data in current astrochemical models are underestimated by up to a factor of approximately nine. Our new data will result in predicted NH+ abundances lower than those calculated by present models. This is in agreement with the sensitivity limits of all observations attempting to detect NH+ in interstellar clouds

Exploring high-energy doubly excited states of NH by dissociative recombination of NH+

We have investigated electron capture by NH+ resulting in dissociative recombination (DR). The impact energies studied of ~4–12 eV extend over the range below the two lowest predicted NH+ dissociative states in the Franck–Condon (FC) region of the ion. Our focus has been on the final state populations of the resulting N and H atoms. The neutral DR fragments are detected downstream of a merged electron and ion beam interaction zone in the TSR storage ring, which is located at the Max Planck Institute for Nuclear Physics in Heidelberg, Germany. Transverse fragment distances were measured on a recently developed high count-rate imaging detector. The distance distributions enabled a detailed tracking of the final state populations as a function of the electron collision energy. These can be correlated with doubly excited neutral states in the FC region of the ion. At low electron energy of ~5 eV, the atomic product final levels are nitrogen Rydberg states together with ground-state hydrogen. In a small electron energy interval near 7 eV, a significant part of the final state population forms hydrogen Rydberg atoms with nitrogen atoms in the first excited ($\rm ^2D$) term, showing the effect of Rydberg doubly excited states below the predicted 2 2Π ionic potential. The distance distributions above ~10 eV are compatible with nitrogen Rydberg states correlating to the doubly excited Rydberg state manifold below the ionic 2 4Σ− level