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  • Physical Chemistry  (405)
  • 04. Solid Earth::04.06. Seismology::04.06.04. Ground motion
  • Wiley-Blackwell  (406)
  • Taylor and Francis
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  • 1
    Digitale Medien
    Digitale Medien
    Disproportionation reactions between alkyl and fluoroalkyl radicals. VII. Difluoromethyl with perfluoro-n-propyl and methyl radicals (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 735-742 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Mixtures of 1,1,3,3-tetrafluoroacetone and perfluorodi-n-propyl ketone have been photolyzed together over the temperature range 50° to 200°C, and the disproportionation/combination ratio for n-C3F7 and CF2H radicals has been determined to be Δ(n-C3F7, CF2H) = 0.072 ± 0.003. A reevaluation of existing data on CH3 and CF2H radicals leads to a value of Δ(CH3, CF2H) = 0.35. The large variations in Δ for the reactions of alkyl and perfluoroalkyl radicals with CF2H radicals are discussed. © John Wiley & Sons, Inc.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550240807
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  • 2
    Digitale Medien
    Digitale Medien
    Disproportionation reactions between alkyl and fluoroalkyl radicals. V. Perfluoro-n-propyl and ethyl radicals revisited (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 1051-1069 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A redetermination of the disproportionation/combination ratio for n-C3F7 and C2H5 radicals gives a value of Δ(n-C3F7, C2H5) = 0.13 ± 0.01, independent of the temperature. The radicals were produced by the photolysis of n-C3F7COC2H5. The previous determinations of this ratio are discussed and are found to be largely incorrect. The values for Δ(CF3, C2H5) and Δ(C2F5, C2H5) are also re-evaluated, and the recommended values are 0.10 ± 0.02 and 0.12 ± 0.02, respectively. Systems involving perfluoroalkyl and ethyl radicals are complicated due to rapid perfluororadical addition to the ethylene formed in the disproportionation process. The extent of this reaction, and its consequences, are discussed and evaluated. The role of the propionyl (C2H5CO) radical in the room temperature photolysis is also assessed. However, it is found that the Δ values determined by the intercept method used in this work are not affected by the secondary reactions that occur. It is concluded that high cross-combination ratios are general to perfluoroalkyl-alkyl radical interactions. For C3F7 and C2H5 radicals the ratio is 2.7-2.8. Above 100°C ratios exceed 3 due to secondary reactions.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550221005
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  • 3
    Digitale Medien
    Digitale Medien
    Erratum (1991)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 23 (1991), S. 103-103 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550230110
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  • 4
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    Site Classification Assessment for Estimating Empirical Attenuation Relationships for Central-Northern Italy Earthquakes (2008)
    Taylor and Francis
    Details
    Publikationsdatum: 2017-04-04
    Beschreibung: The aim of this article is to investigate the ground motion attenuation of the most industrialized and populated regions of Italy, evaluating the capability of different approaches to estimate site dependent models. The 5.2 magnitude earthquake on November 24, 2004 shocked the areas of Northern Italy producing damage of about 215 million euros. The data set, including 243 earthquakes of local magnitude up to 5.2, has been collected in the period December 2002–October 2005 by 30 threecomponent seismic stations managed by Istituto Nazionale di Geofisica e Vulcanologia, Sezione of Milano (INGV-MI). Empirical attenuation relationships have been estimated for horizontal peak ground velocity (PGHV), acceleration (PGHA), displacement (PGHD), and for response spectral acceleration (SA) for periods between 0.1 and 1.5 s. To estimate suitable attenuation models, in particular for sites characterized by thick sedimentary geological formations, a soil discrimination based on EU8 code can lead to wrong evaluations. On the contrary, a classification based on H/V spectral ratios of seismic ambient noise (NHV) allows the models to fit better real and predicted data and to reduce the uncertainties of the process. For each receiver, NHV have been strengthened by additional H/V spectral ratio of earthquake data (EHV), calculated considering different portions of the analysed signals. In order to validate the PGHA attenuation relationship for greater magnitudes, accelerometric records, relative to Central-Northern Italy strong motions occurring in the last 30 years, have been collected and superimposed to our attenuation curves.
    Beschreibung: Published
    Beschreibung: 943-967
    Beschreibung: 4.1. Metodologie sismologiche per l'ingegneria sismica
    Beschreibung: JCR Journal
    Beschreibung: open
    Schlagwort(e): site effects ; 04. Solid Earth::04.06. Seismology::04.06.04. Ground motion
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 5
    Digitale Medien
    Digitale Medien
    Gas phase reactivities of isomeric ions: Methylenediphenylcyclopropane and diphenylmethylenecyclopropane (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 117-130 
    Details
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Gas phase ion/molecule reactions have been used to probe the structure of ions obtained by electron impact upon 1-(diphenylmethylene)cyclopropane and 2,2-diphenyl-1-methylenecyclopropane. The resulting ions of molecular composition C16H14 (m/z 206+) were reacted with charge transfer reagents (6·9 〈 IP 〈 8·8eV), giving evidence for the presence of isomeric ions with different reactivities. The less reactive ion is identified as a trimethylenemethane species (TMM+) in which one cyclopropane bond is broken; the more reactive ions are assigned as vertical ions in which the cyclopropane ring is unaffected. The vertical ions have recombination energies of 8·44 ± 0·05eV, whereas TMM+ has one of 7·41±0·05eV. The TMM+ fraction is not constant; it increases with increasing IP of the reagent. This is attributed to a reagent-catalyzed isomerization of the vertical ion to TMM+. In addition, the reagent ions are observed to undergo a unique reaction with the neutral methylenecyclopropane derivatives: electron transfer and ring opening to yield TMM+. These findings limit the application of the customary equilibrium measurements as a method to determine the substrate IP.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/poc.610020205
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  • 6
    Digitale Medien
    Digitale Medien
    Solvation effects on the relative basicity of propylamines (1995)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 26-30 
    Details
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Slight structural moiecular variations are known to affect different properties of compounds. In solution, different solute-solvent interactions are known also to alter the properties of numerous compounds. Quantitative structure-activity relationships (QSAR) are used regularly to analyze and predict the variations of different properties of compounds that are caused by structural variations and significant solute-solvent interactions. The relative basicities of n-propylamine, dipro;ylamine and tripropylamine were determined in nine different solvents from potentiometric titrations. QSAR that were developed from these experimental basicity values were used to evaluate the type and significance of the solute-solvent interactions. The important interactions that influence basicity variations for the propylamines studied are dipolarity-polarizability interaction between the solute and the solvent and hydrogen bonds from the propylammonium ions to basic solvents. The role of hydrogen bonds from the propylamines to acidic solvents is minor.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/poc.610080106
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  • 7
    Digitale Medien
    Digitale Medien
    Structure of, and internal rotation in, hexakis [4-(2-phenylpropan-2-yl) phenoxy] benzene, and structural comparison with its precursor phenol 4-(2-phenylpropan-2-yl)Phenol (1992)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 5 (1992), S. 628-632 
    Details
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The title compounds (1 and 3, respectively) were studied by X-ray crystal structure analysis. Both are trigonal, space group R3, with lattice parameters a = 27.718(6), c = 8.161(2) Å, Z = 3 and a = 31.267(7), c = 6.560(2), Z = 18, respectively. The dodecamethyl compound 1 is isomorphous with its parent hexakis(4-benzylphenoxy)benzene (2), a known host. However, ‘collapse’ along the c-axial direction has occurred such that the appreciable clathrate cavity of 2 has been replaced by only a very small residual void for 1. Phenol 3 does not pack in discrete [OH]6 hydrogenbonded hexamers; instead, molecules are assembled in infinite chains, linked by OH…O hydrogen bonds of length 2.735(3) Å, which are propagated along threefold screw axes. A variable-temperature CPMAS NMR study of sidechain aryl group rotation in 1 gives a value ΔG≠ of 14.0 ± 0.7 kcal mol-1 (at 42 °C) for the (crystallographically unique) para -disubstituted ring, a similar 14 kcal mol-1 free energy barrier being found hindering rotation of this ring, and of the outer phenyl ring of 1, at 9°C.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/poc.610051003
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  • 8
    Digitale Medien
    Digitale Medien
    Stereochemistry of aminolysis of N-pentafluorophenylcarbonimidoyl dichloride. Crystal and molecular structures of N2-pentafluorophenyl-N1,N1-dibenzylchloroformamidine (1993)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 319-325 
    Details
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: It has been established that the product of the reaction of N-pentafluorophenylcarbonimidoyl dichloride (1) with dibenzylamine, viz. N2-pentafluorophenyl-N1,N1-dibenzylchloroformamidine (4a) is a Z-isomer, whereas according to the concept of stereoelectronic control one might have expected a product with E-configuration. The heat of formation and the geometry of Z- and E isomer of N2-pentafluorophenyl-N1,N1-diethylchloroformamidine (4b) (the latter is a product of the reaction of 1 with diethylamine) were calculated with the semi-empirical MNDO method. The calculated geometry of (Z)-4b was found to be in a good agreement with the experimentally determined structure of 4a. The formation of (Z)-4b is more preferable energetically than that of (E)-4b; the calculated difference in the heats of formation is 2·8 kcal mol-1. Thermodynamic control of the reaction stereochemistry is proposed.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/poc.610060602
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  • 9
    Digitale Medien
    Digitale Medien
    A flash photolysis-resonance fluorescence kinetics study of the reactions of ground-state sulfur atoms. V. Rate parameters for the reaction of S(3P)with cis-2-butene and tetramethylethylene (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 841-857 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rate parameters for the reaction of ground-state atomic sulfur, S(3P), with the olefins cis-2-butene and tetramethylethylene have been determined over a temperature range of ∽280°K. A major finding of this study was that the rate constants for both reactions showed negative temperature dependencies. When k is expressed in the form of an Arrhenius equation, this necessarily leads to negative activation energies: k1 = (4.68 ± 0.70) × 10-12 exp (+0.23 ± 0.09 kcal/mole)/RT (219°-500°K) k2 = (4.68 ± 1.70) × 10-12 exp (+1.29 ± 0.23 kcal/mole)/RT (252°-500°K) Units are cm3 molec-1s-1. When a threshold energy of 0.0 kcal/mole is assumed for reaction (2), the temperature dependence of the preexponential term has a value of T-2. Making the usual simplifying assumptions, neither collision theory nor transition state theory leads to a preexponential factor with a strong enough negative temperature dependence. A comparison of these results with those derived from studies of the reactions of atomic oxygen, O(3P), with the same olefins shows that in both studies simple bimolecular processes were being examined. Also discussed are the possible experimental and theoretical ramifications of these new results.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550050511
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  • 10
    Digitale Medien
    Digitale Medien
    The pyrolysis of 2-nitrosoisobutane and the bond dissociation energies of nitroso compounds (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 813-828 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Study of the reaction by very-low-pressure pyrolysis (VLPP) in the temperature range of 550-850°K yields for the high-pressure Arrhenius parameters \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }\,k_{\rm 1} = (15.6 \pm 0.5) - (36.0 \pm 1.0)/\theta {\rm \,(sec}^{{\rm - 1}})$$\end{document} where θ = 2.303RT in kcal/mole. These in turn yield for the high-pressure second-order recombination of tBu + NO, k-1 = (3.5 ± 1.7) × 109 1./mole·sec at 600°K. For the competing reaction l./mole·sec and E4 ≥ 4.2 kcal/mole. The bond dissociation energy DHo (tBu-NO) was determined to be (39.5 ± 1.5) kcal/mole, both from the equilibrium constant and from the activation energy of reaction (1), obtained from RRKM calculations. A ‘free-volume’ model for the transition state for dissociation is consistent with the data. A limited study of the system at 8-200 torr showed an extremely rapid inhibition by products and a very complex set of products.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550060605
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