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  • 1990-1994  (4)
  • 1980-1984  (6)
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  • 1
    Digitale Medien
    Digitale Medien
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 69 (1991), S. 2692-2693 
    ISSN: 1089-7550
    Quelle: AIP Digital Archive
    Thema: Physik
    Notizen: The determination of temperatures using single-shot coherent anti-Stokes Raman spectroscopy normally requires an accurate measurement of the instrument slit function. This slit function is normally determined at a known temperature, and then assumed to be the applicable function at all temperatures and independent of the optical path which varies with density or temperature gradients. In this communication we show a simple method of determining the width of the slit function from the collected data at the actual temperature and turbulence level. This method depends on local thermodynamic equilibrium and is a generally applicable technique to determine the instrument slit function. It is limited to temperatures in excess of 1100 K, as it requires that there be a nonzero signal in the v=1 vibrational level of N2.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 62 (1991), S. 2093-2099 
    ISSN: 1089-7623
    Quelle: AIP Digital Archive
    Thema: Physik , Elektrotechnik, Elektronik, Nachrichtentechnik
    Notizen: The temperature determined by a single-shot coherent anti-Stokes Raman spectroscopy (CARS) system is directly related to the half width at half maximum of the instrument slit function. Therefore, an accurate knowledge of the instrument slit function is necessary to determine temperature with CARS. However, in turbulent systems, the input slits of the spectrometer may be removed in order to guarantee signal throughput and establish the necessary dynamic range. In this case, the physical input slits of the spectrometer are replaced with apparent slits created by focussing the input beams near the entrance plane of the spectrometer. The slit function will then depend on the physical relationship among all of the optical components, the probe volume, and the dispersive performance of the spectrometer and detector, as well as the optical path through density and temperature gradients which may not be invariant in a turbulent system. The presence of high temperatures and turbulence levels can effect the size of the CARS signal origin and the optical path, and as a result, the slit function is not invariant. Ignoring these changes can result in large root mean square temperatures (decreased precision) as well as mean temperature errors. The variability of the slit width can be accounted for on a shot-to-shot basis by using a two parameter (HWHM of the slit function and temperature) fitting routine. For temperatures greater than 1200 K there is convergence on a best curve implying both a temperature and a slit width. This method can be used alone or in concert with various weighting schemes to improve the precision. There are two major advantages gained by allowing the slit function to vary in a CARS system: (a) it allows an increase in the precision; (b) it allows temperatures to be calculated without the assumption that the slit function does not change with temperature or turbulence or position within the flame. In fact, it allows the temperature to be determined with almost no previous knowledge of the slit function except the general shape. These two advantages combine to significantly simplify the study of turbulent combusting systems with CARS and to improve the precision, both point-to-point and shot-to-shot, of CARS.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 85 (1981), S. 2863-2866 
    Quelle: ACS Legacy Archives
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 109-117 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Thermochemical analysis of the electron capture process of SF6 leads to a rate constant for the reverse process \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm SF}_6^ - \mathop \to \limits^2 {\rm SF}_6 + e^ -,k_2 = 1.5 \times 10^{13 - 31.4/\theta } {\rm s}^{{\rm - 1}} $\end{document}, where θ = 2.303RT, in kcal/mol. The electron affinity of 32±3 kcal/mol is deduced from the observed bimolecularity of the capture process down to 0.1 torr Ar bath gas and estimated entropies of SF6 and SF6-. The capture process is discussed from the view point of the formation of a metastable SF6- electron (SF6·eL-) Langevin complex which appears to have a lifetime of about 2 × 10-13 s. Curve crossing from the SF6·eL- complex to vibrationally excited (SF6-)* appears to have a normal rate and A factor. This is interpreted to indicate near-resonant coupling between the orbiting electron and the vibronic motions of SF6, together with similarity in structure of SF6 and SF6-. It is shown that the apparent slowness of thermal electron ejection from SF6- is a result of an unfavorable equilibrium constant rather than a slow rate.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 677-691 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The bimolecular rate constant for the title reaction has been measured by very-low-pressure reactor techniques at 233 〈 T K 〈 338. The equilibrium constant has also been measured between 253 and 338 K. Our rate constants are in excellent agreement with recent measurements using very different techniques and reaction conditions, and the general agreement probably makes this one of the most accurately measured rateconstants. Transition state models of the reaction rule out a bent TS in favor of a TS with colinear Cl···H···C bonds. The curvature at higher temperatures (〉350 K) is quantitatively accounted for by transition state theory analysis. Tunneling is shown not to play a role. The measured values of K1 allow an experimental value of S° (CH3) to be fixed to only ±2.4 e.u. However, using known values of S° for all species gives ΔH°f298(CH3.) = 35.1 plusmn; 0.1 kcal/mol in excellent agreement with other measured values.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 6
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1311-1319 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reactions of Cl and Br atoms with H2O2 have been studied in the range of 300-350 K using the very-low-pressure-reactor technique. It was found that metathesis to produce HX and HO2 is the only significant process (≤99%). For the reaction of Br \documentclass{article}\pagestyle{empty}\begin{document}$${\rm Br}+{\rm H}_2{\rm O}_2\buildrel{2}\over{\rightarrow}{\rm Hbr} + {\rm HO}_2$$\end{document} k2 (300 K) = 1.3 ± 0.45 × 10-14 and k2 (350 K) = 3.75 ± 1.1 × 10-14 cm3/molecules·s, with an activation energy of 4.6 ± 0.7 kcal/mol. Using an estimated A factor for A2, we find \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} k_2 ({\rm benttransitionstate}) = 1.6 \times 10^{ - 11 - 4.3/\theta } \\ k_2 ({\rm lineartransitionstate}) = 4 \times 10^{ - 12 - 3.5/\theta } \\ \end{array}$$\end{document} suggesting that a best choice is E2 = 3.9 ± 0.4 kcal/mol. The relation of these values to ΔHf0 (HO2) is discussed.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 7
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 815-822 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics and equilibria in the system Br + t-BuO2H ⇆ HBr + t-BuO2· have been measured in the range of 300-350 K using the very low pressure reactor (VLPR) technique. Using an estimated entropy change in reaction (1) ΔS1 = 3.0 ± 0.4 cal/mol·K together with the measured ΔG1, we find ΔH1 = 1.9 ± 0.2 kcal/mol and DHº (t-BuO2-H) = 89.4 ± 0.2 kcal/mol ΔHf·(tBuO2·) = 20.7 kcal/mol and DHº (t-Bu-O2) = 29.1 kcal/mol. The latter values make use of recent values of ΔHf·(t-Bu) = 8.4 ± 0.5 kcal/mol and the known thermochemistry of the other species. The activation energy E1 is found to be 3.3 ± 0.6 kcal/mol, about 1 kcal lower than the value found for Br attack on H2O2. It suggests a bond 1 kcal stronger in H2O2 than in tBuO2H.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 8
    Publikationsdatum: 1991-09-01
    Print ISSN: 0034-6748
    Digitale ISSN: 1089-7623
    Thema: Elektrotechnik, Elektronik, Nachrichtentechnik , Physik
    Standort Signatur Erwartet Verfügbarkeit
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  • 9
    Publikationsdatum: 1991-02-15
    Print ISSN: 0021-8979
    Digitale ISSN: 1089-7550
    Thema: Physik
    Standort Signatur Erwartet Verfügbarkeit
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  • 10
    Publikationsdatum: 1981-10-01
    Print ISSN: 0022-3654
    Digitale ISSN: 1541-5740
    Thema: Chemie und Pharmazie , Physik
    Publiziert von American Chemical Society
    Standort Signatur Erwartet Verfügbarkeit
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