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  • 1
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 6881-6892 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A temperature gradient in a liquid mixture causes a concentration gradient through the Soret effect. We have developed an instrument to measure the Soret effect by observing the bending of a laser beam propagating horizontally through the liquid mixture subjected to a temperature gradient in the vertical direction. Our design of the liquid cell, with a long path length and controlled temperature uniformity, enables us to measure Soret coefficients with an accuracy of 1–3 %, higher than that obtained by previous investigators. In addition, by measuring the dynamic response of the beam deflection after imposition of the temperature gradient, we can also determine the mutual diffusion coefficient. We have applied the technique to mixtures of toluene and n-hexane over the temperature range 5–45 °C and to mixtures of ethanol and water at 25 °C. We have verified that the measured value of the Soret coefficient is independent of the magnitude of the temperature gradient imposed up to 14 K/cm. The Soret coefficients obtained for mixtures of toluene and n-hexane differ from the values obtained by previous investigators with a thermogravitational column method, but they are in good agreement with the results recently obtained by Köhler and Müller with a forced Rayleigh scattering method. For mixtures of ethanol and water, our Soret coefficients agree with the results obtained earlier by Kolodner et al., also with an optical beam-bending technique. © 1996 American Institute of Physics.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2270-2282 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The Soret coefficient ST and collective (mass) diffusion coefficient Dc of polystyrene dissolved in the good-solvent toluene has been measured over a range of concentrations and molecular masses with an optical beam-deflection method. Our measurements indicate that ST scales inversely with the polymer translational diffusion coefficient in dilute solutions, exhibits a power-law scaling with polymer concentration, and an independence of polymer molecular mass in semidilute solutions. These findings are consistent with the known scaling of 1/Dc in dilute and semidilute polymer solutions, the relative insensitivity of the thermal-diffusion coefficient Dth of polystyrene in toluene to polymer concentration, and the relation ST=Dth/Dc from irreversible thermodynamics. We are able to represent our ST and Dc data by theoretically motivated reduced-concentration master curves, but the concentration-molecular mass scaling variables are found to be different for each transport property, a result contrary to theoretical expectations. However, the asymptotic concentration scaling exponents deduced from these data fits are compatible with de Gennes' scaling arguments for Dc and with modern estimates of the chain-size exponent ν for swollen polymers in good solvents. © 1999 American Institute of Physics.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 109 (1998), S. 9038-9051 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: We report turbidity, light scattering, and coexistence curve data for a solution of triethyl n-hexyl ammonium triethyl n-hexyl borate in diphenylether. We recently reported that the present sample shows much higher turbidity than that of K. S. Zhang, M. E. Briggs, R. W. Gammon, and J. M. H. Levelt Sengers [J. Chem. Phys. 109, 4533 (1998)] for an earlier sample. An analysis of the data shows that nonclassical critical behavior is favored in the reduced temperature range from 10−5 to 10−2. At fixed reduced temperature, the correlation length is about twice as large as that of the previous sample. The correlation length amplitude calculated from the fit is 1.4 nm±0.1 nm. A detailed data analysis points out the limitations of turbidity measurements far away from the critical point. The intensity of scattered light was measured at 90°. Multiple scattering is relevant in the wider vicinity of the critical point and was corrected for by a Monte Carlo simulation method. An Ising-type exponent for the correlation length was obtained: ν=0.641±0.003, and the amplitude of the correlation length ξ0=1.34 nm±0.01 nm agrees with that of the turbidity experiment. Mean-field behavior can be ruled out. The refractive indices of coexisting phases were measured in the reduced temperature range from t=10−4 to 0.04. These measurements disagree with results reported by R. R. Singh and K. S. Pitzer [J. Chem. Phys. 92, 6775 (1990)]. The present data lead to an exponent β=0.34±0.01, close to the Ising value. The coexistence curve is much narrower than that of Singh and Pitzer. Crossover could not be detected in any of the experiments. Two-scale-factor universality could be confirmed for this and another ionic system within the experimental uncertainty. © 1998 American Institute of Physics.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    [s.l.] : Macmillan Magazines Ltd.
    Nature 401 (1999), S. 876-876 
    ISSN: 1476-4687
    Quelle: Nature Archives 1869 - 2009
    Thema: Biologie , Chemie und Pharmazie , Medizin , Allgemeine Naturwissenschaft , Physik
    Notizen: [Auszug] Gaspard et al. reply We presented experimental evidence for the existence of microscopic chaos in the mesoscopic motion of a brownian particle in solution. We used standard techniques to analyse long trajectories of a brownian particle and inferred a dynamical entropy ...
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    [s.l.] : Macmillan Magazines Ltd.
    Nature 394 (1998), S. 865-868 
    ISSN: 1476-4687
    Quelle: Nature Archives 1869 - 2009
    Thema: Biologie , Chemie und Pharmazie , Medizin , Allgemeine Naturwissenschaft , Physik
    Notizen: [Auszug] Many macroscopic dynamical phenomena, for example in hydrodynamics and oscillatory chemical reactions, have been observed to display erratic or random time evolution, in spite of the deterministic character of their dynamics—a phenomenon known as macroscopic chaos. On the other hand, it ...
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Springer
    International journal of thermophysics 16 (1995), S. 1439-1453 
    ISSN: 1572-9567
    Schlagwort(e): absorption ; critical ; photothermal deflection ; photothermal method ; spectroscopy ; supercritical ; surface
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Abstract Photothermal deflection is among the most sensitive techniques available for the measurement of small, localized heating, such as that from the absorption of a focused laser beam in the bulk or surface of a material. A thin optical probe beam is deflected by the refractive-index gradients arising from the heating, and the size of the deflection provides the measure of the heating. We describe the use of a critical fluid to enhance the sensitivity of the technique by at least 103. The diverging coefficient of thermal expansion of a pure fluid near the gas-liquid critical point gives this dramatic enhancement when used as a sensing fluid. With sensitivity calculations and measurements in supercritical xenon,T c≈16.7
    Materialart: Digitale Medien
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