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Ultrasonic Broadband Spectrometry of Liquids A Research Tool in Pure and Applied Chemistry and Chemical Physics
Authors:Udo Kaatze  Tatiana O. Hushcha  Frieder Eggers
Affiliation:(1) Drittes Physikalisches Institut, Georg-August-Universität, Bürgerstr. 42-44, D-37073 Göttingen, Germany;(2) Institute of Bioorganic Chemistry and Petrochemistry, Mürmans'ka Street 1, 253094 Kyiv, Ukraine;(3) Max Planck-Institut für Biophysikalische Chemie, Am Fa"beta"berg 11, D-37077 Göttingen, Germany
Abstract:This review is a survey of the many scientific applications of ultrasonic broadbandspectrometry (absorption and velocity measurements with coherent sound waves)in liquids and liquid systems, covering, at present, a frequency range from nearly10 kHz to 10 GHz. Ultrasonic spectrometry has proved to be an almost universalresearch tool in many laboratories, one that is useful for investigation of variouschemical, biochemical, and physicochemical systems. Sound waves traversingliquids induce periodic perturbations in pressure and temperature, which can shiftequilibria, resulting in characteristic sound absorption and velocity dispersionspectra. An analysis of such spectra yields valuable information about thermodynamic and kinetic parameters of the particular system that is often difficult toobtain by other methods. Since such periodic perturbations imposed on the systemare incremental in nearly all cases, the system can be studied under equilibriumconditions. All nonlinear effects (heating, nonconstant fluid compressibility, andothers) are negligible, permitting, for instance, the application of linearized rateequations. In this review, various examples of measured broadband spectra arepresented. Related elementary processes are discussed. Among these are ionicand molecular reactions, including mechanisms of association and complexation,proton transfer, solvation, isomerization, interconversion, side-group rotation,hydrogen-bonding, as well as stacking processes and micelle formation. Specialattention will be given to the extensive research on chemical relaxation.Fundamental early and recent publications are cited and discussed. Many referencesare included with particular emphasis on less well known research and publicationsfrom countries of the former USSR. This review aims at a demonstration of thewidespread applications of modern ultrasonic techniques in many fields ofliquid-state research.
Keywords:Chemical relaxation  elementary reactions  molecular dynamics  rapid kinetics  ultrasonic spectrometry
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