Analysis of liquid surface films by pulsed laser photoacoustic spectroscopy

The photoacoustic generation of plane acoustic waves in strongly absorbing or opaque liquids by pulsed laser radiation is discussed both experimentally and theoretically. The regimes of a confined and a free surface of the liquid are considered. The model which takes the temporal shape of the laser pulses applied in the experiments into account, implies that spectroscopic studies are feasible with direct photoacoustic generation and detection also for opaque liquids. The experiments are performed with a tunable hybrid CO₂ laser and piezoelectric detection. For the first time liquid/liquid interfaces are studied by this technique. We demonstrate that the presence of an absorbing liquid film with a thickness of >1 m on the surface of another liquid amplifies the acoustic signal which is detected in the bottom liquid. The enhancement depends on the thickness and the optical and thermal properties of the film medium. The surface layer can be analyzed on the basis of the photoacoustic spectrum. It is also shown that this non-contact method is surface-film selective and should thus prove useful for pollution analysis of liquid surfaces.     

Methode zur auswertung differentialkalorimetrischer und differentialthermoanalytischer messkurven bei nichtlinearem basislinienverlauf

A method is described for the determination of the base line of differential calorimetric and differential thermoanalytical curves. The exact knowledge of this line is necessary for a quantitative interpretation of such differential measurements. The base line is calculated from measurements of the initial and the final period of the process.In addition, it is shown how to determine the end-point of the exothermic and endothermic processes from the differential curves. Moreover, a method is developed for evaluating the cooling constant.The applicability of the described methods is demonstrated by experimental examples.     

Easy Ruthenium-Catalysed Oxidation of Primary Amines to Nitriles under Oxidant-Free Conditions

A dehydrogenation of primary amine to give the corresponding nitrile under oxidant- and base-free conditions catalysed by simple [Ru(p-cym)Cl₂]₂ with no extra ligand is reported. The system is highly selective for alkyl amines, whereas benzylamine derivatives gave the nitrile product together with the imine in a ratio ranging from 14:1 to 4:1 depending on the substrate. Preliminary mechanistic investigations have been performed to identify the key factors that govern the selectivity.     

Vibro-acoustic study of a viscoelastic sandwich ring immersed in water

This work deals with the reduction of the system composed of a sandwich structure with a viscoelastic core coupled to fluids. Two reduction methods are proposed in this paper to solve this problem in the frequency domain. The first one consists in developing added mass operators to take into account the fluid. The second one is the use of iterative methods to calculate the coupled complex modes of the dissipative problem. This numerical strategy is applied to the response of a bidimensional sandwich ring coupled to internal and external fluids.     

Report on an Unusual Cascade Reaction between Azulenes and 2,3‐Dichloro‐5,6‐dicyano‐1,4‐benzoquinone (=4,5‐Dichloro‐3,6‐dioxocyclohexa‐1,4‐diene‐1,2‐dicarbonitrile; DDQ)

The oxidation of 1‐(3,8‐dimethylazulen‐1‐yl)alkan‐1‐ones 1 with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (=4,5‐dichloro‐3,6‐dioxocyclohexa‐1,4‐diene‐1,2‐dicarbonitrile; DDQ) in acetone/H₂O mixtures at room temperature does not only lead to the corresponding azulene‐1‐carboxaldehydes 2 but also, in small amounts, to three further products (Tables 1 and 2). The structures of the additional products 3 – 5 were solved spectroscopically, and that of 3a also by an X‐ray crystal‐structure analysis (Fig. 1). It is demonstrated that the bis(azulenylmethyl)‐substituted DDQ derivatives 5 yield on methanolysis or hydrolysis precursors, which in a cascade of reactions rearrange under loss of HCl into the pentacyclic compounds 3 (Schemes 4 and 7). The found 1,1′‐[carbonylbis(8‐methylazulene‐3,1‐diyl)]bis[ethanones] 4 are the result of further oxidation of the azulene‐1‐carboxaldehydes 2 to the corresponding azulene‐1‐carboxylic acids (Schemes 9 and 10).     

Near-infrared resonant photoacoustic gas measurement using simultaneous dual-frequency excitation

The simultaneous dual-frequency operation of a resonant photoacoustic gas sensor based on the differential mode excitation photoacoustic (DME-PA) technique is presented. The DME-PA method uses the excitation of two different modes in a resonant photoacoustic cell and the gas concentration is derived from the amplitude ratio of these acoustic modes. With the simultaneous dual-frequency excitation, the amplitude ratio needed by the DME-PA technique is obtained instantaneously, in contrast to the sequential modulation scheme where additional time delays are introduced by changing the modulation frequency. For a given excitation power reaching the photoacoustic cell, and a total acquisition time longer than 7 s, the simultaneous modulation scheme provides an improved measurement uncertainty compared to the sequential scheme. The proposed sensor allows measuring water vapour with a ±150 ppmV uncertainty using current-modulated near-infrared LEDs and a 15 s total acquisition time.     

Magnetic domain formation in itinerant metamagnets

We examine the effects of long-range dipolar forces on metamagnetic transitions and generalize the theory of Condon domains to the case of an itinerant electron system undergoing a first-order metamagnetic transition. We demonstrate that, within a finite range of the applied field, dipolar interactions induce a spatial modulation of the magnetization in the form of stripes or bubbles. Our findings are consistent with recent observations in the bilayer ruthenate Sr(3)Ru(2)O(7).