Oscillatory kinetics and mechanism of the chromate catalyzed decomposition of hydrogen peroxide

Oscillatory change of pH occurs during the chromate-catalyzed decomposition of hydrogen peroxide in a weakly acidic medium at elevated temperature and at high initial concentration of hydrogen peroxide. In a closed system, there are only two or three periods, but sustained oscillation occurs in a CSTR. In a CSTR bistability is also found. In closed systems the temperature exhibits a great maximum (up to 15°C increase), in a CSTR sustained oscillation occurs at a constant stationary temperature.     

Teaching analytical properties

A new way of expounding analytical properties based on their mutual dependence (complementary and contradictory relationships) and their unequivocal connection with analytical quality facets is presented. To this end, the paper provides answers to the obvious questions that arise in dealing with the subject: why?, how?, when? and where to teach analytical properties in the Analytical Chemistry curriculum?     

Book reviews

Ohne Zusammenfassung

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Book reviews

     

Influence of solute mobility on dislocation motion I. Basic model

Dislocation motion in the real lattice of alloys is highly complex. In a certain temperature range the dynamic strain ageing phenomena have been reported. In this paper the influence of mobile solute atoms (as obstacles) on the motion of dislocation is analysed. Both processes are assumed to be thermally activated. A new model based on this assumption is proposed. The dislocation velocity and the friction stress (due to solute-dislocation interactions) are calculated. A change in the friction stress caused by solute mobility is discussed.     

Use of the Apparent Content Curves for the spectrophotometric identification of substances: identification of amphetamines

The possibility of identification of substances which have similar spectral behaviour by means of Apparent Content Curves has been studied. This study is carried out with absorption, excitation and emission spectra of several amphetamines of widespread pharmaceutical use. Results obtained show that amphetamine, phenylpropanolamine, pseudoephedrine, phenylephrine, epinephrine, dopamine and methoxyamphetamine can be identified with a probability of >95%.     

Improvement of the properties of polyarylate reinforced with liquid crystalline polymers

Blends of polyarylate of bisphenol A, PAr, with two commercial main chain liquid crystalline polymers, Vectra A950 and Vectra B950, are studied. From dynamic viscoelastic measurements it is deduced that both systems (PAr/Vectra A950 and PAr/Vectra B950) are immiscible and scanning electron microscopy (SEM) micrographs show the presence of spherical domains of the liquid crystalline polymer when PAr constitutes the matrix. Extrusion capillary measurements reveal that, under conditions of temperature and shear rate similar to those of processing, the viscosity is reduced to approximately 10% of its value when the content of liquid crystalline polymer is only 20%. This great improvement of the rheological properties is observed in both PAr/Vectra A950 and PAr/Vectra B950 blends. The effect of draw ratio on Young's modulus for different compositions is also analyzed, pointing out the reinforcing action of both liquid crystalline polymers on polyarylate: for instance, 20% of Vectra B950 in the blend gives rise to a 700% increase of the modulus of fibres prepared at a draw ratio of 50. SEM of the extrudates reveals that the spherical domains are elongated at the entrance of the capillary giving rise to a microfibrillar morphology which is related to the excellent rheological and mechanical properties of the blends.     

Resolution of binary mixtures of cephalothin and clavulanic acid by using first derivative spectrophotometry

First-derivative spectrophotometric method with a “zero-crossing” technique of measurement has been used for the quantification of two-components mixtures of cephalothin and clavulanic acid. As the absorption bands of these drugs overlap, both direct and derivative spectrophotometric methods have been investigated and evaluated by a rigorous statistical analysis of the experimental data. The first-derivative spectrophotometric method was found to be more accurate, direct and reproducible. Beer's law was valid over the concentration range 2.0–28.0 mg/l for both compounds. The detection limits of cephalothin and clavulanic acid, at a 0.05 level of significance, were calculated to be 0.13 and 0.15 mg/l. The method was applied for determining these antibiotics in mixtures, some of them containing inject-able dosage forms of cephalothin, and so to determine both compounds in saline and glucosed physiological sera.     

Multicommuted fluorometric multiparameter sensor for simultaneous determination of naproxen and salicylic acid in biological fluids.

A combined approach based on solid-phase optosensing and multicommutation principles has been applied to develop a method for the simultaneous analysis of two pharmaceuticals (naproxen and salicylic acid) in biological fluids. The multicommuted flow-through optosensor was based on direct native fluorescence measurements of both analgesics using a non-polar sorbent (C18 silica gel) as a solid sensing zone. The flow system was controlled by Java-written home-made software and designed using three-way solenoid valves for an independent automated manipulation of sample and carrier solutions. Using an optimized sampling time, the method was calibrated in the range of 1 - 25 and 5 - 200 ng mL(-1). The obtained detection limits were 0.3 and 1.3 ng mL(-1) for naproxen and salicylic acid, respectively, with RSD (%) values of better than 2% for both analytes. The proposed methodology was successfully applied to urine, serum and pharmaceutical preparations. Recovery percentages ranging from 96.1 to 104% were obtained for both analytes.