Polyoxyalkylenated amines for breaking water-in-oil emulsions: effect of structural variations on the demulsification efficiency

In the present work, different aliphatic and aromatic amines were ethoxylated after a previous propoxylation (PPPEA) with different degrees of propoxylation and ethoxylation in order to obtain polymeric surfactants having different hydrophilic–lipophilic balance (HLB) values. The influence of the structural variations in the prepared PPPEA on their efficiency as demulsifiers for water-in-oil emulsions was investigated. Synthetic water-in-benzene emulsions stabilized by petroleum asphaltenes was utilized for the completion of this study. The actual propylene oxide (PO)–ethylene oxide (EO) ratios of the PPPEA under investigation was elucidated via ¹H NMR spectroscopy. It was found that each demulsifier practices a maximum demulsification efficiency at an optimum concentration. At this concentration, the demulsifiers’ molecules were believed to form a monolayer by adsorbance at the benzene–water interface. The influences of the number of aromatic rings in the molecule, the degree of substitution in the aromatic rings, the number of amine groups, the number of PO–EO chains and HLB on the demulsification efficiency were accomplished. © 1998 John Wiley & Sons, Ltd.     

Catalytic decomposition of organic peroxides by 4,4′-diamino-trans-stilbene (DTS)/montmorillonite complex: II.p-nitro andp-methyl dibenzoyl peroxide

The kinetics of the induced decomposition ofp-NO₂- andp-CH₃-dibenzoyl peroxide in the presence of 4,4-diamino-trans-stilbene (DTS) were studied in ethanol under both homogenous and heterogeneous conditions. The heterogeneous reaction was carried out in the presence of the DTS/montmorillonite complex. The decomposition reaction was found to be second order and three-halves order for the peroxide concentration in homogeneous and heterogeneous systems, respectively. The reaction was first order for the amine concentration in the homogeneous system. The activation energies for the decomposition reaction were obtained as 54.7±2 and 59.5±3 kJ mol^–1 forp-NO₂- andp-CH₃-dibenzoyl peroxides, respectively, in the homogeneous systems and are higher than the corresponding values of 41±1.5 and 47.6±1 kJ mol^–1 for thep-NO₂ andp-CH₃ derivatives in heterogeneous media.     

Immobilization of transition metal ion complexes and their catalytic activity towards the activation of hydrogen peroxide

Transition metal ion-imidazole complexes have been immobilized on silica, silica–alumina (25%Al₂O₃), and alumina supports by adsorption and functionalization methods. The catalytic activity of these supported complexes in the decomposition of H₂O₂ has been studied. The reaction exhibits first-order kinetics with respect to [H₂O₂] and the quantity of catalyst. The rate of reaction decreases as [H₂O₂]₀ increases. The order of catalytic reactivity is strongly dependent on the type of metal ion, support, and the immobilization method. The complex anchored via adsorption exhibited a higher activity compared to the corresponding complex anchored via functionalization of the surface. The reaction proceed via formation of the peroxo-intermediate, which has an inhibiting effect on the reaction rate. The reaction is enthalpy-controlled as is concluded from the isokinetic relationship. A mechanism is proposed involving the generation of HO₂ radicals from the peroxo-intermediate in the rate-determining step.     

Über das polarographische Verhalten von Zirkonium- und Thorium-Farbstoffkomplexen

Zusammenfassung Das polarographische Verhalten der Solochrom-Violett RS-Komplexe des Zirkoniums und Thoriums wurde untersucht und Proportionalität zwischen der Höhe der Reduktionswellen der Farbstoffkomplexe und der Konzentration der Metallionen im p_H- Gebiet zwischen 2 und 3 festgestellt. Nach eingehender Überprüfung der p_H-Abhängigkeit von Form und Lage der Reduktionswelle konnte eine Arbeitsvorschrift ausgearbeitet werden, die die gemeinsame Bestimmung des Zirkoniums und Thoriums erlaubt und darüber hinaus durch Maskierung des Thoriums mit Acetationen die Möglichkeit zur selektiven Bestimmung des Zirkoniums neben Thorium bietet. Störungen durch Anionen und andere Kationen wurden untersucht und eingehend diskutiert.

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Summary The polarographic behavior of the Solochrom-Violet RS-complexes of zirconium and thorium was studied, and a proportionality was found between the height of the reduction waves of the dyestuff complex and the concentration of the metal ions in the p_H region between 2 and 3. After intensive checking of the p_H-dependence of the form and position of the reduction waves, a working procedure could be worked out, which permits the simultaneous determination of zirconium and thorium, and which furthermore by masking the thorium with acetate ions, creates the possibility of the selective determination of zirconium in the presence of thorium. Interferences by anions and other cations were investigated and discussed at length.

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Rèsumè Etude du comportement polarographique du complexe du violet solochrome RS et du zirconium et du thorium; il a été établi qu'il existait une relation de proportionalité entre les hauteurs des vagues de réduction du complexe coloré et la concentration des ions métalliques dans un domaine de p_H compris entre 2 et 3. Après un contrôle précis de la variation en fonction du p_H des vagues de réduction, en forme et en position, il a été possible d'établir un mode opératoire permettant le dosage global du zirconium et du thorium ainsi que le dosage sélectif du zirconium en présence du thorium lorsqu'on masque ce dernier par des ions acétates. Les perturbations apportées par les anions et d'autres cations ont été étudiées et discutées en détail.

     

Ion-selective electrodes in organic functional group analysis: Microdetermination of hydrazines with the copper electrode

Summary A simple micromethod is described for the determination of hydrazines using the copper ion-selective electrode. The method is based on direct potentiometric titration of the sample in ammoniacal solution of pH 9.5±0.2 with copper(II) ions at room temperature. N-Shaped curves with well-defined inflections at 11 and 12 molar ratios are obtained. This is probably due to the formation of copper monohydrazinate and copper dihydrazinate complexes. Various alkyl and aryl hydrazines and hydrazine salts have been satisfactorily analyzed with an average recovery of 99.4% and a relative standard deviation of ±0.4%. The reaction of hydrazines with Fehling's solution followed by measuring the copper(I) oxide formed using the copper ion-selective electrode also has been investigated.

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Zusammenfassung Eine einfache Mikromethode zur Bestimmung von Hydrazinen mit einer kupferionen-selektiven Elektrode wurde beschrieben. Sie beruht auf der direkten potentiometrischen Titration in ammoniakalischer Lösung mit Cu(II)ionen bei pH 9,5±0,2 bei Zimmertemperatur. N-förmige Kurven mit gut ausgebildeten Spitzen bei Molverhältnissen 11 und 12 wurden erhalten, wahrscheinlich auf Grund der Bildung von Mono- bzw. Dihydrazinatkomplexen des Kupfers. Verschiedene Alkyl- und Arylhydrazine und deren Salze wurden zu 99,4% mit einer Standardabweichung von ±0,4% wiedergefunden. Die Reaktion der Hydrazine mit Fehlingscher Lösung wurde ebenfalls durch Messung des entstandenen Cu(I) mit der erwähnten Elektrode untersucht.

     

Derivations and generating degrees in the ring of arithmetical functions

In this paper we study a family of derivations in the ring of arithmetical functions of several variables over an integral domain, and compute the generating degrees of the ring of arithmetical functions over the kernel of these derivations.     

Weak and strong convergence of an inertial proximal method for solving Ky Fan minimax inequalities

In this paper we present the relaxed inertial proximal algorithm for Ky Fan minimax inequalities. Based on Opial lemma, we propose a weak convergence result to a solution of the problem by eliminating in the algorithm (RIPAFAN) the Browder–Halpern’s factor of contraction. We present after, a first result of strong convergence by adding a strong monotonicity condition. Secondly, we eliminate the strong monotonicity and add a Browder–Halpern’s contraction factor in the algorithm (RIPAFAN) and then ensure the strong convergence to a selected solution with respect to the contraction factor. Some examples are proposed. The first one concerns the convex minimization where the objective function is only controlled with a provided well conditioning. In the second one, we propose monotone set-valued variational inequalities. The last example deals with the problem of fixed point for a nonexpansive set-valued operator.     

Changes produced in etching parameters of CR-39 by high-dose pre- and post-γ irradiation

The effect of post- and pre-high doses of γ–radiation in CR-39 plastic detectors has been studied in the dose range of 3×10¹?10⁶ Gy. Some properties like bulk-etch rate (V _B), track-etch rate (V _T), sensitivity (V _T/V _B) and efficiency have been found out for different gamma doses from a ⁶⁰Co source in CR-39. It is found that V _B and V _T remain almost invariant up to gamma doses of 10⁴ Gy. Then they start increasing slowly till 10⁵ Gy. Between 10⁵ Gy and 10⁶ Gy there is a sharp increase of V _B and V _T values for pre- and post-gamma exposed samples. The present data are compared with the previous literature.