The cloud point extraction of copper(II) with monocarboxylic acids into non-ionic surfactant phase

The possibility to use monocarboxylic acids and their mixtures with amines for copper concentrating by the way of micellar extraction at cloud point temperature, and later atomic absorption spectrometry (AAS) determination was investigated. Under the optimum conditions, preconcentration of 100 ml of water sample in the presence of 1% non-ionic surfactant OP-10, 0.005 M capric acid and 0.01 M octylamine permitted the detection of 0.01 μg ml⁻¹ copper. The proposed method has been applied to the AAS determination of copper in water samples after cloud point extraction.     

Transformation of polymers under the action of mechanical forces

The chemical processes that occur during the processing of polymer materials under the action of mechanical forces are discussed. The chemical modification and blending of polymers in an extruder reactor are considered. Factors that affect the mechanism of dynamic vulcanization and the properties of thermoplastic elastomers are identified. Reactions of formations of statistical, block, and graft copolymers under intensive mechanical action are analyzed.     

Exchange characteristics of monocarboxylic acids and monosulfonic acids onto anion-exchange resins

In the previous paper (N. Kanazawa, K. Urano, N. Kokado, Y. Urushigawa, J. Colloid Interface Sci. 238 (2001) 196), the equilibria of propionic acid and benzoic acid adsorption onto three anion-exchange resins were investigated, and an equation was proposed that summed of the physical adsorption of the carboxylic acid molecule and the ion exchange of the dissociated carboxylate ion. The ion exchange equation, including a selectivity coefficient to chloride ion for each combination between carboxylate ions and anion-exchange resins, could be used in wide ranges of concentration and pH. In this research, ion-exchange equilibria using 16 anion-exchange resins and 9 organic acids including monocarboxylic and monosulfonic acids were investigated. It could be confirmed that the proposed equation applied to the ion exchange with these monoorganic acids. Characteristics of ion exchange between the organic anions and anion exchange were also studied by the selectivity coefficients.     

Complexation forces in aqueous solution. Calorimetric studies of the association of 2-hydroxypropyl-β-cyclodextrin with monocarboxylic acids or cycloalkanols

The formation of complexes between 2-hydroxypropyl-β-cyclodextrin and monocarboxylic acids or cycloalkanols has been studied calorimetrically at 298 K in phosphate buffer, pH 11.3. The forces involved in the association process are discussed in the light of the signs and values of the thermodynamic parameters obtained: association enthalpy, binding constant, Gibbs free energy, and entropy.From this study it was inferred that (i) for monocarboxylic acids, hydrophobic interactions are the primary force determining complexation, as indicated by the small enthalpies and by the high and positive entropies. For the cycloalkanols, instead, enthalpies are negative and entropies positive or negative, depending on the solvent medium employed, namely water or phosphate buffer; (ii) the most important requirement for the formation of the complex is a good spatial fit between the two interacting molecules. A cavity elongation effect occurs because of the presence of the hydroxypropyl groups on the rim of the macrocycle. The relative contribution of hydrophobic and van der Waals interactions varies with the dimensions of the guest molecules; (iii) a linear correlation exists between enthalpy and entropy of complexation, underlying that inclusion is a process dominated by hydration phenomena and ascribed to the modifications experienced by the solvent in the hydration shells of the interacting substances.     

Extraction of ions of rare earth elements with monocarboxylic acids from sulfate media

The extraction of rare earth ions with aliphatic monocarboxylic acids from sulfate solutions and suspensions was studied. The region of disperse interfacial structures, stabilizing the emulsion, was found. Extractable complexes of rare earth carboxylates were determined. The conditions of the extraction conversion of rare earth sulfate salts with monocarboxylic acids were determined.     

Effect of the medium on the oxidation of aliphatic monocarboxylic acids

Oxidation rates and k₂/k₆ ratios are given for some acids from propionic to lauric. The k₂/k₆ ratio is shown to be influenced by the electrostatic effect of the solvent. A linear dependence between the isodielectric values of k₂/k₆ and the number of methylene groups in the acid molecules is described.

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k₂/k₆ . k₂/k₆ k₂/k₆ .

     

Determination of cadmium by differentialn pulse anodic-stripping voltammetry after salting-out extraction into acetonitrile

A selective and specific method is presented for anodic-stripping voltammetric determination of cadmium after extraction with 0.1Mtetrabutylammonium iodide solution in acetonitrile from aqueous ammonium sulphate solutions. The detection limit of this method is 0.2 ng ml (in the acetonitrile extract). Interference from matrices or large amounts of elements reduced at more positive potentials can be eliminated by prior extraction. The method has been applied to trace analysis for cadmium in zinc, lead and indium metals, and some inorganic salts.     

Thermal investigations of the calcium salts of monocarboxylic aliphatic fatty acids

Calcium salts of acetic and mono, di and trichloroacetic acids were investigated with respect to their dehydration and decarboxylation, using a derivatograph. A phase transition was noticed only in the case of calcium acetate. Effects of crucible and diluent on the thermal behaviour of the above salts were also studied. The decomposition products were investigated qualitatively, and from these gaseous products and also from the residue after pyrolysis the probable mechanisms of decompositions have been suggested. Activation energies for the decarboxylation processes were evaluated from the TG curves.

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Zusammenfassung Die Calciumsalze von EssigsÄure sowie von Mono-, Di- und TrichloressigsÄure wurden mittels eines Derivatographen hinsichtlich ihrer Dehydratisierung und Decarboxylierung untersucht. Ein Phasenübergang wurde nur im Falle des Calciumacetats beobachtet. Der Effekt des Tiegels und des Verdünners auf das thermische Verhalten obiger Salze wurde ebenfalls untersucht. Die Zersetzungsprodukte wurden qualitativ geprüft und aus diesen gasförmigen Produkten sowie aus ihren Pyrolyseresten wurde ein wahrscheinlicher Zersetzungsmechanismus vorgeschlagen. Die Aktivierungsenergien der DecarboxylierungsvorgÄnge wurden aus den TG-Kurven ermittelt.

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Résumé La déhydratation et la décarboxylation des sels de calcium des acides acétique, mono, di et trichloroacétique ont été étudiées à l'aide d'un Derivatograph. Seul l'acétate de calcium présente une transition de phase. Les effets respectifs du creuset et du diluant sur le comportement thermique de ces sels ont également été suivis. Les produits de décomposition ont été analysés qualitativement. D'après la nature des gaz émis et celle des résidus de pyrolyse, un mécanisme est proposé pour ces décompositions. Les énergies d'activation des réactions de décarboxylation sont calculées à partir des courbes TG.

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, -, - . . . , . .

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The authors express their most grateful thanks to the Council of Scientific and Industrial Research, New Delhi, for financial assistance.     

Transformations of 3-formylindoles under the action of acids

Under the influence of acids 3-formylindole forms urorosein (the salt of di(indol-3-yl)methylium) which is unstable in solution and decomposes to give a series of indole derivatives, among which 6-(indol-3-yl)-5H,7H-indolo[2,3-b]carbazole and tri(indol-3-yl)methylium salt predominate. N,N′-Dimethylurorosein in solution also forms a mixture of indole derivatives, from which tri(1-methylindol-3-yl)methylium salt, 5N,11N-dimethylindolo[3,2-b]carbazole and its 6-(1-methylindol-3-yl) derivative were isolated. Research Institute of New Antibiotics, RAMN (Russian Academy of Medical Science), Moscow 119867, Russia; Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 631–639, May, 1999.     

Detoxification of acetonitrile — water wastes from liquid chromatography

Summary Acetonitrile is one of the most frequently used solvents in column liquid chromatography. Because of its toxicity, safe disposal of the waste solvent is essential. Combustion in a hazardous waste plant, if available, is recommended. Otherwise the waste can be degraded in the laboratory to acetic acid and ammonia by treatment with sodium hydroxide. The addition of hydrogen peroxide is not necessary. The waste needs to be diluted to 10% acetonitrile in water in order to prevent the formation of a two-phase system on addition of concentrated sodium hydroxide. This reagent must be added in excess; 2.5 mols of sodium hydroxide per mol of acetonitrile are recommended. It was found that the kinetics are of second order, with an activation energy of 89 kJ mol⁻¹ and a frequency factor of 9 × 10⁹. Therefore even at room temperature degradation is possible, although a hydrolysis time of approximately 15 days is needed under these conditions. At 80°C, where refluxing is not necessary, hydrolysis is complete after, e.g., 2 h, depending on the amount of sodium hydroxide added.     

Polarographic determination of indium(III) after salting-out extraction of the bromide complex into acetonitrile

A simple and sensitive method has been developed for the polarographic determination of indium(III) after solvent extraction into acetonitrile, salted-out from aqueous solution with sodium bromide. The extracted indium(III)-bromide complex gives a well-defined d.c. wave with E(1 2 ) = -0.69 V vs. SCE. The wave-height is directly proportional to the concentration of indium(III) from 1.6 x 10(-6) to 3.0 x 10(-4)M with respect to the original aqueous solution. In the a.c. polarographic method, a linear calibration curve is obtained for indium(III) over the concentration range from 1.6 x 10(-6) to 1.5 x 10(-5)M, and interference from most foreign ions can be eliminated. In particular, 10.0 mg of Fe(III) and 2.5 mg of Tl(III) are tolerated when 1.0 g of ascorbic acid is added. The lower limit of determination is 8 x 10(-8)M indium(III) by the square-wave polarographic method.     

Automated liquid-solid extraction of pyrene from soil on centrifugal microfluidic devices

Organic pollutants such as polycyclic aromatic hydrocarbons (PAHs) are present in the environment in increasing concentrations and so are of growing concern. Monitoring these species, particularly on-site, can be both difficult and expensive. This paper presents a novel miniaturised magnetically actuated liquid-solid extraction unit integrated in tandem with a filtration unit and a detection unit on a single centrifugal microfluidic device. A demonstration analyte, pyrene, was rapidly extracted and quantified by UV-absorbance from multiple soil samples. The system showed excellent performance for a system designed for field use. Characterization of two types of passive valves was performed along with an extraction time efficiency study. The system provides a factor of 150 reduction in sample weights and extraction solvent volumes and provides statistically similar recoveries to the conventional method with a pyrene detection limit of 1 ppm (0.03 μg absolute detection limit). The reduction in time and solvent and the potential for field use suggest that this device type may be valuable for environmental monitoring.     

The effect of different monocarboxylic acids on the gelation behaviour of Cu ethoxide

Cu ethoxide becomes soluble in methoxyethanol when formic, acetic, or acrylic acid is added. For the complete dissolution, the minimum molar ratio of an acid to Cu ethoxide is two for formic acid (HOFA), and one for acetic (HOAC) or acrylic (HOAA) acid. The solutions of Cu ethoxide with any amounts of formic acid are incapable of forming gels. Those with acetic or acrylic acid/Cu ratio of 1 are able to convert to gels. For the range of the water concentration from 1.5 to 10 M, the gelation time is strongly dependent on [H₂O] for the solution with HOAC/Cu ratio of 1, while it is almost independent for the solution with HOAA. It is suggested that the differences in the behaviour of soluble Cu species derived from the three acids are attributed to different coordination forms and the bonding strength between ligands and copper ions.