Diphenyl(2-pyridyl)methane as a solvent for thiocyanate complexes of zinc in aqueous mineral acids

Summary Tracer (10^–8 M) zinc can be quantitatively extracted with 0.1M diphenyl(2-pyridyl)methane (DPPM) in benzene from neutral and acidic aqueous thiocyanate solutions in a single extraction. In all cases, extraction times of 1–5 min are sufficient for equilibration. The effects of the concentration of the mineral acids, the reagent, complexing and salting-out agents and phase-volume ratios on the metal extraction are reported. The metal is predominantly extracted through solvation, and the extraction of the metal as Zn(SCN)₂(DPPM)₂ is indicated. Among the common salts only sodium chloride exerts a slight depressing effect on extraction when present in high concentration. The metal can be stripped from the organic phase with aqueous oxalate, citrate or acetate solutions in a single operation. Distribution coefficients and separation factors for a number of metal ions, relative to zinc, are reported for 0.2M potassium thiocyanate media that contain the optimal concentration of mineral acid. The method can be employed for the simultaneous preconcentration of toxic metals such as zinc, copper and mercury from neutral aqueous solution in water pollution studies.

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Diphenyl(2-pyridyl)methan als Lösungsmittel für Zink-Rhodanidkomplexe in wäßrigen Mineralsäuren

Zusammenfassung Zinkspuren (10^–8 M) lassen sich mit einer benzolischen, 0,1 M Lösung von Diphenyl(2-pyridyl)methan (DPPM) aus neutralen oder sauren, wäßrigen Rhodanidlösungen durch eine einzige Extraktion ausschütteln. Jedenfalls sind 1–5 min hinreichend für die Einstellung des Gleichgewichtes. Der Einfluß der Konzentration der Mineralsäure, des Reagens, des Komplexbildners und des Aussalzmittels sowie des Volumenverhältnisses der Phasen auf die Metallextraktion wurde beschrieben. Die Extraktion erfolgt vorherrschend durch Solvatation und zwar als Zn(SCN)₂(DPPM)₂. Unter den gewöhnlichen Salzen beeinträchtigt nur NaCl in hoher Konzentration die Extraktion in geringem Maß. Das Metall kann aus der organischen Phase mit wäßrigen Oxalat-, Citrat- oder Acetatlösungen in einem Arbeitsgang rückextrahiert werden. Die Verteilungskoeffizienten und Trennungsfaktoren für einige Metallionen in bezug auf Zink in 0,2M Kaliumrhodanid bei optimaler Mineralsäurekonzentration wurden angegeben. Das Verfahren eignet sich für die gleichzeitige Anreicherung toxischer Metalle, wie Zn, Cu und Hg aus neutraler Lösung bei der Untersuchung der Gewässerverunreinigung.

     

Evaluation of sorption affinity of cadmium(II) on Haro river sand from aqueous solutions

The sorption of Cd(II) on Haro river sand from deionized water is reported. The sorption system obeyed according to the Freundlich and Dubinin–Radushkevich (D-R) isotherms. The Freundlich parameters 1/n = 0.67±0.05 and of A = 1.38±1.14 mmole·g^-1 have been ascertained. D-R isotherm yields the values of = -0.003741±0.000321 kJ²·mole^-2, X _m = 0.23±0.21 mole·g^-1 and of E = 11.6±0.5 kJ·mole^-1. The influence of common anions and cations on the sorption was examined. Trivalent Bi enhances the sorption whereas Fe, Cr, Al and chromate ions reduce the sorption significantly. Hf(IV) and Ag(I) indicate substantial sorption (61–98%) whereas Gd(III), Re(VII) and Sc(III) show low sorption (<5%). The elements having low sorption can be separated from elements indicating higher sorption using Haro river sand column.     

Tunable near-infrared radiation by difference frequency mixing in a lithium tetraborate crystal

Non-collinear difference frequency mixing is reported for the first time in a lithium tetraborate (Li₂B₄O₇) crystal, and is used to generate near-infrared radiation in the range 1700–2300 nm. Received: 13 July 2000 / Published online: 10 January 2001     

Understanding amylose crystallinity in starch–clay nanocomposites

The amylose–water interaction is part of an important equilibrating process within the starch matrix leading to slow recrystallization of amylose chains and growth of anisotropic properties in the starch matrix. This article highlights the influence of nanoclay on (a) the structural development of amylose crystallinity and (b) the rate of water loss from the starch matrix. By varying the nanocomposites level (1.5–4 wt %), a unique microstructure is obtained that “locks” moisture and it was found that on a per unit weight basis of the starch matrix, addition of 4 wt % nanoclay resulted in additional 8.5% water in the matrix. Also, it was found that increasing the nanoclay from 2 to 4% by weight, the composite modulus jumped by 100% indicating excellent interaction between clay nanocomposites and starch polymer. Analysis of the starch crystallinity data indicates that nanocomposites retard the mobility of the starch molecules (specially the long chain amylose component) to restrict the movement of “associated” water around starch and this increases the “locked” water by ～10%. The results strongly suggest that a new structural unit may be formed by amylose–water–clay interaction which enhances the composites properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 979–987, 2008     

Quantum phase properties of the field in a micromaser: Effect of cooperative atomic interactions, cavity losses and pump fluctuations

In this paper, we study the effect of cooperative atomic interactions, cavity losses, and pump fluctuations on quantum phase properties of the field in a one-photon micromaser. We consider, initial coherent state of the radiation field and atoms initially in the excited and coherent superposition of their atomic states, respectively. We find that quantum phase properties of the field in a micromaser are highly sensitive to two-atom events and cavity losses. Both contribute to the randomization of the well-defined phase structure associated with the initial coherent state. However, the approach towards the randomization is quite different in the two cases. We also find that the fluctuations, associated with the random injection of the atoms, affect the phase structure of the coherent state.     

Generation of tunable infrared radiation in rubidium titanyl phosphate crystal for the optical measurement of number density, absorption cross-section of methane gas

Tunable near-infrared radiation has been generated in a rubidium titany1 phosphate (RTP) crystal by employing non-collinear difference-frequency mixing (DFM) technique. The input radiation sources are Nd:YAG laser radiation and its second harmonic pumped dye laser radiation. For the generation of 2.0 radiation, the maximum value of the conversion efficiency (quantum) obtained in the process is 49% from the dye (0.6945 μm) to the infrared (2.0 μm) radiation in the 7.9-mm-long crystal. The generated tunable mid-infrared radiation has been used to measure the number density, absorption cross-section and minimum detectable concentration of methane gas in its 2ν₃ band in a multi-pass cell at 30.075 Torr pressure. The number density and column density of the methane molecules are found to be 1.068×10¹⁸ cm⁻³ and 3.02×10²¹ cm⁻², respectively, whereas the minimum still-detectable concentration at 1.658 μm wavelength is estimated to be 4.523×10¹⁷/cm³.     

Measurement of effective specific heat of packed bed materials by the continuous flow electrical method

The theory of the continuous flow electrical method for the determination of specific heat of liquids has been extended to the measurements of effective specific heat of packed bed materials consisting of solid-liquid phase systems. Experimental data are reported showing the variation of effective specific heat with mass porosity and saturating liquid specific heat. The weighted arithmetic mean equation of constituent specific heats is in fair agreement with the measured values.     

Dienecobalt tricarbonyl cations

Oxidation of dienedicarbonylcobalt dimers has yielded the novel dienetricarbonylcobalt cations, or, in presence of phosphine, the corresponding mono- and di-substituted salts.