Sorption of trace concentrations of gallium(III) and iodide ions on tin(II) hydroxide

Summary The results of sorption measurements for gallium (III) and iodide ion traces onto tin(II) hydroxide from aqueous heterogeneous systems are given. Since only tagged sorbate was used (⁶⁷Ga and 1311), in the determination of sorption by radioactive tracer method, it was necessary to establish the pH interval of tin(II) hydroxide in/stability. This was done by a turbidimetric method and the pH region of instability between 3 and 9 was found.The sorption results indicate a difference in sorption ability of gallium(III) and iodide as it appears from the dependence of the amount sorbed on contact time between heterogeneous reactants (sorbentsorbate). The amounts sorbed increase with increasing contact times at higher pH values for Ga(III) but remain unaffected for iodide sorption. Thus the sorption of iodide ions seems to be restricted to the solid surface while the sorption results for gallium(III) indicate the diffusion of sorbate into sorbent as a possible parallel mechanism. Those processes could be taken as compatible with the porous-double-layer mechanism which has been proposed in literature for aqueous heterogeneous oxide systems.

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Zusammenfassung In der Arbeit werden Ergebnisse von Sorptionsmessungen für Ga³⁺- und j-Spuren an Zinn(II)-Hydroxid aus wäßrigen heterogenen Systemen berichtet. Zur analytischen Erfassung wurden radioaktives⁶⁷Ga und 131 J verwendet. Die Stabilität von Zinn(II)-Hydroxid wurde durch Trübungsmessungen untersucht. Im pH-Bereich von 3–9 ist das Zinn(II)-Hydroxid als kolloide Suspension instabil.Ga³⁺ und J^– verhalten sich bei der Adsorption unterschiedlich. Die adsorbierte Menge steigt mit zunehmender Kontaktzeit bei hohen pH-Werten von Gallium, bleibt jedoch für Jod unverändert. Die Unterschiede werden gedeutet durch die Annahme, daß Jod nur an der festen Oberfläche adsorbiert wird, während die Galliumionen auch in das Sorbens diffundieren können. Man könnte die Ergebnisse als verträglich mit einem porösen Doppelschichtmechanismus ansehen; ein solcher Mechanismus ist in der Literatur für wäßrige heterogene Oxidsysteme vorgeschlagen worden.

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With 4 figures     

Adsorption configuration and local ordering of silicotungstate anions on Ag(100) electrode surfaces

X-ray reflectivity, cyclic voltammetry, and scanning tunneling microscopy (STM) are used to examine the structure of alpha-SiW12O4(4-) or silicotungstic acid (STA) adsorbed on Ag(100) in acid solution. The voltammetry shows that STA passivates the Ag surface relative to electron transfer to a solution redox species. STM images reveal the formation of a series of lattice structures, one of which can be associated with a commensurate ( radical13x radical13)R33.69 degrees structural model. X-ray reflectivity measurements show uniquely that STA orients with its four-fold axis perpendicular to the Ag(100) surface and that the center of the STA molecule is 4.90 A above the top layer of the Ag substrate. Analysis of bond lengths leads to a footprint of STA on Ag(100), in which the four terminal O atoms are located near the hollow sites and have a Ag-O bond length of 2.06 A. This bond length is consistent with a strong covalent interaction between STA and the Ag surface.     

Distribution of fallout radionuclides through soil surface layer

The distribution of¹³⁷Cs through soil layers has been investigated by field sampling. The investigation deals with¹³⁷Cs concentration found after the Chernobyl accident. The relationship between important soil characteristics, total precipitation and cesium distribution are analyzed. Cesium is strongly sorbed in the top soil layer and its migration downward is limited. Measurements performed over a 3-year period revealed that approximately 20–38 per cent of total¹³⁷Cs is located in the upper soil layer.     

Metal—metal bonding in dinuclear complexes of platinum(I). The crystal and molecular structure of carbonyl(chloro)-bis-μ-[bis(diphenylphosphino)methane]diplatinum hexafluorophosphate

The structure of [Pt₂Cl(CO) (μ-Ph₂PCH₂PPh₂)₂] [PF₆] was determined by $\text{X}$-ray methods and refined to $\text{R}$ = 0.082, using diffractometric intensities of 5646 independent reflections. The crystals are monoclinic, space group $\text{P}$2₁/$\text{n}$, $\text{a}$ = 12.919(3), $\text{b}$ = 15.576(6), $\text{c}$ = 25.151(5)Å, β = 94.82(3)°, $\text{Z}$ = 4. They are built of octahedral hexafluorophosphate anions and dinuclear platinum(I) cations. The latter contain PtCl and PtCO fragments linked to one another by a PtPt σ-bond and by two bridging bis(diphenylphosphino)methane ligands. The platinum atoms are in square planar environments and the dihedral angle between the two coordination planes is 40.1°. Selected bond lengths are: PtPt 2.620(1), PtCl 2.384(5), PtC 1.89(3) and PtP 2.291(5) – 2.308(5)Å.     

Classification of wheat varieties: use of two-dimensional gel electrophoresis for varieties that can not be classified by matrix assisted laser desorpiton/ionization-time of flight-mass spectrometry and an artificial neural network

Analyzing a gliadin extract by matrix assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS) combined with an artificial neural network (ANN) is a suitable method for identification of wheat varieties. However, the ANN can not distinguish between all different wheat varieties. Two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) was applied to three pairs of wheat varieties, which can not be classified correctly by ANN. By 2-D PAGE the varieties in the three pairs can be discriminated and these six wheat varieties can be separated from each other, which could not be separated by MALDI-TOF-MS and NN.     

Optimization of artificial neural networks used for retention modelling in ion chromatography

The aim of this work is the development of an artificial neural network model, which can be generalized and used in a variety of applications for retention modelling in ion chromatography. Influences of eluent flow-rate and concentration of eluent anion (OH-) on separation of seven inorganic anions (fluoride, chloride, nitrite, sulfate, bromide, nitrate, and phosphate) were investigated. Parallel prediction of retention times of seven inorganic anions by using one artificial neural network was applied. MATLAB Neural Networks ToolBox was not adequate for application to retention modelling in this particular case. Therefore the authors adopted it for retention modelling by programming in MATLAB metalanguage. The following routines were written; the division of experimental data set on training and test set; selection of data for training and test set; Dixon's outlier test; retraining procedure routine; calculations of relative error. A three-layer feed forward neural network trained with a Levenberg-Marquardt batch error back propagation algorithm has been used to model ion chromatographic retention mechanisms. The advantage of applied batch training methodology is the significant increase in speed of calculation of algorithms in comparison with delta rule training methodology. The technique of experimental data selection for training set was used allowing improvement of artificial neural network prediction power. Experimental design space was divided into 8-32 subspaces depending on number of experimental data points used for training set. The number of hidden layer nodes, the number of iteration steps and the number of experimental data points used for training set were optimized. This study presents the very fast (300 iteration steps) and very accurate (relative error of 0.88%) retention model, obtained by using a small amount of experimental data (16 experimental data points in training set). This indicates that the method of choice for retention modelling in ion chromatography is the artificial neural network.     

Application of thermal analysis for quantitative nitrogen determination in fertilizers

DSC and DTA techniques have been used to determine nitrogen present in the form of ammonium nitrate in fertilizers. The optimum conditions for the investigations were determined for both techniques. By determining peak area, i.e. the enthalpy of the ammonium nitrate crystal transformation II I, it was possible to determine the nitrogen content in ammonium nitrate and in lime ammonium nitrate by DSC with average deviations of 0.44 and 0.91%,respectively. Using DTA and the enthalpy of the ammonium nitrate crystal transformation IV III, the average deviation of nitrogen determination in lime/ammonium nitrate was 1.09%.

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Zusammenfassung DSC und DTA wurden zur Bestimmung des in Düngemitteln in Form von Ammoniumnitrat vorliegenden Stickstoffs benutzt. Für beide Techniken wurden die optimalen Untersuchungsbedingungen ermittelt. Durch Bestimmung der Peakfläche, d. h. der Enthalpie der Kristalltransformation II I des Ammoniumnitrats konnte der Stickstoffgehalt in Ammoniumnitrat und in Kalk/Ammoniumnitrat mittels DSC mit mittleren Abweichungen von 0.44 bzw. 0.91% bestimmt werden. Aus der Kristalltransformation IV III des Ammoniumnitrats ergibt sich bei Benutzung der DTA-Methode eine mittlere Abweichung von 1.09% für die Stickstoffbestimmung in Kalk/Ammoniumnitrat.

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, . . , , (III) , — . , , 0,44 0,91%. IVIII , - 1,09%.

     

Vibrational spectra of the adduct of 1,8-bis(dimethylamino)naphthalene with dichloromaleic acid (DMAN x DCM)

The infra-red (IR), Raman (R) and inelastic incoherent neutron scattering (IINS) spectra, particularly in low frequency region, of the title ionic adduct were studied. It is shown that all low frequency vibrations (below 200 cm(-1)) of (CH3)2N groups of protonated 1,8-bis(dimethylamino)naphthalene (DMAN)--clearly observed in IINS spectra--are sensitive to the environment, i.e. to the type of counterion forming short contacts with C-H bonds of methyl groups. The internal frequencies were also calculated by ab initio method. The results are consistent with numerous observations of the counteranion effect on the geometry of the protonated DMAN. The conclusions are compared with structural and NMR studies reported recently for the 1,8-bis(dimethylamino)naphthalene with dichloromaleic acid (DMAN x DCM) adduct. The single crystal R polarized spectra taken over the frequency range 20-3200 cm(-1) were analyzed in detail. We have shown that a substantial difference in the IR spectrum of the dichloromaleic acid (DCM) anion in the DMAN adduct and in the potassium salt results from different geometries of OHO hydrogen bonds. In the case of potassium salt the chains of longer intermolecular hydrogen bonds are formed described by means of a double minimum potential.     

Eine Methode zur halbquantitativen Bestimmung kleiner Mengen von Organochlorpestiziden mittels aromatischer Amine mit Hilfe der Ringofenmethode

Zusammenfassung Zur Bestimmung von Toxaphen wurde die Weiszsche Ringofentechnik angewandt, wobei zum Auswaschen der Ringe eine Diphenylamin-Petrolätherlösung benutzt wird und zur Entwicklung der Farbe der Ringe eine kurzfristige Bestrahlung mit UV-Licht Anwendung findet. Die Grenzwerte der Bestimmungen sind 0,5 bis 2,5g Toxaphen mit einer Genauigkeit von 100±2%.Auf die Möglichkeit der Anwendung anderer aromatischer Amine für eine Reihe anderer Organochlorpestizide wird hingewiesen.

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Summary The Weisz ring oven technique was used for determining Toxaphene, whereby a diphenylamine-petroleum ether solution was employed for washing out the rings and a brief irradiation with UV light for the development of the color of the rings. The limiting values of the determinations are 0.5 to 2.5g Toxaphene with an accuracy of 100±2%.The possibility of the application of other aromatic amines for a series of other organo chlorinated pesticides is pointed out.

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Vorgetragen auf dem 1. jugoslawischen Kongreß für Ernährung, Belgrad, 5. bis 7. Dezember 1966.     

Mathematical modeling of physico-chemical characteristics of cement-waste composites in radioactive waste management

An optimization of mortar (as matrix), improved with bentonite clay, used for immobilization of radionuclides⁶⁰Co,¹³⁷Cs,⁸⁵Sr and⁵⁴Mn, is presented. A relatively simple mathematical model is given, which permits minimization of leach rate and permeability and maximization of compressive strength. An optimal solution, based on experimental data, is given. These results will be used for a future Yugoslav radioactive waste storing center.