Mixed-metal ethylenediaminetetraacetates of neodymium and alkaline earths

Conclusions In solution, the complexes M^II(NdA)₂ do not have a polynuclear structure. In the conditions studied, hydroxo polynuclear complexes including EDTA and M^II and Nd³⁺ ions are also not formed. Our results are not inconsistent with the hypothesis that the solid complex Ca(NdA)₂·17H₂O has a polynuclear structure and that the polynuclear character is successively weakened as Ca²⁺ is replaced by Sr²⁺ and Ba²⁺.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1235–1239, June, 1977.     

Clustering of rare earths in GeAs sulfide glass

Clustering of rare-earth dopants in GeAs sulfide glasses was studied by fluorescence spectroscopy of Pr-doped glasses and by EPR measurements of Gd-doped samples. The linewidth of the g  2 resonance of Gd³⁺, as well as the relative intensity of emission from the ¹D₂ level of Pr³⁺, was used as a relative measure of rare-earth clustering. Rare earths were found to have low solubility in uncodoped GeAs sulfide glasses, which also displayed poor fluorescence efficiency due to severe clustering. Codoping such glasses with Ga greatly enhanced rare-earth solubility and dispersal, particularly for Ga:rare earth ratios ≥ 10:1, as evidenced by the narrower EPR resonances and more intense luminescence of Gd- and Pr-doped glasses, respectively. In, P and Sn were also observed to ‘decluster’ rare earths, although less efficiently than Ga, whereas codoping with I was found to have no effect on clustering. These phenomena are explained by a structural model in which (1) rare-earth dopants and codopants are spatially associated and (2) rare-earth dispersal is accomplished by a statistical distribution of codopants in tetrahedral network sites.     

Amperometric complex-formation titration of traces of alkaline earths

Alkaline earth metals were determined in microgram quantities by complexometric titration with EDTA, EGTA and DTPA. The end-point was detected by following the anodic wave of the chelating agent at the rotating mercury electrode. All the alkaline earths can be titrated at the microgram level with reasonable accuracy, and calcium may be titrated with EGTA in the presence of a 1000-fold excess of magnesium.     

Estimation of the alkaline earths metals by sequential titration with sodium tetraphenylborate

Summary Alkaline earths metals were titrated potentiometrically in the presence of polyethylene glycol with sodium tetraphenylborate. The sensor was a coated-graphite rod. The method can be used for the sequential estimation of barium, strontium, and calcium. The solubility of the precipitated species decreases with increasing atomic weight of the metals.

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Bestimmung von Erdalkalimetallen durch sequentielle Titration mit Natriumtetraphenylborat

Zusammenfassung Die Erdalkalimetalle wurden potentiometrisch in Gegenwart von Polyethylenglykol mit Natriumtetraphenylborat titriert. Als Sensor diente eine überzogene Graphitstabelektrode. Sequentiell können Barium, Strontium und Calcium bestimmt werden. Die Löslichkeit der Niederschläge nimmt mit ansteigendem Atomgewicht ab.

     

Systematic investigation of aluminium interferences with the alkaline earths in flame atomic absorption spectrometry

Summary Aluminium interferes with the absorption of Mg and Ca in the air-acetylene flame to such an extent that the corresponding absorbances may fall even to zero. This well-known chemical interference can be overcome with the nitrous oxide-acetylene flame, completely in the case of Mg, however only to a restricted extent in the case of Ca. Mg and Ca with concentrations of the AAS-working range in aqueous solutions and Cl^– or NO ₃ ^– as anions (in an aqueous HCl or HNO₃ matrix, respectively), were determined in the air-acetylene flame with continuously rising Al portions and with (or without) 0.25% Cs as radiation buffer, in order to quantify the degree of these interferences. The same was done to evaluate the extent of the suppression of those interference when using a releaser or protector reagent in both the air-acetylene and the nitrous oxide-acetylene flame. After the decrease of absorption in the air-acetylene flame by forming thermally stable Mg or Ca aluminates, a rapid increase (positive interference) occurs unexpectedly in the presence of Cl^–±Cs and with further rising Al contents. This effect still appears for Ca also in the hotter nitrous oxideacetylene flame, however, only in a restricted extent. In the air-acetylene flame the undisturbed absorptions for Mg and Ca (i.e. the starting data without Al) are nearly reached again within the range of the positive interference. This supports the assumption that in consequence of a continuous equilibrium change in the flame because of the rising Al content and in the presence of Cl^– and ±Cs the formation of only pure Al oxides now generates the release of Mg and Ca (instead of the thermally stable aluminates in the beginning). In the air-acetylene flame interferences of 1000 mg/l Al are completely removed by an addition of 1% releaser-La, when measuring up to 0.2 mg/l Mg and up to 4 mg/l Ca. The extent of releasing Mg and Ca is effective only up to that Al concentration range which leads to the absorption maximum of Mg and Ca. In the nitrous oxideacetylene flame 5000 mg/l Al are compensated when determining up to 1 mg/l Mg. In the case of Ca, which is detected up to 4 mg/l, interferences of 1000 mg/l Al are only avoided by using the nitrous oxide acetylene flame together with 1% releaser-La. The excellent sensitivity of Ca in this flame (in contrast to the air-acetylene flame) permits a strong dilution, lowering thereby the interfering Al concentration, too. For Mg the same option is valid because of its high sensitivity in the air-acetylene flame.     

Present state of complexometry-IV Determination of rare earths

A review of the visual complexometric determination of the rare earths, scandium and yttrium with various volumetric reagents is presented. As in previous parts attention is paid to the complexometric behaviour of these metals and to the problems of interferences in their determinations. Methods for the determination of thorium, scandium and some rare earths in mixtures are described in detail. Recent developments and further possibilities in this field are discussed.     

Determination of yttrium in rare earths by photon activation analysis

The determination of yttrium in the presence of large amounts of the rare earths by the thermal neutron reaction (89)Y(n, gamma)(90)Y is complicated because of frequent problems of sample self-shielding from major constituents of the sample, and the difficulty of separating (90)Y, a pure beta-emitter, from other elements which are very similar chemically. A non-destructive photon activation analysis method has been developed for this determination. Bremsstrahlung from a 35-muA beam of 35-MeV electrons induces the photonuclear reaction (89)Y(gamma, n)(88)Y. Optimum sensitivity is obtained by coincidence counting of the 0.90 and 1.84 MeV gamma-rays associated with the decay of (88)Y. The detection limit is less than 1 mug of yttrium.     

Determination of rare earths in rare-earth concentrates by neutron activation analysis

Neutron activation analysis was applied to the determination of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Yb, Lu and Th in rare-earth concentrates resulting from minerals. High-resolution gamma-ray spectrometry with a Ge(Li) detector was used for the non-destructive determination, and a single comparator method using Co as flux monitor was applied.     

Back titration with mercuric nitrate in alkaline : medium volumetric analysis of binary mixtures of the alkaline earths,magnesium, zinc and cadmium

Mercuric nitiate has proved to be suitable for the back titration of the excess amount of EDTA remaining in solution when this compound has reacted quantitatively either with zinc or cadmium in the presence of one of the three elements barium, strontium and magnesium at pH 8 or 9, or with both cations at pH 11. Advantage is taken of this behaviour for analysing binary mixtures of the above mentioned cations by back titration at lower and higher pH's The end-points are detected potentiometrically, reasonable jumps being obtained; the agreement with the theoretical end-points is satisfactory.     

Simultaneous determination of alkali, alkaline earths and ammonium in natural waters by ion chromatography

An ion chromatographic method has been developed for the determination of alkali (Li(+), Na(+), K(+)), alkaline earths (Ca(2+), Mg(2+), Ba(2+), Sr(2+)) and ammonium ion in waters. The usual difficulties encountered during traditional cation-exchange separations (incomplete resolution for Na(+) and NH(4) (+) present in disproportionate concentration ratios) have been overcome tuning the selectivity of the separation by the introduction of 18-crown-6 ether in the mobile phase using an IonPac CS12A (150x3 mm id) column. After a detailed study of the effect of mobile phase components on separation, a gradient elution from 26 mM methanesulphonic acid (MSA) with a step change at 9 min to 60 mM MSA (0.5 mM 18-crown-6) provided the required baseline separation for the eight selected analytes. The method developed provides the advantage of the determination, in the same analytical run, also of strontium and barium, which is usually performed by spectroscopic techniques. Within-day and between-day repeatability have been assessed, observing between-day RSD included between 0.3 and 1.8% for retention times and 0.6 and 7.2% for peak areas. The method has been finally tested for the analysis of water samples of different provenience (well, tanks, water system) and results compared with those obtained by the laboratory in charge of the control of drinking water for the city of Torino (Italy).     

中温商业SCR催化剂碱和碱土中毒特性研究

在实验室条件下对选择性催化还原(SCR)商业催化剂的碱(K)和碱土(Ca)中毒进行了模拟,并采用液氮吸附、扫描电镜、能谱分析、NH_3-程序升温脱附、H_2-程序升温还原等方法对催化剂中毒前后的物理化学性质变化进行了表征。结果表明,K和Ca的中毒没有破坏商业中温SCR催化剂孔的基本结构,但K和Ca的中毒使催化剂的比表面积和孔容减小。K和Ca的中毒在一定程度上改变了催化剂表面钒的价态,导致了钒的还原能力减弱,同时降低催化剂表面化学吸附氧。钾中毒和钙中毒使催化剂的表面酸量降低。钾和钙中毒造成中温SCR催化剂的脱硝活性降低,并且Ca中毒造成的催化剂活性降低要明显高于K中毒。     

Determination of rare earths in geological samples by neutron activation analysis

The significance of rare earth distribution patterns in trace element geochemistry is briefly reviewed. Established methods for their determination at the Reactor Centre by instrumental and radiochemical techniques are described, and examples of recent applications discussed.     

Determination of light rare earths and other elements in Cuban soils

The objective of the present study was the elaboration of a procedure for the determination of Y, La, Ce, Pr and Nd in soils by spectrophotometry with Arsenazo III preceded by a separation-concentration stage, which includes coprecipitation and ion exchange. Multielement analysis by energy dispersive X-ray fluorescence (including Y, La, Ce and Nd) and flame atomic absorption spectrophotometry was carried out simultaneously in order to obtain a general characterization of the soil samples. Certified reference materials and statistical intercomparison of the obtained results were used to evaluate the accuracy of the methods. The precision was examined by analyzing replicate samples.     

Synthetic and analytical studies on colour reagents-IX The reactions of phthaleinazo compounds with the alkaline earths

Some new phthaleinazo compounds-o,o'-dihydroxyazo compounds-have been prepared by coupling chromotropic acid, R-acid, and 2-hydroxy-3-naphthoic acid with bis-diazotized diaminophthaleins. These compounds have been found to be very sensitive colour reagents for alkaline earths in alkaline media, and in particular, bis(chromotropeazo)phenolphthalein is the most sensitive yet found.     

The flame photometric determination of alkali metals, alkaline earths and copper in nuclear grade uranium

Summary A method, which involves prior chemical separation of uranium from impurities by tributylphosphate extraction, is described for the determination of alkali metals, alkaline earths and copper in nuclear grade uranium. The characteristic emission lines, excited in hydrogen-oxygen flame, are isolated by a small monochromator and recorded photoelectrically.Using 3 g samples 0.005 ppm of Li, 0.001 ppm of Na, 0.05 ppm of K, 1 ppm of Mg, 1.5 ppm of Ba and 2 ppm of Cu can be determined in uranium, with reproducibilities better than ± 3%.Some interelemental interferences are discussed, and the possibilities of their elimination are described.The method can be used without modification for the analysis of uranium containing up to 100ppm of impurities.

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Zusammenfassung Es wird ein Verfahren zur flammenphotometrischen Bestimmung von Alkalien, Erdalkalien und Kupfer in Uran von nuklearem Reinheitsgrad beschrieben, das eine vorherige Extraktion des Urans mit Tributylphosphat verwendet. Die charakteristischen Emissionslinien werden durch eine Wasserstoff-Sauerstoff-Flamme angeregt, durch einen kleinen Monochromator isoliert und photoelektrisch registriert. Mit einer Probe von 3 g können noch 0,005 ppm Li, 0,001 ppm Na, 0,05 ppm K, 1 ppm Mg, 1,5 ppm Ba und 2 ppm Cu mit einer Reproduzierbarkeit von <± 3% bestimmt werden. Störungen durch andere Elemente sowie Möglichkeiten zu ihrer Ausschaltung werden diskutiert. Das Verfahren kann bis zu einem Gehalt von 100 ppm an Verunreinigungen in Uran angewendet werden.

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On leave to the IAEA Vienna, Austria.     

Determination of the glass transition temperature

The definition of the glass transition temperature, T _g, is recalled and its experimental determination by various techniques is reviewed. The diversity of values of T _g obtained by the different methods is discussed, with particular attention being paid to Differential Scanning Calorimetry (DSC) and to dynamic techniques such as Dynamic Mechanical Thermal Analysis (DMTA) and Temperature Modulated DSC (TMDSC). This last technique, TMDSC, in particular, is considered in respect of ways in which the heterogeneity of the glass transformation process can be quantified.     

Triazenide complexes of the heavier alkaline earths: synthesis, characterization, and suitability for hydroamination catalysis

A series of triazenide complexes of the heavier alkaline earths, Ca, Sr and Ba, have been synthesized by either protonolysis or salt metathesis routes. Although complexes of the form [{Ar 2N 3}M{N(SiMe 3) 2}(THF) n ] (M = Ca, n = 2; M = Sr, n = 3; Ar = 2,6-diisopropylphenyl) and [{Ar 2N 3}Ca(I)(THF) 2] 2 could be isolated and characterized by X-ray crystallography, solution studies revealed the propensity of these species to undergo Schlenk-like redistribution with the formation of [{Ar 2N 3} 2M(THF) n ] (M = Ca, n = 1; M = Sr, n = 2). The latter compounds have been synthesized independently. In the case of the large barium dication, attempts to synthesize the heaviest analogue of the series, [{Ar 2N 3} 2Ba(THF) n ], failed and led instead to the isolation of the potassium barate complex [K{Ar 2N 3}Ba{N(SiMe 3) 2} 2(THF) 4]. Single crystal X-ray diffraction studies demonstrated that, although in all the aforementioned cases the triazenide ligand binds to the electrophilic group 2 metal centers via symmetrical kappa (2)- N, N-chelates, in the latter compound an unprecedented bridging mode is observed in which the triazenide ligand coordinates through both terminal and internal nitrogen centers. A series of density-functional theory computational experiments have been undertaken to assist in our understanding of this phenomenon. In further experiments, the calcium and strontium amide derivatives [{Ar 2N 3}M{N(SiMe 3) 2}(THF) n ] (M = Ca, n = 2; M = Sr, n = 3) proved to be catalytically active for the intramolecular hydroamination of 1-amino-2,2-diphenylpent-4-ene to form 2-methyl-4,4-diphenylpyrrolidine, with the calcium species demonstrating a higher turnover number than the strontium analogue ( 2a, TOF = 500 h (-1); 2b, TOF = 75 h (-1)). In these instances, because of ambiguities in the structural charcterization of the precatalyst in solution, such quantification holds little value and detailed catalytic studies have not been conducted.