The atomic absorption spectroscopy of selenium

Selenium can be determined in aqueous solution by atomic absorption spectroscopy at 1960, 2040,2063 or 2075 Å; the sensitivities for these lines with a Techtron 10-cm air-acetylene burner are in the ratio of 1:9:60:93. When a Beckman tripleburner (air-hydrogen) and a triple-pass optical system are used, the most sensitive1960 Å line provides a sensitivity of 0.5 p.p.m. and a detection limit of 1.0 p.p.m. The performence in air-hydrogen and air-acetylene flames is described,and optimum experimental conditions determined.With the Se 1960 Å line and a Techtron 10-cm air-acetylene burner, selenium extracted into methyl isobutyl ketone as its diethyldithiocarbamate complex gives a sensitivity of 0.30 p.p.m.,which is a 2.4-fold increase over that found in aqueous solution.     

Determination of Phosphorus in Detergents by Flame Emission Spectrometry

Abstract

Detergents are decomposed by heating and dissolved in water. Aliquots are ion-exchanged, and the solutions are aspirated into an air-hydrogen flame in contact with a cooled metal surface. The emission intensity of an HPO band at 526.2 mμ is measured. Results are given for four common detergents.     

Peroxide Coordination of Tellurium in Aqueous Solutions

Tellurium–peroxo complexes in aqueous solutions have never been reported. In this work, ammonium peroxotellurates (NH₄)₄Te₂(μ‐OO)₂(μ‐O)O₄(OH)₂ ( 1 ) and (NH₄)₅Te₂(μ‐OO)₂(μ‐O)O₅(OH)?1.28 H₂O?0.72 H₂O₂ ( 2 ) were isolated from 5 % hydrogen peroxide aqueous solutions of ammonium tellurate and characterized by single‐crystal and powder X‐ray diffraction analysis, by Raman spectroscopy and thermal analysis. The crystal structure of 1 comprises ammonium cations and a symmetric binuclear peroxotellurate anion [Te₂(μ‐OO)₂(μ‐O)O₄(OH)₂]^4?. The structure of 2 consists of an unsymmetrical [Te₂(μ‐OO)₂(μ‐O)O₅(OH)]^5? anion, ammonium cations, hydrogen peroxide, and water. Peroxotellurate anions in both 1 and 2 contain a binuclear Te₂(μ‐OO)₂(μ‐O) fragment with one μ‐oxo‐ and two μ‐peroxo bridging groups. ¹²⁵Te NMR spectroscopic analysis shows that the peroxo bridged bitellurate anions are the dominant species in solution, with 3–40 %wt H₂O₂ and for pH values above 9. DFT calculations of the peroxotellurate anion confirm its higher thermodynamic stability compared with those of the oxotellurate analogues. This is the first direct evidence for tellurium–peroxide coordination in any aqueous system and the first report of inorganic tellurium–peroxo complexes. General features common to all reported p‐block element peroxides could be discerned by the characterization of aqueous and crystalline peroxotellurates.     

Emission intensity of cesium in flames of various gas compositions

The emission intensity of cesium at 852.1 nm has been studied in hydrogen flames burning with various mixtures of oxygen and nitrogen. A significant maximum was observed in the relative emission intensity of cesium at an oxygen to nitrogen ratio of 3:2 in the aspirating gas. The effect of Rb⁺, K⁺, Li⁺, Na⁺, and NH₄⁺ ions on cesium emission is much less pronounced in this optimum flame than in a pure oxy-hydrogen flame. The optimum flame (60% oxygen) yields a significantly better calibration curve than can be obtained in either the normal air-hydrogen or oxyhydrogen flame for 0–12 p.p.m. cesium concentrations; the graph is linear over this concentration range.     

Spectral,Optical, and Photocatalytic Characteristics of Quantum-Sized Particles of CdTe

Methods were developed for the synthesis of quantum-sized particles of CdTe, stabilized in aqueous solutions of thioglycolic acid, using H₂Te or NaHTe produced in situ by electrochemical reduction of tellurium. The spectral and optical characteristics of the synthesized CdTe nanoparticles were studied. It was found that they have photocatalytic activity in the reduction of methylviologen with sodium sulfite.     

Coexistence of Tellurium Cations and Anions in Phosphonium-Based Ionic Liquids

Elemental tellurium readily dissolves in ionic liquids (ILs) based on tetraalkylphosphonium cations even at temperatures below 100 °C. In the case of ILs with acetate, decanoate, or dicyanamide anions, dark red to purple colored solutions form. A study combining NMR, UV-Vis and Raman spectroscopy revealed the formation of tellurium anions (Te_n)²⁻ with chain lengths up to at least n=5, which are in dynamic equilibrium with each other. Since external influences could be excluded and no evidence of an ionic liquid reaction was found, disproportionation of the tellurium is the only possible dissolution mechanism. Although the spectroscopic detection of tellurium cations in these solutions is difficult, the coexistence of tellurium cations, such as (Te₄)²⁺ and (Te₆)⁴⁺, and tellurium anions could be proven by cyclic voltammetry and electrodeposition experiments. DFT calculations indicate that electrostatic interactions with the ions of the ILs are sufficient to stabilize both types of tellurium ions in solution.     

New data on the solubility of amorphous silica in organic compound-water solutions and a new model for the thermodynamic behavior of aqueous silica in aqueous complex solutions

Experimental solubilities of amorphous silica in several aqueous electrolyte solutions and in aqueous solutions of organic compounds, and theoretical considerations concerning cavity formation, electrostriction collapse, ion solvation, and long- and short-range interaction of the solvated ions with one another⁽¹⁾ permit the calculation of the partial excess free energies and the activity coefficients of aqueous silica. It is shown that, in the case of non-dissociated aqueous organic solutions, the variation of log m (SiO₂) with the reciprocal of the dielectric constant of the solution is described by a single linear equation independent of the nature of the organic compound. For aqueous electrolyte solutions, a specific linear relationship between log m (SiO₂) and the reciprocal of the dielectric constant occurs for each electrolyte. The success of the equation in reproducing the experimental solubilities of amorphous silica in aqueous solutions of electrolytes and organic compounds supports previous evidence indicating a polar charge distribution in the solvated SiO₂ molecule. Our data permit the calculation of the effective local charge of dissolved SiO₂ molecules and of the short-range interaction parameters between SiO₂ and various ions. The proposed equation of state can be used to calculate the affinity of reactions among SiO₂ minerals and complex aqueous solutions.     

Selective separations by reactive ion exchange : Part III. Preconcentration and separation of oxo anions

A new procedure for simultaneous preconcentration, separation, and determination of permanganate, chromate and vanadate was developed for aqueous solutions containing p.p.b. levels of these anions (and molybdate). The presence of other (non-complexing) ions in p.p.m. concentrations did not interfere. The procedure consisted of reactive adsorption of all three anions as their reduced cations, on iron(II)-treated resin, followed by elution of vanadium(IV) with 0.01 M HNO₃/H₂O₂, manganese(II) with 0.35 M HCl, and chromium(III) with 4M HCl. Concentration factors of 40 were obtained with 1-l “samples” 10 p.p.b. concentrations were determined with standard deviations of 4–5 % by a.a.s. and conventional spectrophotometry.     

The determination of gold,platinum, palladium and rhodium by atomic absorption spectrophotometry with an ultrasonic nebulizer and a multi-element high-intensity hollow-cathode lamp with selective modulation

The use of a multi-element high-intensity hollow-cathode lamp with selective modulation and a 2-MHz ultrasonic nebulizer for the determination of Au, Pt, Pd and Rh by atomic absorption spectroscopy is described. The sensitivities for the various elements in aqueous and organic media were studied. Only some organic solutions could be nebulized satisfactorily; a solution containing 95% acetone proved to be the best. For aqueous solutions, the detection limits (concn. giving 0.004 O.D.) were as follows: Au, 0.03 p.p.m.; Pd, 0.02 p.p.m.; Pt. 0.3 p.p.m.; and Rh, 0.09 p.p.m. For a 95% acetone solution the detection limits were: Au, 0.009 p.p.m.; Pd, 0.012 p.p.m.; Pt, 0.20 p.p.m. and Rh, 0.06 p.p.m. The coefficients of variation for aqueous and organic media were satisfactory.     

ENHANCEMENT OF THE SENSITIVITY OF RADIATIVE and NON-RADIATIVE DETECTION TECHNIQUES IN THE STUDY OF PHOTOSENSITIZATION BY WATER SOLUBLE SENSITIZERS USING A REVERSE MICELLE SYSTEMS*,†

The study of photosensitization processes in aqueous solution is complicated by the unsuit-ability of water as solvent for the commonly used techniques for monitoring radiative and non-radiative relaxation processes. The infrared luminescence method is hampered by the relatively weak intensity of emission and short lifetime of singlet molecular oxygen, O₂(¹Δ_g), in water. Photoacoustic and photothermal detection of the dominant non-radiative relaxation process for O₂(¹Δ_g) is also inhibited by the unfavorable physico-chemical properties of water which reduce the sensitivities of these techniques for the study of sensitizers in aqueous with respect to non-aqueous media. Such problems have been alleviated by incorporating the sensitizer in the aqueous core of aerosol OT reverse micelles. It is demonstrated that the sensitivity of both radiative and non-radiative detection depends not on the local environment of the sensitizer but on the overall composition of the medium, which, in the case of reverse micelle solutions, is predominantly hydrocarbon. This produces a 4.5 and 6-fold enhancement of the sensitivity of luminescence and optoacoustic detection, respectively, in comparison to purely aqueous solution. The utility of the method is demonstrated for Rose Bengal, where quantum yields of intersystem crossing (φ_isc) of 0.78 (LIOAC) and singlet oxygen generation (φ_δ) of 0.81 (LIOAC) and 0.80 (TRLD) were measured. Phenazine was also studied for comparative purposes and to corroborate values obtained for Rose Bengal.     

Détermination du cadmium,de l'indium et du tellure par polarographie impulsionnelle sans séparation préalable

Cadmium, indium and tellurium can be determined without preliminary separation by differential pulse polarography in a specially prepared supporting electrolyte of 0.1 M KI saturated with tartaric acid. In this medium the three peaks are well separated. There is no interference for Cd—In and In—Te mixtures, but Cd—Te mixtures can prove difficult. However, the peak intensity of tellurium is over ten times that of cadmium for the same concentration, and it is possible to determine tellurium near the limit of detection. Cadmium is determined afterwards in more concentrated solution. Indium does not interfere. An application to CdIn₂Te₄ is reported.     

An Ultrastable Matryoshka [Hf13] Nanocluster as a Luminescent Sensor for Concentrated Alkali and Acid

Stable metal clusters that can resist both highly concentrated acid and alkali are unknown. Herein, we present a discrete neutral cluster, Hf₁₃(μ₄‐O)₈(OCH₃)₃₆ ( 1 ), which features extraordinary chemical stability by preserving its crystalline state in concentrated aqueous solutions of both acid (10 m HNO₃) and alkali (20 m boiling NaOH). Importantly, 1 can serve as a luminescent probe for detecting both concentrated alkali (20 m NaOH) and strong acid (1 m HNO₃) with high selectivity and repeatability. DFT studies of the electronic structure and bonding revealed that 1 has an extremely large HOMO–LUMO gap due to strong d π–p π bonding that accounts for the ultrahigh stability.     

Chemisches Verhalten und Bestimmung kleiner Tellur-Mengen

Zusammenfassung 1. Beim Lösen und Aufschließen sind im allgemeinen keine Verluste an Tellur zu befürchten; allerdings sollen Schmelzaufschlüsse nicht in Metalltiegeln durchgeführt werden, da ein Teil des Tellurs im Tiegel zurückgehalten werden kann.Nur beim trockenen Veraschen an der Luft und beim Abrauchen von Ammoniumsalzen treten hohe Verluste auf. 2. Die Abtrennung von Tellurspuren durch Fällen mit H₃PO₂-Lösung ist nicht ganz vollständig; bei Konzentrationen unter etwa 1 g Te/ml sind die Verluste nicht mehr zu vernachlässigen.Zum Anreichern durch Mitfällung sind vor allem Eisen(III)-hydroxid, elementares Arsen und Selen zu empfehlen.Tellur (IV) kann mit zahlreichen Reagentien und organischen Lösungsmitteln aus wäßrigen Lösungen ausgeschüttelt werden. Die Verteilungskoeffizienten nehmen jedoch in der Regel bei sehr kleinen Tellur-Konzentrationen ab. Besonders günstig sind Systeme mit Jodid- und Tetraphenylphosphoniumzugaben.Versuche mit Ionenaustauschern verliefen bei sehr kleinen Tellur-Konzentrationen sämtlich unbefriedigend; entweder war die Abtrennung aus Lösungen oder die Elution von der Säule unvollständig. 3. Die photometrischen Bestimmungsmethoden sind z.T. empfindlich, aber ziemlich störanfällig.Die polarographische Bestimmung kann in verschiedenen Grundlösungen durchgeführt werden; mit dem klassischen Polarographen werden im allgemeinen Empfindlichkeiten von etwa 1 g Te(IV)/ml erreicht, mit moderneren Geräten sollten wesentlich empfindlichere Bestimmungen möglich sein.Die Bestimmung durch Atomabsorption ist etwas weniger empfindlich, aber sehr selektiv und wenig gestört.Als zur Zeit empfindlichste Bestimmungsmethode ist die Aktivierungsanalyse anzusehen; etwas unempfindlicher ist die spektrographische Methode. Die Flammenphotometrie sei nur erwähnt [25].

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Chemical behaviour and determination of small amounts of tellurium

1. Normally, there will be no losses of tellurium during dissolution and decomposition steps. Decompositions should not be performed in metallic crucibles, as tellurium will be retained partly within the crucible. Dry ashing in air and sublimation of ammonium salts cause severe losses of tellurium. 2.Separation of tellurium by precipitation with H₃PO₂ solution is not quantitative; losses cannot be neglected at concentrations <1 g Te/ml.Enrichment of tellurium by coprecipitation can be obtained preferably with iron hydroxide, elemental arsenium, and selenium.Tellurium(IV) can be extracted from aqueous solutions by many different organic solvents, but distribution coefficients decrease with decreasing tellurium concentration. Systems containing iodide and tetraphenylphosphonium ions are preferable.No separation using ion-exchangers have been found satisfactory at low tellurium concentrations. Either separation from solution or elution from the exchanger were not quantitative. 3.Several photometric determination methods are sensitive, but rather strongly influenced by interferences. Polarographic determination can be performed in different basic solutions. Classical polarography gives sensitivities of ca. 1 g Te(IV)/ml, but modern equipment should enable the determination of much lower concentrations.Atomic absorption is not so sensitive, but very selective and free from interferences.At present, the most sensitive determination of tellurium is by neutron activation; optical spectrography is less sensitive. Flame photometry shall be mentioned only [25].

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Diss. Mainz 1967 und Diplomarbeit Mainz 1965.     

A Spectrophotometric and Chromatographic Study on the Products of Radiation-induced Oxidation of 3,5-Dihydroxytoluene in Aqueous Solutions

Aerated aqueous solutions of 3,5-dihydroxytoluene (₇) irradiated with single electron pulses in the dark or under exposure to a light flux were studied by pulse radiolysis and high-performance liquid chromatography. The two types of high-energy particles, -rays and fast electrons, were compared. The complex mechanism of radiation-induced redox reactions occurring in the aqueous solutions of ₇ and giving low-molecular and long-chain oxidation products was experimentally proved. Transient species of the radiation-induced oxidation of ₇ that absorb light in the spectral range of 250–420 nm and have a lifetime longer than a millisecond were observed.     

Spectrometric evidence ford-orbital participation in the lowest excited singlet states of naphthalenethiols

Tellurium can be determined polarographically in the range 10^?5–10^?8M by means of the Te⁰_ads→Te^2- reduction in 1M perchloric acid as supporting electrolyte. Pulse polarography, a.c. polarography and linear sweep cyclic voltammetry can be used to determine tellurium in the p.p.b. range. Copper(II), arsenic(III) and selenium(IV) interfere, but the interferences can be overcome by a standard addition method.     

Effects of salt on the protonation in aqueous solution of triethylenetetramine and tetraethylenepentamine

Protonation constants of triethylenetetramine (trien) and tetraethylenepentamine (tetren) were determined, in NaCl aqueous solutions, at different ionic strengths, at 25°C, using the the pH-metric technique. The behavior of protonation constants as a function of ionic strength can be explained by a model which takes into account the formation of the species AH _q Cl _p [A=amine; q=1...4, p=1,2 (trien); q=1...5, p=1.3 (tetren)].     

Morphology of tellurium electrolytically deposited in a pulsed mode

Morphology of tellurium deposits produced by pulsed electrolysis of 0.005–0.05 M TeCl₄ solutions in dimethyl sulfoxide was studied. The effect of the TeCl₄ concentration and pulsed current parameters on the structure of electrolytically deposited tellurium films was examined.     

Concentration of vacancies in the metal sublattice of cadmium and mercury tellurides solid solutions depending on composition

Calculations for the concentration of vacancies in the metal sublattice of Cd _x Hg_{1 − x} Te ternary compound in dependence on temperature and composition in the range x = 0.2–1.0 are presented. In our calculations, the vacancy concentration was determined according to the reaction of the joining of the crystal lattices of two sites, one of which was occupied by an atom of tellurium while the site in the metal sublattice remained vacant. Using this approach, the concentration of vacancies in the metal sublattice was described via the activity of tellurium, allowing us to use it for solid solutions and a number of cases in which it is difficult to describe the pressure of the metal correctly. The enthalpy of formation was determined for vacancies in HgTe using the experimental data on the concentration of vacancies in Cd _x Hg_{1 − x} Te samples. It was shown that the natural oxide occurring on the surface of the investigated films in air can lead to changes in their electrophysical parameters during heat treatment.     

Influence of electrodeposition conditions on the properties of CdTe films

The results of the influence of electrodeposition conditions on the structural, compositional, optical, and photoelectrochemical properties of CdTe thin films deposited in one-step electrochemical method are presented. The CdTe films were prepared electrochemically from aqueous acidic solution with low ratios of Cd²⁺ ions to Te(IV) ions concentration. Instead of commonly used TeO₂, water-soluble Na₂TeO₃ was used as a source of tellurium ions. The cathodic deposition of CdTe was performed at different constant potentials from solutions containing different cadmium and tellurium ions concentration. As-deposited CdTe thin films were studied by different analytical techniques. The X-ray photoelectron spectroscopy spectra exhibited CdTe formation on the electrode with some amount of tellurium oxides and cadmium oxides. The best quality CdTe deposits, free of TeO₂, were formed in bath containing excess of Cd²⁺ ions and at the potential of ?0.65 V vs. saturated calomel electrode, slightly more positive than E _eq of Cd/Cd²⁺ system. Structural X-ray diffraction studies revealed polycrystallinity of deposits with the highest content of the (111)-oriented cubic (111) form. Optical band gap energy values were found in the range from 1.36 to 1.6 eV for CdTe films prepared at various synthesis conditions. The preliminary photoelectrochemical studies have shown that the variation of the deposition potential as well as bath composition leads to the formation of p- or n-type CdTe films. As-deposited CdTe films were not stable in polysulfide solution under illumination.     

Studies in atomic-fluorescence spectroscopy-IV The atomic-fluorescence spectroscopic determination of selenium and tellurium

Selenium and tellurium are determined down to 0.25 and 0.12 p pm respectively by measuring the atomic-fluorescence signals at 2040 A and 2143 A respectively. Other possible wavelengths of measurement are considered in detail and the effects of some extraneous ions are examined. Microwave-excited electrodeless discharge tubes are used as spectral sources and intensity measurements are made with a Unicam SP 900A atomic-absorption/flame-emission spectrophotometer. Atomic-absorption measurements are also made with the same sources and spectrophotometer. The advantages of atomic-fluorescence methods and the use of electrodeless discharge tubes are discussed.