On the Stark broadening in the Au I and Au II spectra from a helium plasma

The Stark FWHM (Full-Width at Half of the Maximal line intensity, W) of 5 neutral and 26 singly ionized gold (Au I and Au II, respectively) spectral lines have been measured in laboratory helium plasma at approximately 16,600 K electron temperature and 7.4 × 10²² m^− 3 electron density. Five Au I and ten Au II W values are reported for the first time. The Au II W values are compared with recent theoretical data, calculated based on a modified semi-empirical approach, and also with existing experimental W values. Our normalized Stark widths are six times higher than those measured in a laser-produced plasma. Possible explanation of this is recommended here. An agreement (within the accuracy of the experiment and uncertainties of the theoretical approach used) with the recently calculated W data was found in the 6p–7s Au II transition. The calculated hyperfine splitting for the five Au II lines in the 6s–6p transition is also presented. At the stated helium plasma conditions, Stark broadening has been found to be the dominant mechanism in the Au I and Au II line shape formation. A modified version of the linear low-pressure pulsed arc was used as a plasma source operated in helium, with gold atoms as impurities evaporated from the thin gold cylindrical plates located in the homogeneous part of the discharge, providing conditions free of self-absorption. This plasma source ensures good conditions for generation of excited gold ions due to Penning and charge exchange effects.     

Transition probabilities for some infrared O I spectral lines—Application for determining excitation temperatures in low temperature plasmas

Intensities of selected spectral transitions of neutral oxygen emitted from a wall-stabilized arc have been measured. Applying reliable transition probability data taken from literature, Boltzmann plots have been constructed and the temperatures of the plasma have been obtained. At arc plasma conditions ensuring partial local thermal equilibrium, transition probabilities for 4 O I spectral lines from the near infrared spectral range have been obtained. These new results, together with data for two other studied O I spectral lines taken from the National Institute of Standards and Technology data base, are proposed as a suitable set of transition probabilities applicable for diagnostics of low temperature plasmas.     

Syntheses,characterization, and Mossbauer study of Sn(II and Sn(IV) complexes of the cyclopentadienedithiocarboxylate ligand

The preparation and physical characterization of the tetraethylammonium salts of bis(cyclopentadienedithiocarboxylate)stannate(II) and tris(cyclopentadienedithiocarboxylate)stannate(IV) are reported. The coupling constants for the ring protons of the coordinated and uncoordinated ligand indicate that the oxidation state variation of the metal has little effect on the electronic structure of the ligand. The Mössbauer parameters for the Sn(IV) complex (δ = 1.05 ± 0.02 mm/sec with respect to SnO₂, Line width = 1.05 mm/sec) are normal for a pseudo-octahedral complex. The values for the Sn(II) complex are somewhat abnormal for a Sn(II) complex (δ = 0.29 mm/sec, Line width = 1.65 mm/sec) and are interpreted as indicative of metalmetal bonding in the molecular structure.     

Characterization of Cr(III)-Zr(IV) mixed and Sn(II) doped hydrous oxides

Surface and structural properties of chromium-zirconium mixed and Sn(II)doped hydrous oxide gels have been compared with chromium oxide hydrate gel by the use of thermal analysis, IR spectroscopy, X-ray diffraction, electron microscopy and magnetic measurements. The mixed and doped oxide gels were found to have a hexagonal close packed stacking of O, OH and H₂O ligands with chromium ions distributed in octahedral sites with little degree of order among them. The microstructure of the gels are characterized by the presence of large aggregates of chromium hydroxides, fine granular sheets due to HCrO₂ phase and Cr(OH)₃ microcrystallites. Magnetic susceptibility measurements indicate anti-ferromagnetic behaviour of these gels.     

Accurate lifetime measurements of the 2p 3d 1 D 0 and 2p 3d 3 P 2 0 levels in N II with the beam-foil-laser method

We have obtained accurate values for the radiative lifetimes of the 2p 3d ¹ D ⁰ and 2p 3d ³ P ₂ ^o levels in NII by the cascade-free beam-foil-laser spectroscopy method. Our results are (2p 3d ¹ D ⁰)=0.346±0.012 ns and (2p 3d ³ P ₂ ^o )=0.457±0.020 ns. Comparison of these results with experimental and recent theoretical lifetimes reported previously is also made.Senior Research Associate of the Belgian FNRS     

Optical isotope shifts and changes in nuclear charge radii of stable Ti isotopes

Isotope shifts and hyperfine structures in three optical transitions of TiI have been investigated by using laser induced resonance fluorescence in a collimated atomic beam. From the isotope shifts data, changes of the mean square charge radii of the stable titanium isotopes have been determined for the first time. Using a combined analysis with muonic atom data on root mean square nuclear charge radii, improved model independent r ^21/2 values for the odd-even Ti isotopes have been obtained.     

Synthesis,composition and ion exchange properties of Sn(IV) and Cr(III) arsenophosphates: separation of metal ions

This paper deals with the synthesis of the arsenophosphates of various metals. The chemical composition, ion exchange capacity, thermal stability, concentration curves, elution curves, pH-titrations and IR studies have been performed on two materials, namely, Sn(IV) arsenophosphate and Cr(III) arsenophosphate. Their utility has been established by achieving four binary separations of industrial importance such as CuNi, FeCu, FeNi and CoNi on columns.     

Spectrometric Studies on the Complexation of Pd(II), Fe(III) and Pt(IV) with mandelazo I

Abstract

A spectrometric study of the reaction between Pd(II), Fe(III) and Pt(IV) ions, and Mandelazo I was carried out. The optimum conditions favouring the formation of the complexes are extensively investigated. The stoichiometry of the complexes formed in solution (1:2, 1:1, 1:1), their apparent stability constants (5.45 × 10⁹, 2.39 × 10⁶, 4.12 × 10⁵) and the ranges for obedience to beer's law (0.2 – 6.4, 0.25 – 7.0, 1.5 – 42.0 μg/mL) are reported for Pd(II), Fe(III) and Pt(IV), respectively. The effect of some metal ions including Cu(II), Zn(II), Mn(II), Cd(II), Hg(II), Co(II), Ni(II), Be(II), Al(III), Th(IV) and U(VI), on the maximum absorbance of the formed complexes was also investigated.     

Radiative lifetimes of the 6p 2 P 1 2/0 and 6p 2 P 3 2/0 levels in Yb II

Radiative lifetimes have been determined for the 6² P ₁ ^2/0 and 6² P ₃ ^2/0 levels in Yb II using the method of laser-induced fluorescence from sputtered metal vapour. The results, 8.0(2)ns (6² P ₁ ^2/0 ) and 6.3(3)ns (6² P ₃ ^2/0 ), are compared with lifetimes obtained from ab initio manybody perturbation calculations.     

Extraction of Ag(I), Cd(II), In(III), Sn(II), Sn(IV), Sb(III), and U(VI) from aqueous solutions by ketone solutions using single-step batch and continuous SISAK methods1,2

The extraction properties of Ag(I), Cd(II), In(III), Sn(II), Sn(IV), Sb(III), and U(VI) from aqueous KI/H₂SO₄ solution into a mixture of 4-methyl-2-pentanone (methyl isobutyl ketone, MIBK) and cyclohexanone (CHO) were studied. Both single-step batch and SISAK² methods were used. The oxidation of Sn(II) to Sn(IV) by iodine and complexation of Sn(IV) by 2,3-dimercapto-propanol-1 (BAL) were also investigated. A method for rapid and continuous separation of indium from tin was developed for investigation of short-lived indium fission products.     

Establishment of an immunoaffinity chromatography for simultaneously selective extraction of Sudan I, II, III and IV from food samples

The establishment of an immunoaffinity chromatography (IAC) for simultaneously selective extraction of four illegal colorants Sudan dyes (Sudan I, II, II and IV) from food samples was described. The IAC column was constructed by covalently coupling monoclonal antibody (mAb) against Sudan I to CNBr-activated Sepharose 4B and packed into a common solid phase extraction (SPE) cartridge. It was observed that IAC column was able to separately capture Sudan I, II, III and IV with maximum capacity of 295, 156, 184 and 173ng, respectively. The extraction conditions including loading, washing and eluting solutions were carefully optimized. Under optimal conditions, the extraction recoveries of the IAC column for Sudan I-IV at two different spiked concentrations were within 95.3-106.9%. After 50 times repeated usage, 64% of the maximum capacity was still remained. Six food samples randomly collected from local supermarket without spiking Sudan dyes were extracted with IAC column and detected by high performance liquid chromatography (HPLC). It was found that there was no detectable Sudan II, III and IV in all six food samples, but Sudan I with the content of 2.7-134.5ngg(-1) was detected in three food samples. To further verify the extraction efficiency, other three negative samples were spiked with Sudan I-IV at the concentrations of 20ngg(-1) and 50ngg(-1), which were then extracted with IAC column. The extraction recoveries and relative standard deviation (RSD) were 68.6-96.0% and 4.8-15.2%, respectively, demonstrating the feasibility of the prepared IAC column for Sudan dyes extraction.     

土贝母化学成分的研究 IV: 土贝母苷乙, 丙, 丁的结构

从葫芦科(Cucurbitaceae)植物假贝母(Bolbostemma paniculatum [Maxin]Franquet)鳞茎中分离到三个土贝母苷乙, 丙, 丁. 用光谱分析和化学降解鉴定了它们的结构, 土贝母乙, 丙是二个新的大环三萜皂苷, 土贝母丁是3-O-[α-L-吡喃阿拉伯糖基(1→2)-β-D-吡喃葡糖基]-3β, β-18, 20, 26-五羟-(20S)-达马-24-烯, 是从植物假贝母中分离到的仅有四环三萜.     

Polarographic analytical determination of Hg(II), Cu(II), Cd(II), As(III), Sb(III), Ti(IV) and U(VI) in the presence of Fe(III)

The analytical determination of Hg(II), Cu(II), Cd(II), As(III), Sb(III), Ti(IV) and U(VI) in the presence of Fe(III) and 1 M H₂SO₄ are investigated using the polarographic technique. The wave corresponding to the reduction of Fe(III) to Fe(II) was found to be completely suppressed by the addition of 1% pyrogallol. Thus, different mixtures of these elements, viz. Hg(II), Cu(II), Cd(II), As(III) and Fe(III)-mixture (A), Cu(II), Cd(II), Sb(III), As(III) and Fe(III)-mixture (B), and Cu(II), Cd(II), Ti(IV), U(VI) and Fe(III)-mixture (C), were quantitatively determined using 1% pyrogallol and 1 M H₂SO₄ as supporting electrolyte. The i₁/c results give excellent correlations in each case, as indicated from the results of leastsquares regression analysis.     

Speciation analysis of Sn(II) and Sn(IV) using baker’s yeast and inductively coupled plasma optical emission spectrometry

The use of Saccharomyces cerevisiae as a substrate to selectively retain Sn(II) and Sn(IV) has been investigated. Several factors affecting the retention of the analytes by yeast, such as pH, amount of biomass, temperature and time of contact were evaluated. Based on this study, a method for determination of Sn(II) and Sn(IV) combining inductively coupled plasma optical emission spectrometry (ICP OES) and solid phase extraction using Saccharomyces cerevisiae is proposed. The procedure consists of the selective retention of Sn(IV) by yeast at pH = 2.0 while Sn(II) remains in solution. Determination of tin in the solid phase was easily carried out by submitting a slurry of the yeast (0.5 g/40 mL) directly to ICP OES. The precision of the extraction procedure was characterized by an RSD lower than 4%. The detection limits of tin (3σ) in the solid phase and the liquid phase were 1.1 and 0.7 μg L⁻¹, respectively. The proposed approach was evaluated for determination of Sn(II) and Sn(IV) in spiked river water and real samples of industrial waste water (untreated and treated). For all samples, recoveries of spiked Sn(II) and Sn(IV) were between 85 and 112%.     

N → Sn coordination in the complexes of tin halides with pyridine: A comparison between Sn(II) and Sn(IV)

The experimentally well‐known complexation of tin(II) and tin(IV) halides with pyridine (py) leads to structures showing N → Sn coordination. In the present work, the complexes SnX_n·mpy (where X = F, Cl, Br, I; n = 2, 4; m = 1, 2) possessing this kind of coordination were studied using a computational quantum chemical approach. Various aspects in the theoretical picture of these complexes were examined to find similarities and differences in their N → Sn coordination. The aspects included, among others, the physical nature of intermolecular interactions, and their role in establishing the structure and energetic stabilization of the complexes. In this context, the effect of tin valency was inspected in great detail. As proven by several theoretical methods, a largely ionic character with a certain covalent component can be attributed to the studied N → Sn coordination, irrespective of tin valency. All complexes are destabilized by py‐py and three‐body interactions, but the Sn(II) complexes experience it to a greater extent. Marked differences are observed in the structural behavior of N → Sn and SnX_n during complex formation. This affects the energetics of complexation and, in consequence, the penta‐coordinated Sn(IV) center shows a higher propensity to expand its coordination number, compared with the tri‐coordinated Sn(II) center. The present study supplements the experimental characterization of SnX_n·mpy and, in general, it sheds light on the coordination of heteroaromatic nitrogen to tin. The survey of the Cambridge Structural Database revealed that such coordination occurred in a number of crystal structures.     

The first measured Ag I, Ag II and Ag III Stark broadening parameters

The Stark widths (W) and shifts (d) of two neutral (520.908 and 546.550 nm), eleven singly (211.382, 224.643, 224.874, 232.029, 232.468, 233.140, 241.141, 241.323, 243.781, 244.793 and 276.754 nm) and three doubly (216.189, 231.004 and 239.569 nm) ionized silver (Ag I, Ag II and Ag III, respectively) spectral lines have been measured in nitrogen plasma at about 18,000 K electron temperature and electron density ranged between 0.65 × 10²³ and 1.15 × 10²³ m^− 3. They are the first measured W and d values while those of the Ag II and Ag III lines are the first published data in these spectra. The modified version of the linear, low-pressure, pulsed arc was used as a plasma source operated in nitrogen with silver atoms, as impurities, evaporated from silver cylindrical plates located in the homogeneous part of the discharge. No theoretical predictions exist for W and d values of above mentioned spectral lines. Besides, we have checked the transition probability ratio of two investigated Ag I lines. An agreement with theoretical predictions was found.     

On the line intensity ratios of prominent Si II,Si III,and Si IV multiplets

Line intensities of singly, doubly and triply ionized silicon (Si II, Si III, and Si IV, respectively) belonging to the prominent higher multiplets, are of interest in laboratory and astrophysical plasma diagnostics. We measured these line intensities in the emission spectra of pulsed helium discharge. The Si II line intensity ratios in the 3s3p²²D–3s²4p²P^o, 3s²3d²D–3s²4f²F^o, and 3s²4p²P^o–3s²4d²D transitions, the Si III line intensity ratios in the 3s3d³D–3s4p³P^o, 3s4p³P^o–3s4d³D, 3s4p³P^o–3s5s³S, 3s4s³S–3s4p³P^o, and 3s4f³F^o–3s5g³G transitions, and the Si IV line intensity ratios in the 4p²P^o–4d²D and 4p²P^o–5s²S transitions were obtained in a helium plasma at an electron temperature of about 17,000 ± 2000 K. Line shapes were recorded using a spectrograph and an ICCD camera as a highly-sensitive detection system. The silicon atoms were evaporated from a Pyrex discharge tube designed for the purpose. They represent impurities in the optically thin helium plasma at the silicon ionic wavelengths investigated. The line intensity ratios obtained were compared with those available in the literature, and with values calculated on the basis of available transition probabilities. The experimental data corresponded well with line intensity ratios calculated using the transition probabilities obtained from a Multi Configuration Hartree–Fock approximation for Si III and Si IV spectra. We recommend corrections of some Si II transition probabilities.