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.     

Ab initio calculations of infrared transition probabilities in the electronic ground states of AlF and AlF+

Electric dipole moment functions and radiative transition probabilities have been calculated for the electronic ground states of AlF and AlF⁺ from highly correlated CEPA electronic wavefunctions. The dipole moments inv = 0 are calculated to be 1.56 D (experimental value is 1.53 ±0.1 D) for AlF and 5.49 D for AlF⁺. Intense transitions in the microwave and infrared spectral region are predicted for both species.     

Determination of the temperature and enthalpy of the solid-solid phase transition of caesium nitrate by differential scanning calorimetry

The equilibrium temperature of the solid-solid phase transition of high purity caesium nitrate has been measured accurately by stepwise heating and by the extrapolation to zero heating rate method. A mean value of 154.3 ± 0.1 °C was obtained using two different heat flux DSC instruments. A value of 3.44 ± 0.04 kJ mol⁻¹ was determined for the enthalpy of transition.     

Comparison of transition probabilities calculated using different parameters on WBEPM theory for some p‐d and d‐p transitions in excited atomic nitrogen

The transition probabilities between individual and multiplet lines for some quartet terms of excited p‐d and d‐p transition arrays of nitrogen atom have been calculated using the weakest bound electron potential model (WBEPM) theory. For determination relevant parameters, we employed both numerical Coulomb approximation (NCA) method and numerical nonrelativistic Hartree–Fock (NRHF) wave functions for expectation values of radii. The necessary energy values have been taken from experimental energy data in the literature. The expectation values of radii obtained using the two different methods have been employed in the calculation of transition probabilities of all transition arrays. The results obtained have been compared with either each other or NIST data. Good agreement with accepted values taken from NIST has been observed for related excited transitions. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Theoretical calculations of transition probabilities and oscillator strengths for Ti III and Ti IV

Due to the complicated electronic configuration of atoms and ions of the transition metal elements, the studies for properties such as transition probabilities and oscillator strengths for these atoms and ions are not systematic. Because of the existence in a variety of stellar objects and wide use in the field of astrophysics, titanium has long been of interest for many researchers. In this article within the Weakest Bound Electron Potential Model (WBEPM) theory, comprehensive set of calculations for transition probabilities and oscillator strengths for Ti III and Ti IV are performed. Many of our results had no previous experimental or theoretical values, so these predictive results could be of some value to the workers in this field. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

A simple line shape technique for electron number density diagnostics of helium and helium-seeded plasmas

The results of an experimental study of the He I 447.1 nm line and its forbidden component at high electron number density are presented and compared with profiles calculated using computer simulation method. Michelson interferometer at 632.8 nm was used to measure plasma electron number density in the range (1–7) × 10²³ m^− 3 while electron temperatures for the same experimental conditions in the range of 25 000 K to 35 000 K were determined using several spectroscopic techniques. The agreement of experimental overall line shape with computer simulation results is within 10% of what is well within theoretical and experimental uncertainty. This favorable comparison enabled the development of a simple approximate formula for the evaluation of electron number density from the measurement of wavelength separation between peaks of allowed and forbidden lines. This technique of plasma diagnostics is not sensitive to the presence of self-absorption of strong He I allowed line. The derivation of approximate formula with estimated accuracy of 15% was followed by detailed comparison with other experimental and theoretical data.     

Development of a stabilized low temperature infrared absorption cell for use in low temperature and collisional cooling experiments

We have constructed a stabilized low temperature infrared absorption cell cooled by an open cycle refrigerator, which can run with liquid nitrogen from 250 to 80K or with liquid helium from 80K to a few kelvin. Several CO infrared spectra were recorded at low temperature using a tunable diode laser spectrometer. These spectra were analyzed taking into account the detailed effects of collisions on the line profile when the pressure increases. We also recorded spectra at very low pressure to accurately model the diode laser emission. Spectra of the R(2) line in the fundamental band of 13CO cooled by collisions with helium buffer gas at 10.5K and at pressures near 1 Torr have been recorded. The He-pressure broadening parameter (gamma(0) = 0.3 cm(-1) atm(-1)) has been derived from the simultaneous analysis of four spectra at different pressures.     

A comparison of electron ionization mass spectra obtained at 70 eV,low electron energies,and with cold EI and their NIST library identification probabilities

Electron ionization (EI) mass spectra of 46 compounds from several different compound classes were measured. Their molecular ion abundances were compared as obtained with 70‐eV EI, with low eV EI (such as 14 eV), and with EI mass spectra of vibrationally cold molecules in supersonic molecular beams (Cold EI). We further compared these mass spectra in their National Institute of Standards and Technology (NIST) library identification probabilities. We found that

1. Low eV EI is not a soft ionization method, and it has little or no influence on the molecular ion relative abundances for large molecules and those with weak or no molecular ions.
2. Low eV EI for compounds with abundant or dominant molecular ions in their 70 eV mass spectra results in the reduction of low mass fragment ions abundances thereby reducing their NIST library identification probabilities thus rarely justifies its use in real‐world applications.
3. Cold EI significantly enhances the relative abundance of the molecular ions particularly for large compounds; yet, it retains the low mass fragment ions; hence, Cold EI mass spectra can be effectively identified by the NIST library.
4. Different standard EI ion sources provide different 70 eV EI mass spectra. Among the Agilent technologies ion sources, the “Extractor” exhibits relatively abundant molecular ions compared with the “Inert” ion source, while the “High efficiency source” (HES) provides mass spectra with depleted molecular ions compared with the “Inert” ion source or NIST library mass spectra.

These conclusions are demonstrated and supported by experimental data in nine figures and two tables.     

Influence of the Excited States of Atomic Nitrogen N(<Superscript>2</Superscript>D) and N(<Superscript>2</Superscript>P) on the Transport Properties of Nitrogen. Part I: Atomic Nitrogen Properties

In this paper, calculated values of the viscosity and thermal conductivity of atomic nitrogen, taking into account three species (the ground and two excited states), are presented. The calculations, which assume that the temperature dependent probability of occupation of the states is given by the Boltzmann factor, are performed for atmospheric-pressure in the temperature range from 1,000 to 20,000 K. Six collision integrals are used in calculating the transport coefficients and we have introduced new averaged collision integrals where the weight associated at each interacting species pair is the probable collision frequency. The influence of the collision integral values and energy transfer between two different species is studied. These results are compared which those of published theoretical studies.     

Spectroscopic flame temperature measurements and their physical significance—V. Experimental determination of relative transition probabilities for 43 Fe I lines in the 3450–3950 Å wavelength region

Relative transition probabilities, as measured by the atomic emission spectroscopic technique, have been redetermined for 43 lines of Fe I under experimental conditions that in principle should yield accurate values. The Fe free-atoms are formed in a high temperature environment that has been shown to be isothermal and optically thin under the experimental conditions employed. The temperature of the iron atoms was measured by the reversal method, and the emission measurements were made so that the values obtained were strictly proportional to the line radiances. The high degree of correlation of the values reported with those obtained by the hook method is indicative of the overall reliability of these sets of data.     

Method for simultaneous luminescence sensing of two species using optical probes of different decay time, and its application to an enzymatic reaction at varying temperature

Chemical sensing, imaging and microscopy based on the use of fluorescent probes has so far been limited almost exclusively to the detection of a single parameter at a time. We present a scheme that can overcome this limitation by enabling optical sensing of two parameter simultaneously and even at identical excitation and emission wavelengths of two probes provided (a) their decay times are different enough to enable two time windows to be recorded, and (b) the emission of the shorter-lived probe decays to below the detectable limit while that of the other still can be measured. We refer to this new scheme as the dual lifetime determination (DLD) method and show that it can be widely varied by appropriate choice of probes and experimental settings. DLD is demonstrated to work by sensing oxygen and temperature independently from each other by making use of two probes, one for oxygen (a platinum porphyrin dissolved in polystyrene), and one for temperature [a europium complex dissolved in poly(vinyl methylketone)]. DLD was applied to monitor the consumption of oxygen in the glucose oxidase-catalyzed oxidation of glucose at varying temperatures. The scheme is expected to have further applications in cellular assays and biophysical imaging. Figure Principle behind the dual lifetime determination (DLD) method     

Nephelometry and turbidimetry with paired emitter detector diodes and their application for determination of total urinary protein

Two miniature and compact optoelectronic devices fabricated by means of integration of light emitting diodes have been developed for turbidimetric and nephelometric measurements. These devices are operating according to paired-emitter-detector-diode (PEDD) principle. The detectors have been characterized using bovine serum albumin and Exton protein assay as a model analyte and a model analytical method, respectively. The developed detectors have been adapted for measurements under conditions of flow injection analysis (FIA). Under optimized conditions the turbidimetric flow system offers the range of linear response up to 400 mg L⁻¹ with the detection limit at 20 mg L⁻¹. The linear range and detection limit found for optimized nephelometric FIA system are 15–500 mg L⁻¹ and 8 mg L⁻¹, respectively. The PEDD-based FIA systems with the detector operating according to both modes of measurements have been successfully applied for urinalysis offering total protein determination at physiological and pathological levels with high throughput (over 60 injections per hour).     

Estimation of the emission temperature of an electrodeless discharge lamp and determination of the oscillator strength for the I(P3/2) 183.038 nm resonance transition

The 183.038 nm resonance absorption transition of I(²P_3/2) has been studied using a flash photolysis set-up for gas-phase chemistry and a radio frequency powered electrodeless discharge lamp filled with iodine. The dependence of self-absorption and self-reversal on iodine partial pressure in the discharge volume was measured. The optimum iodine partial pressure, with self-absorption minimized and acceptable intensity, is determined to be approximately 2.5×10⁻³ mbar. A method is described to estimate the temperature of the emitting atoms using direct measurements of relative absorption at different absorber concentrations. This yields an emission temperature of 923±50 K. Using this temperature, the oscillator strength for the I(²P_3/2) transition at 183.038 nm is determined to be f=(3.87±0.57)×10⁻³, corresponding to an absorption cross-section at the center of the line of σ=(5.42±0.8)×10⁻¹⁴ cm² atom⁻¹_. This shows a difference from one of two earlier measurements, but is close to the other. The remaining difference from the latter measurement is probably due to tendencies of opposite biases inherent to the experiments.     

制备方法对MnOx-CeO2催化剂理化性质及低温NH3-SCR脱硝性能的影响

随着人们环保意识的增强,氮氧化物(NOx)的危害引起广泛关注.NOx作为首要的大气污染物之一,主要来源于以燃煤电厂为代表的固定源和以机动车为代表的移动源.它不仅能够导致酸雨和光化学烟雾,而且还是PM2.5的重要前驱体,严重危害人类健康和植物生长.因此,NOx的治理迫在眉睫.研究表明,氨选择性催化还原(NH3-SCR)技术是控制固定源NOx排放最经济有效的方法.商业化V2O5-WO3/TiO2和V2O5-MoO3/TiO2脱硝催化剂的最佳工作温度窗口为300?400℃.因此,NH3-SCR脱硝设施通常安装在除尘器和脱硫装置之前以满足最佳工作温度需要.然而,在这种情况下,脱硝催化剂容易因烟气中的飞灰和含硫化合物堵塞、中毒而失活.此外,对于老电厂增加脱硝设施的改造工程,在除尘器和脱硫装置之前没有足够的空间用于安装脱硝设施.因此,开发环境友好型低温NH3-SCR脱硝催化剂显得尤为重要,因为它可以直接安装在除尘器和脱硫装置之后,从而有效减缓脱硝催化剂失活,有利于改造工程的施工.研究表明,锰基催化剂由于其优异的氧化还原性能和氧迁移能力有利于氧化NO为NO2,促进反应沿着"快速NH3-SCR"途径进行,从而表现出优异的低温脱硝性能.然而,其N2选择性、抗水性能和工作温度窗口还有待改善.因此,开发既具有高催化活性又具有宽工作温度窗口、优异抗水性能以及理想N2选择性的低温脱硝催化剂仍是一个富有挑战性的课题.二氧化铈(CeO2)由于具有优异的氧化还原性能、良好的储/释氧能力、丰富的氧空位以及Ce4+/Ce3+的轻易切换而被广泛用于NH3-SCR反应.因此,将锰氧化物(MnOx)与CeO2相结合而制备的MnOx-CeO2催化剂可能会表现出优异的低温脱硝性能.而催化剂的理化性质和催化性能还强烈地依赖于其制备方法.因此,本文采用不同方法(机械混合法、浸渍法、水热法、共沉淀法以及溶胶-凝胶法)制备了一系列MnOx-CeO2催化剂用于低温NH3-SCR反应,并运用X射线衍射(XRD)、拉曼光谱(Raman)、氮气物理吸附、氢气程序升温还原(H2-TPR)、氨气程序升温脱附(NH3-TPD)、X射线光电子能谱(XPS)以及原位漫反射红外光谱(in situ DRIFTS)等表征技术对催化剂进行了系统分析.重点考察了制备方法对MnOx-CeO2催化剂理化性质和催化性能的影响.结果表明,低温脱硝性能有如下顺序:水热法>溶胶-凝胶法>共沉淀法>浸渍法>机械混合法.这与催化剂表面Ce3+和Mn4+含量、氧空位和表面吸附氧物种浓度以及酸量和酸强度顺序一致.这些性质都与MnOx和CeO2之间的电子相互作用(即Mn3++Ce4+?Mn4++Ce3+)密切相关.特别是水热法制备的MnOx-CeO2催化剂(MnCe-HTM)由于Mnn+掺入到CeO2晶格形成铈基固溶体(含Mn-O-Ce结构)以及水热过程中的高温高压环境加强了MnOx和CeO2之间的电子相互作用,从而表现出优异的理化性质、最佳的低温脱硝性能以及理想的抗水性能.     

The use of a gold-containing membrane for ion-sensitive electrodes and their application in analysing systems. I

Summary Pellets of a material, resulting from the precipitation of silver salts (AgCl, AgBr, AgI and Ag₂S) onto finely divided gold (particle size less than 3 m) showed a selective ion-sensitive behaviour for halogens, silver and sulphide, resp. Silver iodide on gold turned out to be sensitive for cyanide as well.Electrodes with this type of membrane combined a low redox sensitivity with good mechanical strength and chemical resistance and with a low membrane impedance (1–500 kOhm mm^–1 as a maximum). Settling times vary in the range of 0.1–10 sec. A linear Nernstian response was shown in the ranges 10^–1×10^–5 M (chloride), 10^–1 –10^–6 M (bromide, iodide, cyanide) and 10^–1–10^–7 M (silver, sulphide). In order to obtain good cleaning facilities for heavy duty applications (e. g. measurements in slurries) the membrane pellet was mounted in the electrode body in a way that its cylindrical side contacted the solution to be measured or monitored.

---

Verwendung einer goldhaltigen Membran für ionensensitive Elektroden und ihre Anwendung in analytischen Systemen. IHerstellung und Charakteristik ionensensitiver Elektroden

Zusammenfassung Tabletten eines Materials, das durch Fällung von Silbersalzen (AgCl, AgBr, AgJ und Ag₂S) auf fein-pulverisiertem Gold (Teilchengröße weniger als 3 m) entstand, wurden zur Fertigung selektiver ionen-sensitiver Elektroden für Halogene, Silber und Sulfid eingesetzt. Silberjodid auf Gold war auch für Cyanid empfindlich. Diese Elektroden vereinigen eine niedrige Redox-Empfindlichkeit mit einer guten mechanischen und chemischen Stabilität sowie einer niedrigen Elektrodenimpedanz (Höchstwert: 1–500 kOhm mm^–1). Der Signalwert bildet sich in 0,1–10 sec. Das Elektrodensignal ist proportional der Ionenaktivität gemäß dem Nernstschen Gesetz im Bereich von 10^–1–3·10^–5 M (Chlorid), 10^–1–10^–6 M (Bromid, Jodid, Cyanid) und 10^–1–10^–7 M (Silber, Sulfid). Die Tablette ist im Elektrodengehäuse so montiert, daß nur die cylindrische Außenseite von der zu messenden Flüssigkeit berührt wird. Die Reinigung der Elektrode im anspruchsvollen Dauerbetrieb (z. B. kontinuierliche Messungen in Festkörper enthaltenden Abwässern) wird durch diese Anordnung erheblich vereinfacht.

     

Preparation of polythiophene/WO_3 organic-inorganic hybrids and their gas sensing properties for NO_2 detection at low temperature

Polythiophene/WO3(PTP/WO3)organic-inorganic hybrids were synthesized by an in situ chemical oxidative polymerization method,and char- acterized by X-ray diffraction(XRD),transmission electron microscopy(TEM)and thermo-gravimetric analysis(TGA).The Polythiophene/ WO3 hybrids have higher thermal stability than pure polythiophene,which is beneficial to potential application as chemical sensors.Gas sensing measurements demonstrate that the gas sensor based on the Polythiophene/WO3 hybrids has high response and good selectivity for de- tecting NO2 of ppm level at low temperature.Both the operating temperature and PTP contents have an influence on the response of PTP/WO3 hybrids to NO2.The 10 wt%PTP/WO3 hybrid showed the highest response at low operating temperature of 70-C.It is expected that the PTP/WO3 hybrids can be potentially used as gas sensor material for detecting the low concentration of NO2 at low temperature.     

Development of new glass composite membranes and their properties for low temperature H2/O2 fuel cells.

A new glass electrolyte formed by constant amounts of titanium oxide (TiO2) and various amount of phosphotungstic acid (PWA) doped P2O5-SiO2 is prepared using the sol-gel process. The structural formation is confirmed by Fourier infrared spectroscopy (FTIR) and from thermogravimetric and differential thermal analysis (TG/DTA) measurements, the glasses display good thermal stability. Further characterisation is undertaken by N2 adsorption/desorption measurements, proton conductivity and hydrogen permeability analyses and a H2/O2 fuel cell test is also performed. The glass materials with large pores and specific surface area are suitable for use as the electrolyte in H2/O2 fuel cells. The effect of TiO2 processing with constant amount of PWA in phosphosilicate glasses, is investigated and discussed. The hydrogen permeability is 1.57x10(-11) mol cm(-1) s(-1) Pa(-1) at 110 degrees C for 0.8 mm thick glass; a power density of 46.3 mW cm(-2) at 125 mA cm(-2) and a current density of 175 mA cm(-2) is obtained (T=28 degrees C, relative humidity).