Simulation of the Radiation-Chemical Conversion of Mercury Vapor in Power-Plant Flue Gases in the Presence of Hydrogen Chloride

The effect of HCl on the conversion of mercury vapor in the electron-beam treatment of power-plant flue gases for removing nitrogen and sulfur oxides was investigated. A kinetic scheme for the process consists of the liquid-phase oxidation of Hg by O₃molecules and OH radicals followed by the adsorption of liquid-phase oxidation products on soot particles, which are removed from the gas flow using filters. It was found that almost complete removal of mercury vapor is attained at typical radiation doses and process temperatures at soot concentrations higher than 100 g/m³(STP). At a soot concentration lower than 100 g/m³(STP) and an HCl concentration higher than 50 mg/m³(STP) in the gas phase, biologically active HgCl₂is formed in considerable amounts.     

The behavior of molecules in microwave-induced plasmas studied by optical emission spectroscopy. 1. Plasmas at atmospheric pressure

The behavior of molecules in different atmospheric microwave-induced plasmas (MIPs) has been studied by means of optical emission spectroscopy. This is in order to obtain more insight into molecular processes in plasmas and to investigate the feasibility of emission spectroscopy for the analysis of molecular compounds in gases, e.g. flue gases. Various molecular species (i.e. N₂, CO₂, H₂O, SF₆ and SO₂) have been introduced into discharges in argon or in molecular gases such as carbon dioxide or nitrogen. The plasmas were created and sustained by a guide-surfatron or a torch in the power range of 150 W to 2 kW. Only nitrogen sometimes yielded observable emission from the non-dissociated molecule (first and second positive system). Using other molecular gases, only dissociation and association products were observed (i.e. atomic species and diatomic molecules such as CN, C₂, CO, OH, NH and N₂⁺). The intensities of these products have been studied as a function of the concentration of introduced molecules, the position in the plasma and the composition of the plasma environment. Since in most cases the same diatomic association products are seen, observed associated molecules can only to some extend be related to the molecules originally present in the plasma gas. Therefore, it will be difficult to use atmospheric microwave discharges for the analysis of gas mixtures under the experimental conditions studied.     

Time-based on-line preconcentration cold vapour generation procedure for ultra-trace mercury determination with inductively coupled plasma atomic emission spectrometry

A time-based sequential dispensing on-line column preconcentration procedure for mercury determination at trace levels by cold vapour generation inductively coupled plasma atomic emission spectrometry (CV-ICP-AES), by means of a unified module of a preconcentration column and a gas–liquid separator (PCGLS) is described. The complex of mercury formed on-line with ammonium pyrrolidine dithiocarbamate (APDC) is retained on the surface of the hydrophobic poly(tetrafluoroethylene) (PTFE) turnings, which are packed into the lower compartment of the PCGLS. Subsequently, mercury vapour is generated directly on the PTFE turnings by reductant SnCl₂ and separated from the liquid mixture via the PCGLS by argon purge gas. The outlet of the PCGLS is connected directly to the torch adapter of the plasma without the normal spray chamber and nebulizer. With 60-s preconcentration time and 12.0 mL min^–1 sample flow rate, the sampling frequency is 30 h^–1. The calibration curve is linear over the concentration range 0.02–5.0 g L^–1, the detection limit (c_L) is 0.01 g L^–1 and the relative standard deviation (s_r) is 3.1% at the 1.0 g L^–1 level. The proposed method was evaluated by analysis of BCR CRM 278 (Mytilus Edulis) reference material and applied to the determination of total mercury in digested urine, blood and hair samples.     

The Chemistry of Methane Remediation by a Non‐thermal Atmospheric Pressure Plasma

The destruction of methane by a nonthermal plasma in atmospheric pressure gas streams of nitrogen with variable amounts of added oxygen has been investigated. The identities and concentrations of the endproducts are determined by online FTIR spectroscopy and the plasma chemistry is interpreted using kinetic modelling. For a deposited energy of 118 kJ m^–3, the destruction is 12% in nitrogen decreasing monotonically to 5% in air. The major endproducts are HCN and NH₃ in nitrogen and CO, CO₂, N₂O, NO and NO₂ for gas streams containing oxygen. The chemistry in pure nitrogen is predominantly due to reactions of electronicallyexcited nitrogen atoms, N(²D). The addition of oxygen converts the excited state nitrogen into nitrogen oxides reducing the methane destruction which then arises by O and OH reactions yielding CO and, to a lesser extent, CO₂. The modelling correctly predicts the magnitude of the methane destruction as a function of added oxygen and the concentrations of the endproducts for processing in both nitrogen and air.     

Spectrophotometric determination of mercury with 5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine by flow injection analysis

5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine (m-Cl-TPPS₄) was synthesized and used for the Spectrophotometric determination of mercury by flow injection analysis. A pseudo-first-order reaction kinetic mechanism was proposed with a rate constant of 0.8 min^–1 for Hg(II) withm-Cl-TPPS₄ in the presence of 8-hydroxyquinoline in a medium of 1.0M acetic acid and sodium acetate buffer solution (pH 6.22). In the optimum conditions of reaction temperature (85 ° C), stopped-flow time (60 s) and sampling volume (100 l), the method's relative standard deviation was 0.82% (n = 12) at 5.0 g ml^–1 mercury, with a linear range of 0–12.0 g ml^–1 and an analytical frequency of 60h^–1. The detection limit (3) was 0.025 g ml^–1. Interference studies showed that most metal ions co-existing with Hg²⁺ could be tolerated at 100-fold excess levels, but Zn²⁺, Cu²⁺ and Mn²⁺ needed to be masked. The method has been applied to the analysis of water samples with satisfactory results.     

A microwave induced plasma system for the maintenance of moderate power plasmas of helium,argon, nitrogen and air

A microwave induced plasma system capable of maintaining stable plasmas of each of the gases helium, argon, nitrogen and air is presented. The system is capable of operation at powers of up to 500 W. The TM₀₁₀ cavity design is similar to that previously described in the literature with some modifications. A demountable torch facilitates centering of diffuse plasmas of helium, nitrogen and air by providing 6 flows directed tangentially within the quartz tube. This torch was not useful for argon plasmas. Toroidal argon plasmas were maintained with a threaded quartz tube arrangement. The heat generated by these plasmas was dissipated by an outer sheath of coolant air. Details of the design and preliminary characterization of each plasma system is presented.     

Determination of the Nitrogen Atom Density in the Afterglow of a Nitrogen and Helium,Nonequilibrium, Atmospheric Pressure Plasma

Three methods have been examined for evaluating the concentration of nitrogen atoms in the afterglow of a nonequilibrium, helium-stabilized, atmospheric pressure plasma. These are nitric oxide titration, absolute emission intensity of N₂(B ³_g) and temporal decay of the N₂(B ³_g) emission. To employ the second method, the rate constants for the recombination of N atoms into N₂(B ³_g), at different vibrational levels of the B state, were determined. The third newly developed method has three advantages over the other two techniques: (1) it can predict the N-atom density for the entire afterglow, (2) it does not require calibration of the N₂(B ³_g) emission intensity, and (3) it does not disturb the gas flow. According to these measurements, the atmospheric pressure plasma produced a high density of nitrogen atoms, exceeding 4.0×10¹⁵ cm^–3 at the edge of the discharge for 10 Torr N₂ in 745 Torr He at 375 K and 15.5 W/cm³.     

The CO2 Reforming of Natural Gas in a Pulsed Corona Discharge Reactor

The conversion of CO ₂ and (CH ₄+CO ₂ ) mixtures to CO, at room temperature and atmospheric pressure conditions, in pulsed corona discharges, was investigated. Conversion of pure CO ₂ was 16.8% at 10 cm ³ -min ^–1 flow rate, which corresponds to 75 mol-min ^–1 rate of conversion. The CO ₂ conversion was improved to 38% (85 mol-min ^–1 by feeding the reactor with CH ₄+CO ₂ gas mixture (1:1 ratio), simultaneously with CH ₄ conversion of 46% (102.7 mol-min ^–1 ) at 10 cm ³ -min ^–1 flow rate of feed gases and 9 W power conditions. Rate of CO production is increased from 110 to 180 mol-min ^–1 with the variation of feed gas (CH ₄+CO ₂ mixture, 1:1 ratio) flow rate from 10 to 40 cm ³ -min ^–1 at 9W, which corresponds to energy efficiency of 2.5 to 4.1%. Highest energy yield of 25 g/kWh for CH ₄ conversion, 29 g/kWh for CO ₂ conversion, and 33 g/kWh for CO production were achieved.     

Hydrodynamics and heat transfer in a plasma spouted bed reactor

The literature reveals very little intformation about plasma spouted bed hydrodynamics. Spouting of corindon particles with diameters ranging from 0.4 to 3.36 mm with argon plasma was conducted in a 90-mm-diameter column in the temperature range 300–1300°C. It was found that the maximum spoutable height (H_m) decreases with increasing particle diameter and decreasing mean bed temperature. A relation between the inlet plasma velocity and H_m is proposed. Concerning heat transport phenomena in the annulus, measurements and calculations indicate a large axial diffusivity but a poor radial mixing. Typical values of D_z and D_r are proposed on the basis of an identification procedure.Notation Ar Archimede number - Ar d ³ p (p — f) _f g ² - C_p specific heat - d_p particle diameter - d_e core diameter (or spout diameter) - D_i fluid inlet orifice diameter - D_e column diameter - D_r and D_z radial and axial diffusivity, respectively - g acceleration due to gravity - H packed static bed height - H_b bed height - H_m maximum spoutable bed height - P power     

Diagnostics and decomposition mechanism in radio-frequency discharges of fluorocarbons utilized for plasma etching or polymerization

Optical emission (180–800 nm) and mass spectroscopy have been used to study the CF₄, CF₄+O₂, C₂F₆, C₂F₆+H₂, CF₃Cl, and C₂F₄ decomposition in radio-frequency discharges. The analysis of the stable and unstable discharge products has allowed the suggestion of decomposition channels for the various gases and to classify the fluorinated gases according to their predominant etching or polymerizing characteristics on the basis of the active species present in the plasma. A new broad emission continuum centered at =290 nm (FWHM=66 nm) has also been identified and it has been tentatively assigned to CF⁺ ₂.     

Secondary ion emission of selected transition metals under nitrogen oxides

The emission of various positive secondary ions has been investigated for polycrystalline targets of Ti, V, Cr, Nb, Ta, Co, Ni, Cu, Pd and Pt, which were bombarded by Ar⁺ ions under dynamic SIMS (DSIMS) conditions in the presence of the gaseous nitrogen oxides N₂O, NO and NO₂ at fixed pressure and under residual gas. Besides ions of the Me⁺ type several fragmentary ions (e.g. N⁺, O⁺, NO⁺, MeN⁺ and MeO⁺) and also cluster ions Me _x O _y ⁺ (x 2, 0 y 2) were detected. Signals of a more molecular type with respect to the reactant gas, e.g. MeNO⁺, were only found for Co, Ni, Cu, Pd and Pt. From this, one may infer that for the other targets the nitrogen oxides will exist preferentially in a dissociatively adsorbed state at the metal surface. Several aspects of secondary ion emission can be explained assuming a different degree of oxidation for the metals under the influence of reactant gas.Part of the dissertation     

Determination of gaseous nitrogen in gas mixtures using low pressure microwave induced plasma emission spectrometry

A microwave induced plasma emission spectrometer operating at low energy (30 W) and low plasma gas pressure (2.510^-2 Pa) has been used for the quantitative measurement of molecular nitrogen in natural gases. The samples have been introduced into the plasma using a counterflow principle to produce emission spectra of diatomic molecular fragments in low excitation states (advantage: minimized interferences). The N₂ concentration has been determined by measuring the intensity of the N₂-line at 337.13 nm (C³_u-B³_g-system; (0,0)vibrational transition) and of the NH-line at 336.03 nm (A³_i-X^2--system; (0,0)-vibrational transition). A linear correlation between concentration and signal intensities has been obtained in the range of 0.00% to 14.24% (v/v). The method possesses a detection limit of 0.01 ppm (v/v) for the determination of N₂, and a reproducibility of 1.33% (RSD).     

Total organochloride and organobromide determinations in aqueous samples by microwave induced plasma-optical emission spectrometry

The element specific detection of the adsorbable organic halogen (AOX) parameter in waters has been investigated by adsorption of the halogenated analytes on activated carbon, incineration to yield carbon dioxide and hydrogen halide, trapping of the halide on a 0.01 M sodium hydroxide solution and online introduction of the halogen formed by continuous oxidation into a microwave induced plasma (MIP). Detection has been carried out by optical emission spectrometry (OES) in the visible spectral region.The performance of three microwave cavities for MIP-OES running at atmospheric pressure (Beenakker, Surfatron and Microwave Plasma Torch) as well as a reduced pressure Surfatron were investigated for halide analysis. The Surfatron device operated at 30 torr provided the best detection limits: 3ng.ml^–1 for chloride and 8 ng.ml^–1 for bromide; consequently, it was the plasma chosen for AOX analysis.On-line continuous oxidation of organic compounds using KMnO₄ in H₂SO₄ medium and in batch catalytic dechlorination with a Fe/Pd system were investigated as alternatives to the incineration method for the destruction of organic halogens to render inorganic halides are also investigated.Finally, the optimized method has been applied successfully to the determination of organochloride and organobromide in spiked river waters, being the recoveries in the interval 92–105%.     

Formation and Characterization of Large (Ar) n , (N2) n , and Mixed (Ar) n (N2) m van der Waals Clusters Produced by Supersonic Expansion

This paper reports the formation and characterization of large (Ar) _n , (N₂) _n , and mixed binary (Ar) _n (N₂) _m van der Waals clusters produced at room temperature in the process of supersonic expansion. The average cluster size is determined by the buffer gas induced beam-broadening technique. For both Ar and N₂ clusters, power variations of the average cluster size with the gas stagnation pressure P ₀ give size scaling as . The average cluster sizes of argon vary from 2950 to more than 30900 atoms per cluster with the argon gas stagnation pressures ranging from 4 to 14 bars, and of nitrogen vary from 600 to more than 10400 molecules per cluster with the nitrogen gas stagnation pressures ranging from 8 to 38 bars. The mixed binary (Ar) _n (N₂) _m cluster is produced by supersonic expansion of an Ar–N₂ mixture. The large mixed binary (Ar) _n (N₂) _m clusters with the average sizes n + m between 1000 and 16000 are obtained. In coexpansion of Ar–N₂ mixture, we find that the argon concentration becomes higher in the beam than before the expansion. This finding is discussed and may be helpful for further insight into the phenomenon of clustering.     

Gas permeability of block copolymers of styrene and butadiene

The permeability of styrene-butadiene block copolymer foils with different composition prepared by casting and pressing has been investigated for the gases Ar, CO₂, and CH₄ at pressure difference of 400 mbar and at the temperature range 298 T [K] 333.The permeation process can be described by the solution diffusion mechanism. The diffusion coefficients decrease in the sequence of the gases Ar, CO₂, and CH₄ and the solubility coefficients increase in the sequence Ar, CH₄, CO₂.The dependence of the permeability on the composition of the block copolymer can be interpreted by the help of percolation theory and the effective medium theory. It follows the critical volume fraction of the percolation of the transport phase _PB ^c (= 0,23) and the coordination numberz (= 4) giving an information concerning the multiphase structure of the block copolymer.Presented in part at the 33^rd Annual Meeting of the Colloid-Gesellschaft, Graz, Austria, September 14–16, 1987.     

Study on the Melting Process of Nitrocellulose by Thermal Analysis Method

The melting process of NC is studied by using modulated differential scanning calorimetry (MDSC) technique, the microscope carrier method for measuring the melting point and the simultaneous device of the solid reaction cell in situ/RSFT-IR. The results show that the endothermic process in the MDSC curve is reversible. It is caused by the phase change from solid to liquid of the mixture of initial NC, decomposition partly into condensed phase products. The values of the melting point, melting enthalpy (H_m), melting entropy (S_m), the enthalpy of decomposition (H_dec) and the heat-temperature quotient (S_dec) obtained by the MDSC curve of NC at a heating rate of 10 K min^–1 are 476.84 K, 205.6 J g^–1, 0.4312 J g^–1 K^–1, –2475.0 J g^–1 and –5.242 Jg^–1K^–1, respectively. The MDSC results of NC with different nitrogen contents show that with increasing the nitrogen content in NC, the absolute values of H_m, S_m, H_dec and S_dec increase.This revised version was published online in November 2005 with corrections to the Cover Date.     

Analysis of organobromine compounds and HBr in motor car exhaust gases with a GC/microwave plasma system

Summary In this investigation an analytical procedure for the determination of different organobromine compounds in motor car exhaust gases is developed in order to obtain a total balance of these compounds in this type of exhaust gas. For this purpose, adsorption sampling on Tenax GC combined with thermal desorption and a fast cold trap injection into the GC column system is used. A special capillary cold trap/thermodesorption system for a fast injection within 1 s is developed. The chromatographically separated fractions are identified by their retention times and elementspecific detection with a microwave plasma detector. Methyl bromide, 1,2-dibromoethane, and vinyl bromide are analysed in exhaust gases in cases where the gasoline contains 1,2-dibromoethane as an additive (leaded gasoline). The analysed bromine contents, which correspond to these organobromine compounds, are in the range of 90–190 g/m³, 15–85 g/m³, and 5–20 g/m³, respectively. The portion of the organobromine compounds is 22–44% of the total bromine which is emitted by the exhaust gases. The other portion contains mainly inorganic particulate bromide, which can be separated by filters. The concentration of the organobromine compounds decreases with increasing motor temperature. After conversion into 2-bromocyclohexanol and after gas chromatographic separation HBr is detected to be 5.8 g bromine per m³ exhaust gas, which corresponds to approximately 1% of the total bromine emission. 1,2-Dichloroethane is analysed in the range of 5–35 g Cl/m³, whereas the concentration of tetraalkyl lead in the exhaust gases is less than the detection limit of 6.7 g Pb/m³. The average bromine/lead ratio found in the filterable portion of the exhaust gases is 0.30 (by weight); the same ratio calculated for total bromine emission including the organobromine compounds is 0.47. Compared with the bromine/ lead ratio in gasoline of 0.39 this means that at least 17% of the total lead in the gasoline is not directly emitted with the motor car exhaust gases.

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Analyse von bromorganischen Verbindungen und HBr in Autoabgasen mit einem GC/Mikrowellenplasma-System

     

Bestimmung von Argon neben Stickstoff und Sauerstoff in pulvermetallurgisch hergestellten Werkstoffen mit einem modifizierten Tr?gergas-Hei?extraktionsger?t

Summary The modification of a commercial carrier-gas fusion instrument for the simultaneous determination of argon is described. In order to separate argon from nitrogen, a gas-chromatographic column with molecular sieve was incorporated between the absorption traps for H₂O and CO₂ and the thermal conductivity detector. A computing integrator was used for the evaluation of the detector signals. The calibration was done by introduction of defined volumes of dry air into the carrier-gas line. The conditions for the liberation of argon from samples of ODS-alloys and the separation from the other extracted gases were optimized. Results of analysis of powders and compact samples were compared with the results obtained by means of a vacuum-fusion instrument. In the concentration range 25 to 50 g/g argon the relative standard deviations were 1.5 to 3% (six determinations). With powders of 3 to 5 g/g relative standard deviations of about 8% were achieved. The limit of detection for 1 g samples was found to be ca. 0.5 g/g.     

Speciation of volatile mercury species present in digester and deposit gases

Volatile mercury compounds have been speciated in gases evolved from fermentation of sewage sludge as well as municipal waste. The species were trapped by sequential sampling, using a noble‐metal trap in series with an activated‐carbon trap. Thermally desorbed Hg⁰ and (CH₃)₂Hg were separated by GC at 70 °C and detected by cold vapour atomic fluorescence spectroscopy after thermal reduction. The amounts of mercury detected in the sewage gas correspond to concentrations in the range 50–110 ng m⁻³ for both species whereas the deposit gases were found to contain only elemental mercury. Monomethylmercury species could not be positively identified in any of the gas samples. Copyright © 1999 John Wiley & Sons, Ltd.     

Transfer chemical potentials for cobalt(III) and chromium(III) complexes from water into aqueous methanol; their relevance to reactivity trends for cobalt(III)-chloride aquation

Summary We report solubilities of a number of cobalt(III) and chromium(III) complex salts in methanol-water mixtures. From these, and published solubilities of salts of other complexes of these metals, we have calculated transfer chemical potentials from water into aqueous methanol for a variety of cationic and anionic complexes of cobalt(III) and chromium(III), using the assumption _m(Ph₄As⁺) + _m(BPh ₄ ^– ). The established trends are discussed in terms of electrostatic factors and of the hydrophilicity or hydrophobicity of the ligands present. The effects of single ion assumptions on conclusions of initial state-transition state analyses of solvent effects on reactivity are assessed with particular reference to aquation of thetrans-[Co(en)₂Cl₂]⁺ andtrans-[Co(py)₄Cl₂]⁺ cations.On leave from the Faculty of Science, Sohag, Egypt.