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1.
Some important analytes in ICP-MS are interfered by plasma argon or argon species, such as ArO+ and 56Fe, 40Ar and K or Ca. One approach to overcome this interference is the use of reduced forward power and a metal shield inserted between torch and load coil. These so called cold plasma conditions reduce the background caused by argon species and the formerly interfered analytes can be easily detected in the ng/g-range. Other elements in the lower mass region also profit from these conditions even when they are not interfered in normal plasma mode. The limits of detection are improved due to reduced background noise level and enhanced ion transmission. On the other hand, the reduced power fed to the plasma lowers the analytical performance and makes it susceptible to matrix effects. Elements of higher mass generally show higher detection limits compared to normal plasma mode.  相似文献   

2.
Some important analytes in ICP-MS are interfered by plasma argon or argon species, such as ArO+ and 56Fe, 40Ar and K or Ca. One approach to overcome this interference is the use of reduced forward power and a metal shield inserted between torch and load coil. These so called cold plasma conditions reduce the background caused by argon species and the formerly interfered analytes can be easily detected in the ng/g-range. Other elements in the lower mass region also profit from these conditions even when they are not interfered in normal plasma mode. The limits of detection are improved due to reduced background noise level and enhanced ion transmission. On the other hand, the reduced power fed to the plasma lowers the analytical performance and makes it susceptible to matrix effects. Elements of higher mass generally show higher detection limits compared to normal plasma mode. Received: 30 November 1998 / Revised: 4 February 1999 / Accepted: 8 February 1999  相似文献   

3.
Electronic excitation (Texc) and rotational (Trot) temperatures were determined for a parallel plate capacitively coupled rf plasma operating at atmospheric pressure. Texc was calculated from the slope of the Boltzmann plot using Fe and He as the thermometric species and Pb excitation temperature was calculated using the two line method. Over a power range from 100 W to 250 W, excitation temperatures are 3255–3900 K for He, 3540–4500 K for Pb, and 4300–4890 K for Fe. The rotational temperature was measured using both OH and N2+ molecular spectra and the values are in the range of 828–911 K and 845–956 K respectively over a power range of 75–275 W. Signal-to-noise ratios, signal-to-background ratios, and absolute detection limit for lead (0.33 ng) and silver (24 pg) are also reported.  相似文献   

4.
Addition of nitrogen to an argon ICP in LA-ICP-MS has been found to increase sensitivity and consequently reduce oxide to metal ratios (MO+/M+) for the reference elements Ce and Th. Addition of about 1% v/v N2 to the coolant flow increased sensitivity, reducing MO+/M+ ratios from about 0.6% to about 0.2%. Addition of about 12% N2 to the cell flow had a similar effect, being greatest at a higher forward rf plasma power (1700 W). The increased sensitivity may be useful in practical analyses; N2 consumption is very small.  相似文献   

5.
The pulsed power operation mode of a radiofrequency (rf) glow discharge time‐of‐flight mass spectrometer was investigated, for several ions, in terms of intensity profiles along each pulse period. Particular attention was paid to the plateau and transient afterglow regions. An rf pulse period of 4 ms and a duty cycle of 50% was selected to evaluate the influence of discharge parameters in the afterglow delay and shape of Ar+, Ar2+ and several analytes (Br, Cl, Cu) contained in polymeric layers. Pulse shapes of Ar+ and Ar2+ ions vary with pressure and power. At low pressures the highest intensity is observed in the plateau while at higher pressures (>600 Pa) the afterpeak is the dominant region. Although the influence of the applied power is less noticeable, a widening of the afterglow time regime occurs for Ar+ when increasing the power. Maximum intensity of the argon signal is measured in the afterglow at 30 W, while the area of such afterpeak increases with power. The maximum intensity of Ar2+ is obtained at the highest power employed (60 W) and the ratio maximum intensity/afterglow area remains approximately constant with power. Analytes with ionization potentials below (Cu) or just above (Br) the argon metastable energy show maxima intensities after argon ions decay, indicating they could be ionized by collisions with metastable Ar atoms. Chlorine signals are observed in the afterglow despite their ionization potential is well above the energy of argon metastable levels. Moreover, they follow a similar pattern to that observed for Ar2+, indicating that charge‐transfer process with Ar2+ could play a significant role. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

6.
The decomposition of N2O in a 13.56-MHz parallel-plate system was studied usingin situ Fourier transform infrared (FTIR) spectroscopy. Areas of two infrared absorption bands of N2O recorded at 8 cm–1 resolution were used to estimate relative gas-phase dissociation as a function of rf power and flow rate at 500 mT. Flow rate was found to strongly affect band areas over the range of powers investigated (10–90 W). The effect of rf power on band areas diminished above 40 W, probably due to poor plasma confinement. Distortion of the band shapes by the plasma permitted rotational temperatures to be estimated. Rotational temperature increased essentially linearly with power at constant flow rate, reaching 450 K at 80 W, but was independent of flow rate at constant power. Rotational temperatures were also found to depend on the temperature of the electrodes, which were heated by plasma exposure. No infrared-active product species were observed even under batch conditions where all N2O was irreversibly dissociated. This lack of detectable products and a 50% pressure rise observed in a batch study suggest that N2 and O2 are the primary stable discharge products.  相似文献   

7.
A novel analytical technique for isotopic analysis of dissolved and particulate iron (Fe) from various marine environments is presented in this paper. It combines coprecipitation of dissolved Fe (DFe) samples with Mg(OH)2, and acid digestion of particulate Fe (PFe) samples with double pass chromatographic separation. Isotopic data were obtained using a Nu Plasma MC-ICP-MS in dry plasma mode, applying a combination of standard-sample bracketing and external normalization by Cu doping. Argon interferences were determined prior to each analysis and automatically subtracted during analysis. Sample size can be varied between 200 and 600 ng of Fe per measurement and total procedural blanks are better than 10 ng of Fe. Typical external precision of replicate analyses (1S.D.) is ±0.07‰ on δ56Fe and ±0.09‰ on δ57Fe while typical internal precision of a measurement (1S.E.) is ±0.03‰ on δ56Fe and ±0.04‰ on δ57Fe. Accuracy and precision were assured by the analysis of reference material IRMM-014, an in-house pure Fe standard, an in-house rock standard, as well as by inter-laboratory comparison using a hematite standard from ETH (Zürich). The lowest amount of Fe (200 ng) at which a reliable isotopic measurement could still be performed corresponds to a DFe or PFe concentration of ∼2 nmol L−1 for a 2 L sample size. To show the versatility of the method, results are presented from contrasting environments characterized by a wide range of Fe concentrations as well as varying salt content: the Scheldt estuary, the North Sea, and Antarctic pack ice. The range of DFe and PFe concentrations encountered in this investigation falls between 2 and 2000 nmol L−1 Fe. The distinct isotopic compositions detected in these environments cover the whole range reported in previous studies of natural Fe isotopic fractionation in the marine environment, i.e. δ56Fe varies between −3.5‰ and +1.5‰. The largest fractionations were observed in environments characterized by redox changes and/or strong Fe cycling. This demonstrates the potential use of Fe isotopes as a tool to trace marine biogeochemical processes involving Fe.  相似文献   

8.
Electron energy distribution functions (EEDF) and related properties in the bulk region of the rf CO plasma at the reduced rf field frequency /p0=×107 sec–1 torr–1 have been calculated by solving the time-dependent spatially homogeneous Boltzmann equation in the presence of second-kind collisions and have been interpreted on a microphysical basis. The results show that second-kind collisions (vibrational and electronic) strongly affect the temporal evolution of EEDF, of the mean energy, and of the mean collision frequencies for vibrational and electronic excitation processes, as well as for ionization. In particular, second-kind collisions in the CO rf bulk plasma strongly decrease the modulation of the mean ionization frequency during its periodical alteration in the rf field. Furthermore, the effect of second-kind collisions on an approximate determination of the time-averaged EEDF in the rf bulk plasma using the so-called effective-field appriximation has been estimated.  相似文献   

9.
Distribution of polymer deposition in an inductively coupled rf discharge system is studied as a function of level of discharge power with acetylene and styrene as monomers. When a fixed flow rate is used, the discharge power has a relatively small effect on the pattern of distribution of polymer deposition as long as values of W/FM, where W is discharge wattage, F is flow rate, and M is molecular weight of monomer, are maintained above a critical level to maintain full glow in the reaction tube. It has been shown that plasma polymerization of two monomers which have different molecular weights can be compared in a fair manner by selecting conditions to yield similar value of W/FM.  相似文献   

10.
To avoid mass interferences on analyte ions caused by argon ions and argon molecular ions via reactions with collision gases, an rf hexapole filled with helium and hydrogen has been used in inductively coupled plasma mass spectrometry (ICP–MS), and its performance has been studied. Up to tenfold improvement in sensitivity was observed for heavy elements (m > 100 u), because of better ion transmission through the hexapole ion guide. A reduction of argon ions Ar+ and the molecular ions of argon ArX+ (X = O, Ar) by up to three orders of magnitude was achieved in a hexapole collision cell of an ICP–MS (“Platform ICP”, Micromass, Manchester, UK) as a result of gas-phase reactions with hydrogen when the hexapole bias (HB) was set to 0 V; at an HB of 1.6 V argon, and argon-based ions of masses 40 u, 56 u, and 80 u, were reduced by approximately four, two, and five orders of magnitude, respectively. The signal-to-noise ratio 80Se/ 40Ar2 + was improved by more than five orders of magnitude under optimized experimental conditions. Dependence of mass discrimination on collision-cell properties was studied in the mass range 10 u (boron) to 238 u (uranium). Isotopic analysis of the elements affected by mass-spectrometric interference, Ca, Fe, and Se, was performed using a Meinhard nebulizer and an ultrasonic nebulizer (USN). The measured isotope ratios were comparable with tabulated values from IUPAC. Precision of 0.26%, 0.19%, and 0.12%, respectively, and accuracy of 0.13% 0.25%, and 0.92%, respectively, was achieved for isotope ratios 44Ca/ 40Ca and 56Fe/57Fe in 10 μg L–1 solution nebulized by means of a USN and for 78Se/80Se in 100 μg L–1 solution nebulized by means of a Meinhard nebulizer. Received: 15 December 2000 / Revised: 26 March 2001 / Accepted: 27 March 2001  相似文献   

11.
Four helium plasma sources operating at atmospheric pressure have been developed for analytical emission spectrometry by applying a synchronically rotating field with three or more phases operating at 1 kHz, 27 MHz or 2.45 GHz. The plasma takes the form of a disk and has minimum field strength at the axis. Thus, a channel is formed at the center through which the sample in the form of wet aerosol or a chemically generated vapor of halogen may be introduced. A dual-flow concentric ceramic injector was used to supply helium plasma gas and the sample to the plasma. The helium plasma operated at low power levels (40-300 W) and low gas flow rates of below 3 L min− 1 and was self-igniting. The acoustic, radio-frequency (rf) and microwave-driven plasmas can withstand wet aerosol loadings of 5, 30 and 100 mg min− 1, respectively, generated by an ultrasonic nebulizer without a desolvation unit. The plasma physical characteristics were compared at these three frequencies under otherwise similar operating conditions. The helium excitation temperature, OH rotational temperature and electron number density increased with increasing frequency in ranges of 2800-4000 K, 1100-3200 K and 0.1-7 × 1014 cm− 3, respectively. To demonstrate the effect of frequency on the plasma excitation efficiency the emission intensity from halogen ions was evaluated using chemical vapor generation with continuous sampling without desiccation. Using 3-phase microwave, 6-phase microwave, 4-phase rf and 1 kHz helium plasma sources the detection limits (3σ) for chlorine at 479.40 nm were 26, 60, 230 and 1200 ng mL− 1, respectively. The microwave-driven plasma was the densest and had the highest excitation potential toward chlorine and bromine ions.  相似文献   

12.
The interference standard method (IFS) is evaluated to improve the accuracy of the determination of S, Mn and Fe in meat and grain samples by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS). Due to ICP-QMS relatively low resolution, polyatomic interferences caused by 16O2+, (16OH)2+, 40Ar14NH+, and 40Ar16O+, for example, can compromise determinations at m/z 32, 34, 55, and 56, respectively. In IFS, differently from traditional internal standard methods, plasma naturally occurring species are used to correct for variations in the interference signal rather than the analyte signal. The method is based on the hypothesis that the interfering ion and the IFS probe present similar behaviors in the plasma, and that by using the analytical (analyte plus interference)/IFS signal ratio one could reduce variations due to interference and, consequently, improve accuracy. In this work, this strategy is evaluated in real sample applications and significant improvements on accuracy are observed for 32S, 34S, 55Mn, and 56Fe determinations. Recoveries ranging from 72% for Mn to 105% for Fe in two different standard reference materials are obtained using the 38Ar probe. These analytes are successfully determined in meat and grain samples with concentrations ranging from 4.42 μg g−1 for Mn in corn to 7270 μg g−1 for S in chicken liver. The method is compared with other strategies such as internal standardization and mathematical correction. No instrumental modification or introduction of foreign gases is required, which is especially attractive for routine applications.  相似文献   

13.
Pulverized coal plasma gasification   总被引:11,自引:0,他引:11  
A number of experiments on the plasma-vapor gasification of brown coals of three types have been carried out using an experimental plant with an electric-arc reactor of the combined type. On the basis of the material and heat balances, process parameters have been obtained: the degree of carbon gasification (c), the level of sulfur conversion into the gas phase (s), the synthesis gas concentration (CO+Hz) in the gaseous products, and the specific power consumption for the gasification process. The degree of gasification was 90.5-95.0%, the concentration of the synthesis gas amounted to 84.7–85.7%, and the level of sulfur conversion into the gas phase was 94.3–96.7%. Numerical study of the process of plasma gasification of coals was carried out using a mathematical model of motion, heating, and gasification of polydisperse coal particles in an electric-arc reactor of the combined type with an internal heat source (arc). The initial conditions for a conjugate system of nonlinear differential equations of the gas dynamics and kinetics of a pulverized coal stream interacting with the electric arc and oxidizer (water vapor) agree with the initial conditions of the experiments. The computation results satisfactorily correlate with the experimental data. The mathematical model can be used for the determination of reagent residence time and geometrical dimensions of the plasma reactor for the gasification of coals.Nomenclature c i volume concentration of components (kmol m–3) - x longitudinal coordinate (m) - f i source members, determined by variation of the ith component due to chemical reactions in unit volume in unit time (kmol m–3s–1) - velocity (m s–1) - M s ash mass in one particle (kg) - C D particle drag coefficient - 3.14 - r s particle radius (m) - d particle diameter (m) - density (kg m–3) - C p heat capacity of components (J molt– K–1) - Q j thermal effect of reaction (J kmol–1) - Ej activation energy of reaction - N l volume concentration of particles of thelth fraction (m–3) - T temperature (K) - emissivity factor of coal particles - 5.67 × 10–8, blackbody emissivity coefficient (W m–2 K–4) - P pressure (Pa) - S reactor cross section (m2) - D reactor diameter (m) - V reactor volume (m3) - L R reactor length (m) - F W friction force on the wall (N) - f g friction coefficient - residence time (s) - Nu Nusselt number - Re Reynolds number - Pr Prandtl number - thermal conductivity of gas (J m s–1 K–1) - R 8.3 × 103, universal gas constant (J kmol K–1) - µ i molecular mass of component (kg kmol–1) - dynamic viscosity coefficient of gas (kg m–1 s–1) - thermal efficiency of plasma reactor - qarc specific heat flow from arc (W m–3) - P 1 heat supplied in vapor at T = 405 K (W) - P 2 heat loss to wall (W) - P 3 heat loss in the gas and slag separator chamber (W) - P 4 heat loss in the synthesis gas oxidation chamber (W) - P 5 heat loss in the slag catcher (W) - P 6 heat carried away in the off-gas (W) - P heat input of arc (W) - P arc electric power of arc (W) - Qsp specific power consumption (kw Hr kg–1) - d w specific heat flow to wall (W m–2) - c degree of carbon gasification (%) - s level of sulfur conversion into gas phase (%)  相似文献   

14.
Langmuir probe studies have been performed on rf (27.1 MHz) discharges in O2 under planar reactor conditions to determine the axial variation of the plasma parameters (positive ion density, electron temperature, and dc space potential) as a function of pressure (20–220 Pa) and power (10–150 W) or current (0.1–2 A). By monitoring the second derivative of the I–V probe characteristics, the suppression of the rf component in the probe circuit can be optimized. Referring to this problem, numerical studies provide relations for the determination of the residual rf component as well as of the dc component of the plasma potential at incomplete rf compensation. The positive ion density is obtained from the ion saturation currents. Here the effect of collisions between ions and neutral particles within the probe sheath (for p> 100 Pa) is considered. The electron energy distribution function is found to be of the Maxwellian type for all discharge conditions investigated here. If the pressure and the power exceed critical values, the axial charge carrier distribution is characterized by a valley formation in the bulk plasma center. This fact demonstrates that secondary electron emission due to ion impact on the electrode surfaces and following ionization by these electrons near the sheaths in front of the electrodes are significant processes for sustaining the discharge. At low pressures (p60 Pa) the dc plasma potential was found to be identical with the half-peak maintaining voltage of the discharge, in agreement with the model idea of a symmetric rf planar discharge where the rf voltage drop across the bulk plasma can be neglected. For growing pressure, however, the plasma system moves gradually toward a situation where the V-I characteristics of the discharge are significantly controlled by processes in the bulk plasma. This transition depends on the current density.  相似文献   

15.
The plasma homo- and copolymerizations of tetrafluoroethylene (TFE) and chlorotrifluoroethylene (CTFE) in a capacitively coupled tubular reactor (TR) with external electrodes were studied by means of microgravimetry and FT-IR and XPS analyses. The deposition rates for CTFE/TFE plasma copolymers, as well as the ratios of IR absorbances at 1180 and 1225 cm−1, and the XPS-derived Cl/C and F/C ratios, varied regularly with mol % CTFE in the feed, all of which results were dependent upon the rf power at which the plasma copolymerizations were conducted. The deposition rates for the plasma homopolymers of TFE (PPTFE) and CTFE (PPTCFE) depended markedly on rf power (W) and monomer molar flow rate (F). The F/C ratio for PPTFE was nearly independent of the composite parameter,W/FM (whereM is the monomer molecular weight), while for PPCTFE, the F/C ratio decreased significantly and the Cl/C ratio increased slightly with increase inW/FM. The percentage of carbon as CF3 was 20–24% in PPTFE and 7–14% in PPCTFE. Plots of deposition rate versusW/FM for PPTFE and PPCTFE obtained in a TR differed considerably from corresponding plots in the literature for the same homopolymers prepared in a glass-cross or bell-jar reactor.  相似文献   

16.
Spatially resolved ion-atom emission intensity ratios for Sr, Ca, Mg, Cd and Zn have been measured at rf power settings of 1.00, 1.25, 1.50, 1.75 and 2.0 kW at a vertical height of 16 mm above the load coil. Measured values of electron density have been used to construct a theoretical local thermal equilibrium (LTE) framework, and ion-atom emission intensity ratios calculated from this framework have been compared to experimentally measured values. The measured ion-atom emission intensity ratios were found to be within an order of magnitude of these calculated LTE ratios.The experimental degree of ionization for these five elements was determined for the various rf input powers. These values have been compared to the analagous LTE values. Both degree of ionization and departure from LTE were found to be strongly correlated with the ionization potential of the element.The radial spatial dependence of the degree of ionization for Cd at an rf power of 1.25 kW has been measured for aerosol flow rates of 0.6, 0.8 and 1.21 m−1 for vertical heights of 4, 8, 12, 16 and 20 mm above the load coil. The spatial distribution of electron number density was measured at an rf power of 1.25 kW and at aerosol flow rates of 0.6, 0.8 and 1.21 m−1 and a correlation between degree of ionization and electron density identified. Finally the relative concentration of Cd ions has been calculated from ion spatial emission profiles and plasma operating conditions which produce a maximum in the ion density identified.  相似文献   

17.
Xenon is added to the axial channel of an argon inductively coupled plasma (ICP) at doses up to 1.5% of the aerosol gas flow. Emission is collected from the gas flowing into the sampling orifice of a mass spectrometer (MS). These Xe doses have little effect on the electron density ne or on the intensities of Fe (I) emission lines. Certain Fe (II) lines are enhanced when Xe is added, particularly those from Fe+ states that can be populated by near-resonant charge transfer between Xe and neutral Fe. Calculations based on measured values of ne indicate that Xe+ should be present at densities of up to 7 × 1014 cm−1, which should be sufficient Xe+ to drive the proposed charge transfer reactions.  相似文献   

18.
Addition of Cationic Lewis Acids [M′Ln]+ (M′Ln = Fe(CO)2Cp, Fe(CO)(PPh3)Cp, Ru(PPh3)2Cp, Re(CO)5, Pt(PPh3)2, W(CO)3Cp to the Anionic Thiocarbonyl Complexes [HB(pz)3(OC)2M(CS)] (M = Mo, W; pz = 3,5‐dimethylpyrazol‐1‐yl) Adducts from Organometallic Lewis Acids [Fe(CO)2Cp]+, [Fe(CO)(PPh3)Cp]+, [Ru(PPh3)2Cp]+, [Re(CO)5]+, [ Pt(PPh3)2]+, [W(CO)3Cp]+ and the anionic thiocarbonyl complexes [HB(pz)3(OC)2M(CS)] (M = Mo, W) have been prepared. Their spectroscopic data indicate that the addition of the cations occurs at the sulphur atom to give end‐to‐end thiocarbonyl bridged complexes [HB(pz)3(OC)2MCSM′Ln].  相似文献   

19.
Stable complexes are required during the ion chromatographic (IC) separation of Fe‐polycarboxylic acid complexes. Electrospray ionization mass spectrometry (ESI‐MS) was used to identify 1:1 stoichiometric complexes of Fe[HEDTA], Fe[EDTA]1? and Fe[DTPA]2?, and the spectra showed that these Fe complexes were stable in solution. Furthermore, inductively coupled plasma mass spectrometry (ICP‐MS) using an octopole reaction system (ORS) reduced polyatomic ion 40Ar16O+ interference in the detection of 56Fe via the addition of either H2 or He to the ORS, with He at a flow rate 3.5 mL min?1 being the optimum collision gas. Finally, IC/ICP‐MS was used for the separation and detection of Fe complexes with an eluent containing 30 mM (NH4)2HPO4 at pH 8.0, but only Fe[HEDTA], Fe[EDTA]1? and Fe[DTPA]2? were observed within 10 min with reasonable resolution. Detection limits in the range of 10–13 µg L?1 were achieved using He as the collision gas. The proposed method was used for the determination of Fe species in soil solutions. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

20.
Plasma at atmospheric pressure can be obtained by surface wave propagation with a surfatron. If the plasma is produced within a quartz tube, it is constricted to a diameter of approx. 1 or 2 mm but its length can attain some tens of centimeters with microwave power as low as 100 W. This plasma is quite uniform along the axis, with a typical electron density of 3 × 1014 electrons/cm3. Since the excitation and gas temperatures are lower than 4000 K, the plasma is far from local thermodynamic equilibrium. High stability and repeatability is achieved with an argon flow of 0.2–17 l/min. Applications are foreseen in the field of optical spectroscopy and plasma chemistry.  相似文献   

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