Gases, noble from analyses

In this section we will discuss an example of recent laboratory work on the impact of sulfur on palladium catalysts formulations compared to other noble metal formulations. The laboratory studies discussed here have been performed using an apparatus which simulates the exhaust gas generated from a vehicle under several operating modes. The simulated exhaust gas is then heated to a controlled level and directed to a sample core taken from a commercial automotive converter. Quantitative analysis of pollutant and other gas species (CO, HC, NOx, COj and Oj) is performed using gas bench analyzers prior to and following the catalyst sample to determine the conversion efficiency for HC, CO and NOx. 

Hiyagon H (1994b) Constraints on rare gas partition coefficients from analysis of olivine-glass from a picritic mid-ocean ridge basalt-Comments. Chem Geol 112 119-122 Hiyagon H, Ozima M (1982) Noble gas distribntion between basalt melt and crystals. Earth Planet Sci Lett 58 255-264... 

The determination of noble gases in water can be divided into three successive analytical steps (1) noble gas extraction from the water, (2) purification and separation of the extracted noble gases, and (3) quantitative (mass spectrometric) analysis. For extended discussions of methods for noble gas analysis in waters (and other terrestrial fluids) the readers are referred to Clarke et al. (1976), Rudolph (1981), Bayer et al. (1989), Stute (1989), Groning (1994), Ludin et al. (1997), and Beyerle et al. (2000a). 

Surface composition analysis by LEIS is based on the use of noble gas ions as projectiles, making use of the superb surface sensitivity of LEIS under these conditions. A consequence of this surface sensitivity is that the LEIS energy spectrum consists of lines, one per element, if the masses differ sufficiently. The lines are narrow, because inelastic energy losses play a minor role here. Thus, the information on the atomic species present is deduced from the energy of the back-scattered ions, which can be converted to the mass of the scattering center. (Eig. 3.55 [3.141]). In Eig. 3.55 it is shown that the mass range, where LEIS is sensitive, depends on the projectile mass. 

Another very important technique for fundamental consideration of multicomponent systems is low energy ion scattering (LEIS) [Taglauer and Heiland, 1980 Brongersma et al., 2007]. This is a unique tool in surface analysis, since it provides the ability to define the atomic composition of the topmost surface layer under UHV conditions. The signal does not interfere with the subsurface atomic layers, and therefore the results of LEIS analysis represent exclusively the response from the outer surface. In LEIS, a surface is used as a target that scatters a noble gas ion beam (He, Ne, ... 

Fig. 3.13. Total (tot, upper solid line) and elastic (el, lower solid line) cross sections for positron-noble gas scattering near the positronium formation threshold from the R-matrix analysis of Moxom et al. (1994). Graphs (a)-(e) correspond to helium through to xenon. The data points shown are total cross section measurements from the literature (see Chapter 2 and Moxom et al., 1994, for details) except for the solid diamonds for helium, which are the

Thus, the noble gases are trace elements par excellence. As an example, a not unreasonable value of Xe concentration in a rock is some 10 11 cm3 STP/g (about 3 x 108 atoms/g), or 0.00006ppb. It is nevertheless quite feasible to perform an adequate analysis on a 1-g sample of such a rock, in the sense of a sample to blank ratio in excess of 102, 5-10% uncertainty in absolute abundance, and 1% or less uncertainty in relative abundances of the major isotopes. Detection limits are much lower than this, and for the scarcer isotopes the blank and thus the quantity necessary for analysis are two to three orders of magnitude lower. It is worth noting that the reason why such an experiment is possible is the same reason why noble gases are so scarce in the first place their preference for a gas phase and the ease with which they can be separated from more reactive species. 

In concluding this section, it is pertinent to take note of a special kind of isotopic fractionation ubiquitous, often quite severe, and arguably the most important source of fractionation that must be taken into consideration in noble gas geochemistry. This fractionation arises in mass spectrometric analysis contributory effects can and do arise in gas extraction and transport through the vacuum system, in the ion source (especially when a source magnet is used), in beam transmission, and in ion collection and detection (especially when an electron multiplier is used). As noted in Section 1.3, sample data are corrected for instrumental (and procedural) discrimination, which is calibrated by analysis of some standard gas (usually air). This is a roundabout and imperfect near-equivalent to the 8 value convention, which is the norm in stable isotope geochemistry (O, C, H, S, N, etc.). The reproducibility of instrumental discrimination inferred from repeated calibration analysis is usually quite satisfactory, but seldom is any care taken to try to match operating conditions in samples and calibration analyses. It is thus a matter of faith - undoubtedly quite... 

Ion Bombardment Conditions. A base pressure of 10 9 Torr is maintained in this chamber the noble gas pressure (He, Xe) rises to about 10"7 Torr during the ion bombardment. The ion beam is rastered on (1.5 x 1.5) mm2 areas at normal incidence 4He-2 keV ions are used for the ISS analysis when Xe-4 keV ions are used for SIMS. The incident ion current is measured with the aid of a moveable Faraday cup. Since the investigated samples are electrical insulators, charge neutralization is performed with low energy electrons ( 10 eV) emitted from a heated W filament. 

Vibrational spectroscopy is successfully employed to quantitative analysis of gases, especially if real time and on-line analyses are needed. In order to compensate the effects of pressure broadening, it is worthwhile to carry out all measurements at the same total pressure. To this end, the sample is placed in an inert gas, such as nitrogen or a noble gas, and the pressure raised to a defined value. The partial pressure instead of the concentration is used in the Lambert-Beer law. The calibration curve is valid only at the calibration temperature. If the temperature of the sample deviates from this temperature, the partial pressure has to be corrected by the Gay-Lussac law. 

Nitrogen obtained from air was found to have density 1.2572 g/1 at 0 C and I atm, whereas nitrogen made by chemical methods had a density 1.2505 g/1. Rayleigh and Ramsay then repeated Cavendish s experiments, and showed by spectroscopic analysis that the residual gas was indeed not nitrogen but a new element. They then searched for the other stable noble gases and discovered them. 

For most of the chemical elements, the relative abundances of their stable isotopes in the Sun and solar nebula are well known, so that any departures from those values that may be found in meteorites and planetary materials can then be interpreted in terms of planet-forming processes. This is best illustrated for the noble gases neon, argon, krypton, and xenon. The solar isotopic abundances are known through laboratory mass-spectrometric analysis of solar wind extracted from lunar soils (Eberhardt et al., 1970) and gas-rich meteorites. Noble gases in other meteorites and in the atmospheres of Earth and Mars show many substantial differences from the solar composition, due to a variety of nonsolar processes, e.g., excesses of " Ar and... 

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