Valence monitoring

We have seen that the 4d excitations of the lanthanides have well-ddined multiplet structure, which is characteristic the 4f population. 4d excitations therefore provide very characteristic fingerprints the f count. This can be used to monitor the valence of rare earth atoms in compound systems, and valence changes during surface reactions have been followed by reflection EELS, taking advantage surface sensitivity of the method. In section 5.4 some illustrative examples valence monitoring by EELS will be discussed. 

The special properties of rare earth metals and their compounds manifest themselves in some interesting electron energy loss phenomena. In the valence region the low energy (A 3-4 eV) one-electron transitions merit further study both by theory and experiment, while the surface divalency of Sm metal shows up in an anomalous plasmon-like excitation. The core region reveals a rich variety of quasi-atomic excitations with particularly strong resonance losses associated with 5p -> 5d and 4d - 4f transitions. These phenomena lead on the one hand to convenient surface valence monitors and on the other to non-dipole excitations unseen by other spectroscopies. 

The reduction of molybdate salts in acidic solutions leads to the formation of the molybdenum blues (9). Reductants include dithionite, staimous ion, hydrazine, and ascorbate. The molybdenum blues are mixed-valence compounds where the blue color presumably arises from the intervalence Mo(V) — Mo(VI) electronic transition. These can be viewed as intermediate members of the class of mixed oxy hydroxides the end members of which are Mo(VI)02 and Mo(V)0(OH)2 [27845-91-6]. MoO and Mo(VI) solutions have been used as effective detectors of reductants because formation of the blue color can be monitored spectrophotometrically. The nonprotonic oxides of average oxidation state between V and VI are the molybdenum bronzes, known for their metallic luster and used in the formulation of bronze paints (see Paint). 

Shorter-wavelength radiation promotes transitions between electronic orbitals in atoms and molecules. Valence electrons are excited in the near-uv or visible. At higher energies, in the vacuum uv (vuv), inner-shell transitions begin to occur. Both regions are important to laboratory spectroscopy, but strong absorption by make the vuv unsuitable for atmospheric monitoring. Electronic transitions in molecules are accompanied by stmcture... 

Los Alamos is processing a wide variety of residues, including Pu-Be neutron sources, polystyrene-Pu02-U02 blocks, incinerator ash, Pu-U alloys and oxides, Pu-Zr alloys and oxides, Pu-Np alloys and oxides, Pu-Th alloys and oxides, etc. Processes have been developed for these scrap items (see Figure 2), but we need to know more about Pu-Np separations Pu-Th separations oxalate precipitations for both plus 3 and plus 4 valences valence stabilization dissolution methods for high-fired impure oxides in-line alpha monitors to measure extremely low concentrations of Pu and Am in HNO3 solutions and solubility of various mixtures of Pu02 and UO2 under a variety of conditions. 

A miniaturized MB spectrometer MIMOS II was developed for the robotic exploration of Mars, where it provided fundamental information about mineralogical composition and alteration processes, helped to classify rocks and soils, aided geologic mapping, was instrumental in assessing habitability of past and present environments, and identified potential construction resources for future human explorers. The applicability of the instrument as a process monitor for oxygen production and prospecting tool for lunar ISRU has been demonstrated. The characterization of air pollution sources and the study of mixed-valence materials as a function of depth in soil are examples of terrestrial in situ applications. MIMOS lla with additional XRF capability will open up new applications. 

The mixed-valence iron oxides provide an experimental test-bed for studying the evolution of charge-transfer processes from the localized-electron to the itinerant-electron regimes. Moreover, it is possible to monitor the influence of the charge transfer on the interatomic magnetic coupling since the iron ions in oxides carry localized magnetic moments. 

Over the past 10 years a multitude of new techniques has been developed to permit characterization of catalyst surfaces on the atomic scale. Low-energy electron diffraction (LEED) can determine the atomic surface structure of the topmost layer of the clean catalyst or of the adsorbed intermediate (7). Auger electron spectroscopy (2) (AES) and other electron spectroscopy techniques (X-ray photoelectron, ultraviolet photoelectron, electron loss spectroscopies, etc.) can be used to determine the chemical composition of the surface with the sensitivity of 1% of a monolayer (approximately 1013 atoms/cm2). In addition to qualitative and quantitative chemical analysis of the surface layer, electron spectroscopy can also be utilized to determine the valency of surface atoms and the nature of the surface chemical bond. These are static techniques, but by using a suitable apparatus, which will be described later, one can monitor the atomic structure and composition during catalytic reactions at low pressures (< 10-4 Torr). As a result, we can determine reaction rates and product distributions in catalytic surface reactions as a function of surface structure and surface chemical composition. These relations permit the exploration of the mechanistic details of catalysis on the molecular level to optimize catalyst preparation and to build new catalyst systems by employing the knowledge gained. 

Process monitoring poses two additional challenges compared to these automated fluidic separation methods. First, methodology for automated sample preparation must be developed, and second, the entire sample preparation-separation-detection system must be developed to operate on-line or at-site under unattended computer control, including sample transport through all the steps. Sample preparation is particularly critical for nuclear-waste and nuclear-process streams due to the complexity of the sample matrix and the uncontrolled valence states of several of the potential analytes. 

As indicated previously, NMR may be used simply as an analytical technique for monitoring the decomposition of a reactant or formation of a product. In addition, NMR and ESR merit a special mention due to their importance in studying the dynamics of systems at equilibrium these so-called equilibrium methods do not alter the dynamic equilibrium of the chemical process under study. They have been used to study, for example, -transfer reactions, valence isomerisations, conformational interconversions, heteronuclear isotopic exchange processes (NMR) and electron-transfer reactions (ESR). These techniques can be applied to the study of fast or very fast reactions by analysis of spectral line broadening [16,39],... 

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