Iron analysis spectroscopy

Feathers, J. K., M. Berhane, and L. May (1998), Firing analysis of South-Eastern Missouri Indian pottery using iron Mossbauer spectroscopy, Archaeometry 40, 59-70. 

A. M. Sofikitis, J. L. Colin, K. V. Desboeufs and R. Losno, Iron analysis in atmospheric water samples by atomic absorption spectroscopy (AAS) in water-methanol. Anal. Bioanal. Chem., 378(2), 2004,... 

The detailed chemistry of these films is stiU controversial older works based on elemental analysis with SEM-EDX showed that the film contained Zn, S, P, C and O [14]. XPS [15] and AES [16,17] have also been used to provide chemical differentiation for the different elements P was claimed to be present as a phosphate and S as a sulfide, the corresponding cation being zinc or iron. XANES spectroscopy revealed that the chemical nature of P and S in the tribofikns was different from that of the pure ZnDTP substances and depends on the alkyl group used in ZnDTP [18]. With isopropyl ZnDTP, phosphorus is found to correspond closely to metaphosphate (polyphosphate with a cyclic structure) whereas with u-butyl ZnDTP pyrophosphates are found. This is important when discussing the results obtained from commercial ZnDTP, which often consist of a blend of ZnDTP molecules containing different alkyl groups [3]. 

The buildup of soluble corrosion products can be used to monitor corrosion kinetics. This method has been used extensively in oil field corrosion inhibitor testing, particularly in sweet (CO2) systems with only small amounts of HjS present [29]. Iron analysis in the laboratory is most rapidly done on the bench with the Hach method (Phenantridine) [.30], although a host of other wet chemical methods are applicable. Instrumental methods include Atomic Absorption Spectroscopy (AAS) and Inductively Coupled Argon Plasma Spectroscopy (ICAP). While both these methods are well suited for high volume routine analysis, care must be taken that the samples are not contaminated by even traces of hydrocarbons. This includes soluble hydrocarbons such as methanol, chelating compounds such as EDTA, or scale inhibition products. Also used in the laboratory is Ion Chromatography (IC). This latter method is even more sensitive to sample composition and not recommended on a routine basis. 

The migration of K to the surface of the reduced catalyst [40] has been demonstrated by energy dispersive X-ray analysis [28], by field iron mass spectroscopy [222, 223], by chemisorption of CO, CO2, N2and H2 [207, 220] by scanning Auger electron spectroscopy [209-211], and by high-voltage electron microscopy [224]. 

Ion Scattering Spectroscopy (ISS) is one of the most powerful and practical methods of surface analysis available. However, it is undemtilized due to a lack of understanding about its application and capabilities. This stems from its history, the limited number of high-performance instmments manufactured, and the small number of experienced surface scientists who have actually used ISS in extensive applications. Ironically, it is one of the easiest and most convenient sur ce analytical instruments to use and it provides usehil information for almost any type of solid material. 

X-ray absorption spectroscopy has been performed on the isolated Rieske protein from bovine heart mitochondrial bc complex 69) as well as on the Rieske-type cluster in Burkholderia cepacia phthalate dioxygenase (PDO) (72). The analysis performed by Powers et al. 69) was significantly hampered by the fact that the presence of two histidine ligands was not fully recognized therefore, only the results obtained with the dioxygenase where the mononuclear iron has been depleted will be considered here. Table VII gives a comparison of the distances obtained from the fit of the EXAFS spectra assuming an idealized Rieske model and of the distances in the crystal structures... 

Contact shifts give information on the electronic structure of the iron atoms, particularly on the valence distribution and on the magnetic coupling within polymetallic systems. The magnetic coupling scheme, which is considered later, fully accounts for the variety of observed hyperfine shifts and the temperature dependence. Thus, through the analysis of the hyperfine shifts, NMR provides detailed information on the metal site(s) of iron-sulfur proteins, and, thanks to the progress in NMR spectroscopy, also the solution structure 23, 24 ). 

The applications of EPR spectroscopy reviewed in the present chapter are based on the sensitivity of the spectrum displayed by iron-sulfur centers to various characteristics, such as the redox state of the center, the distribution of the valences on the iron ions, the nature and the geometry of the ligands, and the presence of nearby paramagnetic species. Although considerable progress has been made during the past few years in the quantitative analysis of these various effects in the case of the conventional iron-sulfur centers described in Section II, the discovery of centers exhibiting unusual EPR properties as... 

Diazoalkanes are u.seful is precursors to ruthenium and osmium alkylidene porphyrin complexes, and have also been investigated in iron porphyrin chemistry. In an attempt to prepare iron porphyrin carbene complexes containing an oxygen atom on the /(-carbon atom of the carbene, the reaction of the diazoketone PhC(0)C(Ni)CH3 with Fe(TpCIPP) was undertaken. A low spin, diamagnetic carbene complex formulated as Fe(TpCIPP)(=C(CH3)C(0)Ph) was identified by U V-visible and fI NMR spectroscopy and elemental analysis. Addition of CF3CO2H to this rapidly produced the protonated N-alkyl porphyrin, and Bit oxidation in the presence of sodium dithionitc gave the iron(II) N-alkyl porphyrin, both reactions evidence for Fe-to-N migration processes. ... 

A mechanistic proposal, which is based on the mthenium-catalyzed dehydration reaction reported by Nagashima and coworkers [146], is shown in Scheme 44. Reaction of a primary amine with hydrosilane in the presence of the iron catalyst affords the bis(silyl)amine a and 2 equiv. of H2. Subsequently, the isomerization of a gives the A,0-bis(silyl)imidate b and then elimination of the disiloxane from b produces the corresponding nitrile. Although the disiloxane and its monohydrolysis product were observed by and Si NMR spectroscopy and by GC-Mass-analysis, intermediates a and b were not detected. 

The scanning transmission electron microscope (STEM) was used to directly observe nm size crystallites of supported platinum, palladium and first row transition metals. The objective of these studies was to determine the uniformity of size and mass of these crystallites and when feasible structural features. STEM analysis and temperature programmed desorption (TPD) of hydrogen Indicate that the 2 nm platinum crystallites supported on alumina are uniform In size and mass while platinum crystallites 3 to 4 nm in size vary by a factor of three-fold In mass. Analysis by STEM of platinum-palladium dn alumina established the segregation of platinum and palladium for the majority of crystallites analyzed even after exposure to elevated temperatures. Direct observation of nickel, cobalt, or iron crystallites on alumina was very difficult, however, the use of direct elemental analysis of 4-6 nm areas and real time Imaging capabilities of up to 20 Mx enabled direct analyses of these transition metals to be made. Additional analyses by TPD of hydrogen and photoacoustic spectroscopy (PAS) were made to support the STEM observations. 

A unique situation is encountered if Fe-M6ssbauer spectroscopy is applied for the study of spin-state transitions in iron complexes. The half-life of the excited state of the Fe nucleus involved in the Mossbauer experiment is tj/2 = 0.977 X 10 s which is related to the decay constant k by tj/2 = ln2/fe. The lifetime t = l//c is therefore = 1.410 x 10 s which value is just at the centre of the range estimated for the spin-state lifetime Tl = I/Zclh- Thus both the situations discussed above are expected to appear under suitable conditions in the Mossbauer spectra. The quantity of importance is here the nuclear Larmor precession frequency co . If the spin-state lifetime Tl = 1/feLH is long relative to the nuclear precession time l/co , i.e. Tl > l/o) , individual and sharp resonance lines for the two spin states are observed. On the other hand, if the spin-state lifetime is short and thus < l/o) , averaged spectra with intermediate values of quadrupole splitting A q and isomer shift 5 are found. For the intermediate case where Tl 1/cl , broadened and asymmetric resonance lines are obtained. These may be the subject of a lineshape analysis that will eventually produce values of rate constants for the dynamic spin-state inter-conversion process. The rate constants extracted from the spectra will be necessarily of the order of 10 -10 s"F... 

Nixon277 compared atomic absorption spectroscopy, flame photometry, mass spectroscopy, and neutron activation analysis as methods for the determination of some 21 trace elements (<100 ppm) in hard dental tissue and dental plaque silver, aluminum, arsenic, gold, barium, chromium, copper, fluoride, iron, lithium, manganese, molybdenum, nickel, lead, rubidium, antimony, selenium, tin, strontium, vanadium, and zinc. Brunelle 278) also described procedures for the determination of about 20 elements in soil using a combination of atomic absorption spectroscopy and neutron activation analysis. 

The usual techniques for the determination of particle sizes of catalysts are electron microscopy, chemisorption, XRD line broadening or profile analysis and magnetic measurements. The advantage of using Mossbauer spectroscopy for this purpose is that one simultaneously characterizes the state of the catalyst. As the state of supported iron catalysts depends often on subtleties in the reduction, the simultaneous determination of particle size and degree of reduction as in the studies of Fig. 5.10 is an important advantage of Mossbauer spectroscopy. 

---