Abstract: This paper is the first in a series of three that describe the application of emission Mossbauer spectroscopy to the in situ study of the cathodic and anodic behavior of cobalt. A brief review of the emission technique is given, along with a review of the chemical effects and Auger "after effects" that are associated with this experimental method. The surface sensitivity required to study thin anodic films was obtained by electrodepositing from 20 to 200A thick Co57 active layers on cobalt surfaces. Emission Mossbauer spectra from Fe57 daughter ("probe") atoms were obtained during polarization (vs. SCE) of specimens in buffered borate, pH 8.5. The specimens were free of surface oxide during cathodic polarization at −1100 mV. The spectra of specimens polarized at low passivating potentials, −100 mV, indicated the presence of both +2 and +3 charges. The +3 oxidation state of the Fe57 probe in the anodic film formed at this potential may arise from Auger after effects or chemical effects rather than from +3 states of the parent Co57. At higher passivating potentials +200 and +500 mV only the +3 oxidation state was observed. The existence of +2 oxidation state cannot be ruled out, however, because of the possibility for stabilization of defect charge states. Evidence for the +4 oxidation state in addition to +3 was found for specimens polarized at potentials in the transpassive range, +800 mV.

Abstract: A process for the selective oxidation of ammonia to nitric oxide in the presence of elemental nitrogen with minimal oxidation thereof, which comprises combining the ammonia with a predetermined amount of oxygen containing gas to give at least 1% stoichiometric excess of oxygen for the oxidation of the ammonia to nitric oxide; and passing the resulting mixture over a ceramic catalyst of the following empirical formula at an elevated temperature: W.sub.k X.sub.n J.sub.(1-k-n) ZO.sub.(3±m) wherein W is Zirconium, Tin or Thorium or mixtures thereof; X is an alkaline earth metal or mixture thereof; J is Scandium, Yttrium, a rare-earth element or mixture thereof; Z is a metal of the first transition series or a mixture thereof, at least 0.01% of said metal having an oxidation state other than +3; k is a number having a value between 0 and about 0.1; m is a number having a value of from 0 to about 0.26; and n is a number having a value from 0 to about 0.51, provided when n has a value of 0, k has a value between 0 and about 0.05.

Abstract: The binding energies of some inner-shell electrons in atoms of complexes [MoCl2O2L2], [MoCl3OL2], [MoCl4L2], and [MoCl3L3] are reported [L = PPh3, PMePh2, PMe2Ph, PEtPh2, MeCN, EtCN, tetrahydrofuran (thf), pyridine (py), ½ 2,2′-bipyridine (bipy), ½ 1,10-phenanthroline (phen), or ½ 1,2-bis(diphenylphosphino)ethane (dppe)]. Over this limited range of complexes, the metal binding energies are a function of the proportions of the anionic to neutral ligands, rather than of the metal oxidation state. The binding energies of the nitrogen atom in complexes of the donor py do not appear to correlate with simple inferences concerning atomic charges.

Abstract: The title complex, obtained by azide oxidation of a dimeric molybdenum(III,III) complex, is diamagnetic; it has four identical Mo's in a rectangular planar arrangement with alternate µ-oxo-µ-hydroxo (Mo–Mo 2·41 A) and µ-oxo bridges.

Abstract: A process for the production of oxygenated organic compounds including a substantial proportion of acetic acid by oxidizing a C 3 to C 7 saturated aliphatic hydrocarbon in the liquid phase with molecular oxygen in the presence of an inert reaction medium and a cobalt catalyst, between 5 and 90% in a continuous reaction and 11 and 90% in a batch reaction of the cobalt being introduced in the +3 oxidation state. The process is particularly applicable to the embodiment wherein the catalyst solution is recycled to the oxidation reaction. In order to achieve this a low-residue time distillation unit is preferably employed.

Abstract: 1. We have oxidized Co, Ni, and Cu by organic halogen-containing compounds and by bromine under mild conditions. 2. By reacting the metals Co, Ni, and Cu with organic halogen-containing compounds (RX) and Br2 in polar aprotic solvents (L) we have obtained complexes with the general formula NX2Ln, where n≤6, in which the metal is in oxidation state +2.

Abstract: The X-ray Kβ1β′-emission spectra of the lower oxides of Mn have been studied. From this study it is concluded that Mn is present in the bi-, ter- and quadrivalent states in the oxides of apparently tervalent manganese, in approximately equal proportions.

Abstract: Saturated hydrocarbons are isomerized using a catalyst comprising a combination of a platinum group component, a cobalt component, a tin component and a halogen component with a porous carrier material. The cobalt and platinum group components are reduced to the metallic state while the tin is present in a positive oxidation state.

Abstract: In Chapter 4 it was shown how the chemical isomer shift and quadrupole splitting in diamagnetic compounds are dependent on the oxidation state and covalent bonding of the resonant atom. The chemical isomer shift in paramagnetic compounds is governed by the same principles, and it was therefore convenient to consider the influence of covalency in high-spin Fe2+ and low-spin Fe(III) compounds in Section 4.5. However, the presence of an unpaired electron can result in magnetic and quadrupole interactions which are intimately related to the orbital state of the atom. It is therefore appropriate to consider these separately. The major part of this chapter is concerned with iron chemistry, but the ideas expressed are also applicable to other elements, and some of these are discussed separately at the end of the chapter.

Abstract: The applicability of X-ray photoelectron spectroscopy to the determination of the oxidation state of vanadium in minerals is studied. Using this technique, vanadium-rich aegirine (Na, Ca) (Fe, V)Si2O6 is found to contain vanadium as trivalent state.