Thermal reactions of the CF3
2+ dication with argon lead to the formation of an ArCF2
2+ dication, a new type of metastable species with an argon−carbon bond. None of the other rare gases undergo a similar reaction with CF3
2+. For the lighter rare gases (He and Ne), no reactions with CF3
2+ other than those due to electronically excited reactant ions are observed, whereas for the heavier rare gases (Kr and Xe), the prevailing reactive pathways involve single-electron transfer. At elevated collision energies, single-electron transfer predominates for collisions with all rare gases (He−Xe).
Electrospray ionization of an aqueous solution of nickel(II) sulfate provides direct experimental evidence for the formation of triple ions of the type [Ni(2)(SO(4))(H(2)O)(n)](2+) and [Ni(SO(4))(2)](2-), whose existence in aqueous solution has previously been proposed based on relaxation spectroscopy [Chen et al. J. Sol. Chem. 2005, 34, 1045]. Formally, these triple ions are formed by aggregation of the solvated ions Ni(2+) and SO(4)(2-), respectively, with the neutral ion pair NiSO(4). In addition, also higher adducts are observed, e.g. the "pentuple ions" [Ni(3)(SO(4))(2)(H(2)O)(n)](2+) (n = 7-9) and [Ni(2)(SO(4))(3)](2-), of which the dicationic is extensively hydrated, whereas the anionic is not. The structures of the dinuclear nickel clusters are derived from ab initio calculations and their infrared spectra are compared with experimental data obtained for the gaseous ions [Ni(2)SO(4)(H(2)O)(5)](2+) and [Ni(2)(SO(4))(3)](2-), respectively. The calculations show that the structures are crucially controlled by the degree of solvation of nickel ion. Explicit consideration of solvating water molecules within the first coordination sphere suggest that the dicationic triple ion [Ni(2)SO(4)](aq)(2+) is bent and thus bears a permanent dipole moment, whereas the [Ni(SO(4))(2)](aq)(2-) dianion tends to be quasi-linear. The experimental and theoretical data for the gaseous ions thus support the elegant, but indirect, deductions previously made based on solution-phase studies.
Corrosion of pristine AB5-type metal alloy LaMm-Ni4.1Al0.3Mn0.4Co0.45 in the aqueous solutions of alkali metal hydroxides of diverse composition and concentration was tested. Correlation was observed between the alloy corrosion intensity in various hydroxide solutions, and its electrochemical capacity in these electrolytes. Mm(OH)3, CoO(OH), and nickel metal aggregates were detected among the products of selective oxidation of the alloy. High intensity corrosion of the alloy was observed in RbOH and CsOH solutions leading to formation of ternary oxides at the surface of the alloy. Presence of rubidium and cesium ions in the electrolyte were found to create an additional driving force for lanthanides (La and Ce) to leave the lattice of the alloy, thus, enhancing its corrosion. Corrosion, together with mechanical degradation, were found to be the main reasons of deactivation of LaMm-Ni4.1Al0.3Mn0.4Co0.45 alloy upon elongated electrochemical treatment.
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