Stability constants are measured for complexes of Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) with some 5-substituted-1,10-phenanthrolines, and are tabulated with other constants reported in the literature. It is found that the order of stabilities for the 1:1 complexes follows the expected series: Fe(II) < Co(II) < Ni(II) < Cu(II) > Zn(II). The 1:3 complexes follow an anomalous order which is attributed to non-uniformity in the metal ions with respect to the symmetry of the octahedral configuration. An important implication in this interpretation is that, the iraBS-configuration of bis-(l,10phenanthroline)-copper(II) is sterically unstable.
The effect of hydrogen ion concentration on the kinetics of formation and dissociation of the mono-(1,lO-phenanthro1itie)-nickel(I1) complex is examined. Two mechanisms are proposed as possible reaction paths. One mechanism is the acidcatalyzed reaction of an unstable intermediate formed between the ligand and nickel(I1) ; the other mechanism is the reaction of the l,l0-phenanthrolium ion with nickel (I1) t o form an intermediate. Both mechanisms fit the general expression klr = ([H+] + 0.0043)/(2.62 [H+] + 0.258) lo6 1. mole-' sec.-l. The equilibrium constants of the mono-, bis-and tris-(1,lO-phenanthro1ine)-nickel(I1) complexes are Kt = 2.5 X lo*, K2 = 8 X lo*, Kt = 2.8 X 10-8, respectively.
Details of the processes occurring during sample atomization from a “microarc” discharge have been studied photometrically, by use of high-speed color cinematography and through current-voltage waveforms. The microarc studied here is an atmospheric-pressure inert-gas glow discharge supported between 0.25 mm diameter tungsten wires; quiescent argon-1% H2 provides reactive-sputtering conditions and improved behavior in the presence of oxygen impurities. Excitation temperatures of ca. 5000°K are measured for the argon glow. Samples of Na, Al, and Sr illustrate the influence of volatile, refractory, insulating, and electron-emitting sample properties on the temporal-spatial-electrical behavior of the discharge. The step-by-step events occurring in the discharge are described qualitatively and a variety of processes are invoked to explain sample volatilization, including sputtering, chemical reactions, and purely thermal effects. In the first stages of the discharge, instabilities are related to the placement and insulating character of deposits. With heating, electron emission becomes important in directing the discharge to or away from the sample; abnormal glow wandering and glow-to-arc transitions can ensue. Improved stability is achieved by uniformly depositing multi-element samples along the electrode, which localizes the initial discharge and promotes ablative cooling of the sample and electrode.
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