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J . Phys. Chem. 1984,88, 5269-5213 constant and shows only the influence of temperature on the rate constants. We think that the deconvolution of the electrophoretic patterns will provide a new way to elucidate the structure and the reactivity, in solutions, of complexes which are in slow exchange as observed by tracers.
entities. We think, however, that some of the observed peaks reveal the kinetics of the interactions with the eluent, more than the existence of a definite entity in solution. On the other hand, the electrophoretic method does not introduce foreign species, as does the eluent in chromatography, and produce a physical separation based upon the differences in electrical mobilities. We think in conclusion that some chromatographic results should be reexamined.
Conclusion The present study provides a new way of understanding the meaning of the practical electrophoretic patterns in complex Appendix. Preparation of the Ru Experimental Solutions electrolyte solutions. The apparent pattern can be produced either by the migration of several separated species or by the kinetics The Ru solutions used for paper electrophoresis and diffusion of exchange between these species during the migration process. coefficient measurements were either labeled with lo3Ruor IMRu. This phenomenon provides a way to evaluate the rate constants They were prepared according to a process described by Martin', of these reactions, which can be useful, as in the present case, when in which either metallic Ru or RuC1, was attacked in a nickel other nonclassical methods, such as spectroscopic or electrocrucible by a molten mixture of NaOH or NazOz. After complete chemical techniques, are not available. For nitrato complexes of dissolution and cooling the radioactive Ru was added together RuNO present in 2 M HNO, we found that at 294 K mainly two with the amount of water necessary to dissolve the solidified melt. species were present. Their charges are 1+ and 2+ corresponding Then HNO, was added in order to obtain a solution at least 1 to the complexes R u N O ( N O ) ~ + . ~ Hand ~ O R U N O ( N O ~ ) ~ + . ~ H ~ O .M in HNO,. Sodium persulfate was added to oxidize Ru ions These results are qualitatively in agreement with the finding of into R u 0 4 which can then be selectively extracted into CC1,. Brown et alS2who used paper chromatography and solvent exImmediately after this, back-extraction was carried out using a traction to identify the aqueous RuNO(II1) complexes in nitric 2 M H N 0 3 solution containing 0.05 M hydrazine. This Ru-laacid solutions. The exchange rate of NO3- was also estimated beled solution was acidified to 10 M H N 0 3 and kept in the dark by solvent extraction, taking advantage of the better extractability in order to avoid the photochemical reaction of R U N O ( N O ~ ) ~ - ~into H ~tributhyl O phosphate.8s6 At room RuNO(I11) h v - Ru3+ N O temperature the half-reaction time is in the range 15-30 min; this value does not disagree with our results. However, the time followed by necessary to run the separation was not quoted and it is difficult to appreciate the influence of kinetic effects. 4Ru3+ 4H+ + N02R u N O ~ "+ 3Ru4+ + 2H20 Moreover, the present example allows us to formulate strong The concentration of Ru was determined by spectrophotometry restrictions upon the application of chromatographic methods to after the transformation of the Ru-nitrato complexes into Ruthe characterization of new species in solution: in some cases the (bpy)32+whose absorption coefficient at 453 nm is 14 500. use of eluents can give a great variety of chromatographic peaks, which are interpreted as characteristic of the existence of different Registry No. NO?-, 14797-55-8.
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Matrix Reactions of Ozone with Gallium, Indium, and Thallium Atoms Susan M. Sonchik,la Case Western Reserve University, Cleveland, Ohio 44106
Lester Andrews, Department of Chemistry, University of Virginia, Charlottesville, Virginia 22901
and K. Douglas Carlson* Divisions of Chemistry and Materials Science and Technology, Argonne National Laboratory, Argonne. Illinois 60439 (Received: February 24, 1984; In Final Form: May 25, 1984)
Frozen matrices of nitrogen containing Ga, In, and T1 atoms and ozone were prepared by matrix isolation techniques and studied by infrared absorption spectroscopy. Analyses of the spectra based on isotopic oxygen substitution have shown that the reagents yield the charge-transfer species M+O
