Date of Award
Doctor of Philosophy
The behavior of the mercurous ion has been studied in dilute aqueous solutions. The ion was found to be unstable toward dismutation according to the equation: Hg++2&rlhar2;K Hg+++Hgaq . Values of 5.3 x 10-9 and 5.6 x 10-9 have been measured for the dismutation constant K at 25°C by making use of a radioactive tracer technique in which mercury was distributed between non-polar solvents and dilute aqueous solutions of mercurous nitrate;The above values for the dismutation constant are in fair agreement with the values 1.8 x 10-9 to 3.6 x 10 -9 which were calculated by a different approach. The latter figures were obtained as the product of the reported concentration ratios [Hg++]/[ Hg++2 ], in the presence of liquid mercury, and the solubility of the metal in aqueous solutions determined in this study (3.0 x 10-7 g atoms/liter);Although the possibility of dissociation of the mercurous dimer into monomeric mercurous ions cannot be completely excluded, the results of this study can be satisfactorily interpreted without considering this effect. The results indicate that a dissociation constant as large as 1 x 10 -7 is highly unlikely;The solubility of mercury in several organic solvents was determined and compared with solubilities calculated with Hildebrand's "solubility parameter" equation. The agreement was reasonable with saturated hydrocarbons as solvents, but with carbon tetrachloride, benzene, and benzene derivatives as solvents the observed solubilities were considerably smaller than those predicted by the solubility equation;Mercuric iodide-iodide ion equilibria have been studied at 25°C. Use was made of the extraction of mercuric iodide into benzene from dilute aqueous solutions of mercuric nitrate containing excess potassium iodide to study the following equilibria: HgI2+I- &rlhar2;K1 HgI-3 and HgI2+2I-&rlhar2; K2HgI=4. K1 and K2 were determined to be (5.0 +/- 0.1)103 and (5.1 +/- 0.1)10 5 respectively.
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Herbert Charles Moser
Moser, Herbert Charles, "Radiochemical studies of mercury and its ions in dulute solutions " (1957). Retrospective Theses and Dissertations. 12739.