Cobalt ions, equilibrium distribution

Cfs-butene should lead initially to the anti form trrms-butene should lead initially to the syn form and 1-butene should give rise initially to both. The equilibrium distribution of syn and anti forms usually differs greatly from the equilibrium distribution of cis- and frans-butene for cobalt complexes 59, 60) the syn form, precursor of irans-butene, is by far the most stable. By way of contrast for the corresponding carbanion, the cis anion seems by far the more stable. This preference for the cis carbanion is presumed to be the source of the high initial cis-to-trans ratio in the initial products of base catalyzed isomerization. In the base catalyzed isomerization of more complex cf-s-olefins (cfs-S-methyl-stilbene), the ions corresponding to syn and anti are not interconvertible and cis-trans isomeriza-... 

The most important point is the effect of thermal history upon the equilibrium level of cobalt and zinc ions in solution. Within experimental error, the results obtained with the 45 °C—two day systems are identical to the 45°C systems which had received a prior one-day treatment at 5°C. The duration of the experiments has very little effect upon the equilibrium distribution, as evidenced by the fact that the results obtained by longterm equilibrations at both temperatures and for both ions were nearly identical to those shown in Table III. Most important however is the finding that the equilibrium levels of cobalt and zinc at 5°C are significantly higher than these which are obtained after a 45°C treatment. This indicates that the 5°C distribution over the various possible sites, as induced by a 45°C pretreatment, differs from the normal low-temperature distribution in that a significant portion of the adsorbed bivalent ions which participate in the 45°C equilibrium no longer do so at 5°C. In other words, when returned to 5°C, part of the solid-phase metal ions appear irreversibly sequestered in sites where they are out of reach at low temperature. 

FIGURE 2.2 The equilibrium distribution of cobalt ions as a function of equilibrium cobalt ion concentration for cobalt-calcium ion exchange at a constant pH value. T = 33°C pH 6.5. (Reprinted from Nagy et al. 1997, with permission from Elsevier.)... 

The adsorption of hydrolyzing ions Cr and Co on siUca gel was investigated [78], and speciation of mononucleus hydroxy species in the equiUbrium aqueous phase was also considered to calculate the equilibrium distribution between the soUd phase and bulk solution over the broad range of pH s. Although the different surface complexes of chromium and cobaltic assumed to form on surface sites of silica were not proved by any independent method, the fitting procedure was executed successfully, if only all the possible equilibria were accounted for in the SCMs. 

For TIOA with hydrochloric acid the concentration-based equilibrium constant for salt formation" according to reaction (8.2-6) is 1.51 x 10 and the equilibrium constant for amine-hydrochloride salt dimerization" is 8.0 M Combination of these parameters and the ion-complex stability constants with experimental metal-distribution data allows determination of the equilibrium constants for reactions (8.2-5) or (8.2-7). This completes the description of the amine-metal extraction-phase equilibria. For cobalt(II) in acidic sodium chloride solutions the equilibrium constant" for reaction (8.2-7) with TIOA is 2.0 X 10 and that for coppeifll) is 370 The corresponding value for zinc" is 7.5 x 10 Af -In spile of these relative values, the order of selectivity of TIOA for extraction of the metals is Zn > Cu > Co because of the relative extent of chloride complex formation. For the same reason, zinc stripping is difficult in this system, and copper has a tendency to be reduced to cuprous, which also complexes and extracts extensively. 

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