On an Expression of Extraction Constants without the Interfacial Equilibrium-Potential Differences for the Extraction of Univalent and Divalent Metal Picrates by Crown Ethers into 1,2-Dichloroethane and Nitrobenzene

An idea on interfacial equilibrium-potential differences () which are generated for the extraction of univalent metal picrate (MPic) and divalent ones (MPic2) by crown ethers (L) into high-polar diluents was improved. These potentials were clarified with some experimental extraction-data reported before on the M = Ag(I), Ca(II), Sr(II) and Ba(II) extraction with 18-crown-6 ether (18C6) and benzo-18C6 into 1,2-dichloroethane (DCE) and nitrobenzene (NB). Consequently, it was demonstrated that the? values from the extraction-experimentally obtained logKD,Pic ones are in agreement with or close to those calculated from charge balance equations in many cases, where the symbol, KD,Pic, denotes an individual distribution constant of Pic﹣ into the DCE or NB phase. Also, it was experimentally shown that extraction constants based on the overall extraction equilibria do not virtually contain the? terms in their functional expressions.

An Electrochemical Understanding of Extraction of Silver Picrate by Benzo-3<i>m</i>-Crown-<i>m</i>Ethers (<i>m</i>= 5, 6) into 1,2-Dichloroethane and Dichloromethane

Two extraction constants (Kex± and Kex) for extraction of silver picrate (Ag﹢Pic﹣) by benzo-15-crown-5 ether (B15C5) and benzo-18-crown-6 one (B18C6) into 1,2-dichloroethane (DCE) and dichloromethane (DCM) were determined at 298 K and given values of ionic strength. Here, Kex± and Kex were expressed as [AgL﹢]o[Pic﹣]o/[Ag﹢][L]o[Pic﹣] and [AgLPic]o/[Ag﹢][L]o[Pic﹣], respectively: L symbolizes B15C5 or B18C6 and the subscript “o” denotes the organic phase composed of DCE or DCM. Individual distribution constants (KD,Pic) of picrate ion, Pic﹣, into the two diluents were also determined with the determination of Kex. From comparison of these KD,Pic values with those standardized, interfacial potential differences () at extraction equilibria were evaluated. Then, using these values, relations of the experimentally-determined logKex± or logKex values with their electrochemically-standardized ones were precisely discussed. Consequently, it was indicated that logKex± should be expressed as a function of .

Elucidation of Abnormal Potential Responses of Cation-Selective Electrodes with Solid-State Membranes to Aqueous Solutions of CuCl2 and CdI2

An empirical solution to abnormal potential responses, showing peaks of emf, of commercial Cu2+- and Cd2+-selective electrodes with solid-state membranes was proposed for aqueous solutions of CuCl2 and CdI2. The two-step processes of Mn+ + Yn? (s: solid phase) MY(s) and MY(s) + 2X? X2MY2?(s) (n = 1, 2) at a test solution/electrode-interface were considered as a model. Here, Mn+, Yn?, and X? refer to a divalent or univalent cation, functional groups of electrode materials, and a halide ion (X? = Cl?, Br?, I?), respectively. By applying electrochemical potentials to these processes at n = 2, we derived an equation. Regression analyses based on the equation reproduced well the plots of emf versus log 2(*[M]t) for the Cd(II) and Cu(II) systems: *[M]t denotes a total concentration of species relevant to M2+ in a bulk of the aqueous solution. Also, we obtained log Ks(CdBr2) = 4.28 ? 0.22, log Ks(CdI2) = 6.98 ? 0.05, log Ks(CuCl2) = 3.96 ? 0.09, and log Ks(CuBr2) = 11.4 at 25?C. The magnitude in ?log Ks reflected that in the logarithmic solubility product, log {*[M2+](*[X?])2}, for bulk water, where *[M2+] or *[X?] denotes a molar concentration of the bulk solu-tion of M2+ or X? at equilibrium, respectively. Moreover, a mixture of CuSO4 with NaCl at the molar ratio of 1:1 yielded a plot similar to that of CuCl2.