It is well known that the reactions of crown ethers (Ls) with alkali, alkaline-earth metal ions and other cations in water (w) and various organic (o) solvents give complex ions which have various stabilities. 1,2 We have determined the stability constants of these complex ions by ion-transfer polarographic measurements. [3][4][5] In one of these studies, the DeFord-Hume method was applied for the analysis of polarographic waves 6,7 arising from ion transfer facilitated by L across a w/nitrobenzene (NB)-interface. Then, the overall stability constants of 1:1 and 1:2 (metal to ligand) complexes in the NB solution saturated with water were determined using Cs + and dibenzo-18-crown-6 ether (DB18C6). 3 The determinations of the stability constants were controlled by the following conditions: theoretically examined the determination methods of the stability constants and stoichiometry of the 1:p complexes with Ls, which are in limiting cases, i.e., KD,L = 10 -3 and ≥ 10 3 , in the o-phase, and then verified the methods for p = 1 to 4 by cyclic voltammetric experiments. 9 The studies described above were based on the experimental condition that Ls are highly soluble either in the o-phase or in the w-phase. Hence, it is interesting to examine the determination method of successive formation constants of the complexes in the o-phase while using Ls with intermediate KD,L values.In the present work, we examined the ion transfer of Rb + and Cs + at a w/NB-interface facilitated by benzo-15-crown-5 ether (B15C5) and benzo-18-crown-6 one (B18C6), and then determined at 25˚C the overall stability constants (βp NB /mol -p dm 3p ) of 1:p complexes (p = 1, 2) with the Ls in an NB solution saturated with water.
ExperimentalChemicals B18C6 (Tokyo Chemical Industry Co., Ltd.) was recrystallized from hexane and dried in vacuo. 10 B15C5 (Merck-Schuchardt) was dried in vacuo for 8 h before use. Commercial RbCl and CsCl (Merck) were dried in vacuo for 8 h and then kept in a desiccator. Tetrabutylammonium tetraphenylborate (TBA·TPB) was prepared by a previously described method. 3 Nitrobenzene was purified by a method reported by Osakai et al.
11All other chemicals were of analytical grade and were used without further purification.Water purified with Milli-Q Labo (Millipore) was employed to prepare all of the aqueous solutions. The purities of the chlorides were checked by precipitation titration with AgNO3. The aqueous solutions of their chlorides and the NB solutions of Ls were prepared by direct weighing. The NB-and w-phases were saturated with w and NB, respectively, at 25˚C before use.
Electrochemical measurementsIn order to control or measure the potential difference (∆φ) at the NB/w-interface, the following galvanic cell was employed:where the test interface is indicated by an asterisk. The temperature of the cell was controlled at 25 ± 0.5˚C by using a thermostated water bath. The obtained ∆φ values were standardized based on the extrathermodynamic or Ph4As·BPh4 assumption, as described by Rais, 12 and designated as V vs. TPh(A...