Distribution of Ag(I), Li(I)-Cs(I) Picrates, and Na(I) Tetraphenylborate with Differences in Phase Volume between Water and Diluents

Abstract

Ionic strength conditions in distribution experiments with single ions are very important for evaluating their distribution properties. Distribution experiments of picrates (MPic) with M = Ag(I) and Li(I)-Cs(I) into o-dichlorobenzene (oDCBz) were performed at 298 K by changing volume ratios (V org /V) between water and oDCBz phases, where "org" shows an organic phase. Simultaneously, an analytic equation with the V org /V variation was derived in order to analyze such distribution systems. Additionally, the AgPic distribution into nitrobenzene (NB), dichloromethane, and 1,2-dichloroethene (DCE) and the NaB(C 6 H 5 ) 4 (=NaBPh 4 ) one into NB and DCE were studied at 298 K under the conditions of various V org /V values. So, extraction constants (K ex ) for MPic into the org phases, their ion-pair formation constants (K MA,org ) for MA = MPic in the org ones, and standard distribution constants ( S D,M K ) for the M(I) transfers between the water and org bulk phases with M = Ag and Li-Cs were determined at the distribution equilibrium potential (dep) of zero V between the bulk phases and also the K ex (NaA), K NaA,org , and S D,A K values were done at 4 A BPh − − = . Here, the symbols K ex , K MA,org , and S D,M K or S D,A K were defined as [MA] org /[M + ][A − ], [MA] org /[M + ] org [A − ] org , and [M + ] org /[M + ] or [A − ] org /[A − ] at dep = 0, respectively. Especially, the ionic strength dependences of K ex and K MPic,org were examined at M = Li(I)-K(I) and org = oDCBz. From above, the conditional distribution constants, K D,BPh4 and K D,Cs , were classified by checking the experimental conditions of the I, I org , and dep values. BPh − into some diluents. The S D,Ag K values were obtained from NB, DCE, oDCBz, and dichloromethane (DCM) systems with the reported S D,Pic K value [5] [8] [11] of picrate ion (Pic − ), the S D, j K values at j = Li + -Cs + from oDCBz one with that [5] of Pic − , and the S D,BPh4 K values from NB and DCE ones with the S D,Na K value [8] of Na + . In the experiments corresponding to the above systems, volume ratios (=V org /V = r org/w ) of the both phases were changed and accordingly an equation for analyzing such systems was derived; V org and V refer to an experimental volume (L unit) of the org phase and that of the w one, respectively. Also, the K ex , K MA,org , and K D,MA values were obtained at 298 K from the same combinations of M + A − and the diluents. Here, the symbols K ex , K MA,org , and K D,MA were defined as [MA] org /[M + ][A − ], [MA] org /[M + ] org [A − ] org , and [MA] org /[MA], respectively. Moreover, extraction, ion-pair formation, and distribution properties for the above systems were S. Ikeda et al.