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....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.展开更多
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...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 (Vorg/V) between water and oDCBz phases, where “org” shows an organic phase. Simultaneously, an analytic equation with the Vorg/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(C6H5) 4 (=NaBPh4) one into NB and DCE were studied at 298 K under the conditions of various Vorg/V values. So, extraction constants (Kex) for MPic into the org phases, their ion-pair formation constants (KMA,org) for MA = MPic in the org ones, and standard distribution constants () 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 Kex (NaA), KNaA,org, and values were done at A-=BPh-4. Here, the symbols Kex, KMA,org, and or 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 Kex and KMPic,org were examined at M = Li(I)-K(I) and org = oDCBz. From above, the conditional distribution constants, KD,BPh4 and KD,Cs, were classified by checking the experimental conditions of the I, Iorg, and dep values.展开更多
CdI2 in water was extracted with 18-crown-6 ether (L) into 10 diluents at 298 K. The following equilibrium constants were determined or evaluated: some extraction constants (Kex/mol-3·dm9 & Kex,ip/mol-2·...CdI2 in water was extracted with 18-crown-6 ether (L) into 10 diluents at 298 K. The following equilibrium constants were determined or evaluated: some extraction constants (Kex/mol-3·dm9 & Kex,ip/mol-2·dm6 for CdLI2, Kex±/mol-2·dm6 for CdLI+ with I-, & Kex2±/mol-1·dm3 for CdL2+ with 2I-), conditional distribution constants (KD,I for I-, KD,CdLI for CdLI+, & KD,CdL for CdL2+) between the two phases, and an ion-pair formation constant (K1,org/mol-1·dm3) for CdLI+ and that (K2,org/mol-1·dm3) for CdLI2 in the organic (org) phases. Using the K1,org and K2,org values, acidities of the complex ions, CdL2+ and CdLA+ (A- = I-, Br-, & Cl-), in the 11 diluents were classified by applying the HSAB rule. Especially, the CdLA+ ions were classified as the soft acids in 9 diluents. Also, molar volumes (Vj/cm3·mol-1) of j = CdLI2 and CdL2+ were determined with the regular-solution-theory plot of logKex,ip vs. logKD,L and its pseudo-plot of logKD,CdL, respectively. Here, KD,L denotes the distribution constant of L between the two phases. So, sizes among CdLA2 and CdL2+ were compared by using the Vj values. Additionally, some distribution equilibrium potentials (dep/V) between the water and org bulk phases were topically calculated from an equation of KD,I with KSD,I, where the symbol KSD,I shows a standard distribution constant of I- at dep = 0 V for a given diluent.展开更多
文摘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.
文摘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 (Vorg/V) between water and oDCBz phases, where “org” shows an organic phase. Simultaneously, an analytic equation with the Vorg/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(C6H5) 4 (=NaBPh4) one into NB and DCE were studied at 298 K under the conditions of various Vorg/V values. So, extraction constants (Kex) for MPic into the org phases, their ion-pair formation constants (KMA,org) for MA = MPic in the org ones, and standard distribution constants () 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 Kex (NaA), KNaA,org, and values were done at A-=BPh-4. Here, the symbols Kex, KMA,org, and or 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 Kex and KMPic,org were examined at M = Li(I)-K(I) and org = oDCBz. From above, the conditional distribution constants, KD,BPh4 and KD,Cs, were classified by checking the experimental conditions of the I, Iorg, and dep values.
文摘CdI2 in water was extracted with 18-crown-6 ether (L) into 10 diluents at 298 K. The following equilibrium constants were determined or evaluated: some extraction constants (Kex/mol-3·dm9 & Kex,ip/mol-2·dm6 for CdLI2, Kex±/mol-2·dm6 for CdLI+ with I-, & Kex2±/mol-1·dm3 for CdL2+ with 2I-), conditional distribution constants (KD,I for I-, KD,CdLI for CdLI+, & KD,CdL for CdL2+) between the two phases, and an ion-pair formation constant (K1,org/mol-1·dm3) for CdLI+ and that (K2,org/mol-1·dm3) for CdLI2 in the organic (org) phases. Using the K1,org and K2,org values, acidities of the complex ions, CdL2+ and CdLA+ (A- = I-, Br-, & Cl-), in the 11 diluents were classified by applying the HSAB rule. Especially, the CdLA+ ions were classified as the soft acids in 9 diluents. Also, molar volumes (Vj/cm3·mol-1) of j = CdLI2 and CdL2+ were determined with the regular-solution-theory plot of logKex,ip vs. logKD,L and its pseudo-plot of logKD,CdL, respectively. Here, KD,L denotes the distribution constant of L between the two phases. So, sizes among CdLA2 and CdL2+ were compared by using the Vj values. Additionally, some distribution equilibrium potentials (dep/V) between the water and org bulk phases were topically calculated from an equation of KD,I with KSD,I, where the symbol KSD,I shows a standard distribution constant of I- at dep = 0 V for a given diluent.
