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


Two extraction constants (Kex± and Kex) for extraction of silver picrate (AgPic) 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 .

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Kudo, Y. , Ogihara, M. , Katsuta, S. and Takeda, Y. (2014) An Electrochemical Understanding of Extraction of Silver Picrate by Benzo-3m-Crown-m Ethers (m = 5, 6) into 1,2-Dichloroethane and Dichloromethane. American Journal of Analytical Chemistry, 5, 433-444. doi: 10.4236/ajac.2014.57052.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Kudo, Y., Harashima, K., Katsuta, S. and Takeda, Y. (2011) Solvent Extraction of Sodium Permanganate by Mono-Benzo 3m-Crown-m Ethers (m = 5, 6) into 1,2-Dichloroethane and Nitrobenzene: A Method Which Analyzes the Extraction System with the Polar Diluents. International Journal of Chemistry, 3, 99-107.
[2] Kudo, Y., Horiuchi, N., Katsuta, S. and Takeda, Y. (2013) Extraction of Cadmium Bromide and Picrate by 18-Crown-6 Ether into Various Less-Polar Diluents: Analysis of Overall Extraction Equilibria Based on Their Component Equilibria with Formation of Their Ion Pairs in Water. Journal of Molecular Liquids, 177, 257-266.
[3] Kudo, Y., Takahashi, Y., Numako, C. and Katsuta, S. (2014) Extraction of Lead Picrate by 18-Crown-6 Ether into Various Diluents: Examples of Sub-Analysis of Overall Extraction Equilibrium Based on Component Equilibria. Journal of Molecular Liquids, 194, 121-129.
[4] Levitskaia, T.G., Maya, L., Van Berkel, G.J. and Moyer, B.A. (2007) Anion Partitioning and Ion-Pairing Behavior of Anions in the Extraction of Cesium Salts by 4,5”-Bis(tert-ocytlbenzo)dibenzo-24-Crown-8 in 1,2-Dichloroethane. Inorganic Chemistry, 46, 261-272.
[5] Markin, V.S. and Volkov, A.G. (1989) The Gibbs Free Energy of Ion Transfer between Two Immiscible Liquids. Electrochimica Acta, 34, 93-107.
[6] Kudo, Y., Harashima, K., Hiyoshi, K., Takagi, J., Katsuta, S. and Takeda, Y. (2011) Extraction of Some Univalent Salts into 1,2-Dichloroethane and Nitrobenzene: Analysis of Overall Extraction Equilibrium Based on Elucidating Ion-Pair Formation and Evaluation of Standard Potentials for Ion Transfers at the Interfaces between Their Diluents and Water. Analytical Sciences, 27, 913-919.
[7] Rais, J. (1971) Individual Extraction Constants of Univalent Ions in the System Water-Nitrobenzene. Collection of Czechoslovak Chemical Communications, 36, 3253-3262.
[8] Kakiuchi, T. (1996) Partition Equilibrium of Ionic Components in Two Immiscible Electrolyte Solutions. In: Volkov, A.G. and Dreamer, D.W., Eds., Liquid-Liquid Interfaces Theory and Methods, CRC Press, Boca Raton, Chapter 1.
[9] Takeda, Y., Ezaki, T., Kudo, Y. and Matsuda, H. (1995) Distribution Study on Electroneutral and Protonated Amino Acids between Water and Nitrobenzene. Determination of the Standard Ion-Transfer Potentials of Protonated Amino Acids. Bulletin of the Chemical Society of Japan, 68, 787-790.
[10] Bard, A.J. and Faulkner, L.R. (2001) Electrochemical Method: Fundamentals and Applications. 2nd Edition, John Wily & Sons, Inc., New York, 60-62.
[11] Marcus, Y. (1983) Thermodynamic Functions of Transfer of Single Ions from Water to Nonaqueous and Mixed Solvents: Part 1-Gibbs Free Energies of Transfer to Nonaqueous Solvents. Pure & Applied Chemistry, 55, 977-1021.
[12] Kudo, Y., Katsuta, S. and Takeda, Y. (2012) Evaluation of Overall Extraction Constants for the Crown Ether-Complex Ions of Alkali and Alkaline-Earth Metal with Counter Picrate Ions from Water into Nitrobenzene Based on Their Component Equilibrium Constants. Journal of Molecular Liquids, 173, 66-70.
[13] Takeda, Y. (2002) Extraction of Alkali Metal Picrates with 18-Crown-6, Benzo-18-Crown-6, and Dibenzo-18-Crown-6 into Various Organic Solvents. Elucidation of Fundamental Equilibria Governing the Extraction-Ability and -Selectivity. Bunseki Kagaku (Analytical Chemistry), 51, 515-525.
[14] Kudo, Y., Usami, J., Katsuta, S. and Takeda, Y. (2004) Solvent Extraction Silver Picrate by 3m-Crown-m Ethers (m = 5, 6) and Its Mono-Benzo Derivative from Water into Benzene or Chloroform: Elucidation of an Extraction Equilibrium Using Component Equilibrium Constants. Talanta, 62, 701-706.
[15] Kudo, Y., Takahashi, Y. and Katsuta, S. (2013) Distribution of Picric Acid into Various Diluents. Journal of Chemistry, 2013, Article ID: 896506.
[16] Kudo, Y., Takeda, Y. and Matsuda, H. (1991) Ion-Transfer-Polarographic Study of Distribution Equilibrium of Metal Complex Cations with Several Crown Ethers between Nitro-benzene and Water. Bunseki Kagaku (Analytical Chemistry), 40, 779-784.
[17] Kudo, Y., Miyakawa, T., Takeda, Y. and Matsuda, H. (1996) Ion-Transfer Polarographic Study of the Distribution of Alkali and Alkaline-Earth Metal Complexes with 3m-Crown-m Ether Derivatives (m = 6, 8) between Water and Nitrobenzene Phases. Journal of Inclusion Phenomena and Molecular Recognition in Chemistry, 26, 331-341.
[18] Makrlík, E., Vaňura, P. and Daňková, N. (1999) Contribution of the Thermodynamics of Complexes of Alkali Metal Cation with 18-Crown-6 in the Water-Nitrobenzene System. Journal of Radioanalytical and Nuclear Chemistry, 240, 579-583.

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