Abstract
Thermodynamics and kinetics of hydrophilic ion transfers across water|n-octanol (W|OCT) interface have been electrochemically studied by means of novel three-phase and thin-film electrodes. Three-phase electrodes used for thermodynamics measurements comprise edge plane pyrolytic graphite, the surface of which was partly modified with an ultrathin film of OCT, containing hydrophobic lutetium bis(tetra-tert-butylphthalocyaninato) (Lu[tBu4Pc]2) as a redox probe. The transfers of anions and cations from W to OCT were electrochemically driven by reversible redox transformations of Lu[tBu4Pc]2 to chemically stable lipophilic monovalent cation \({\left( {{\text{Lu}}{\left[ {t{\text{Bu}}_{4} {\text{Pc}}} \right]}^{ + }_{2} } \right)}\) and anion \( {\left( {{\text{Lu}}{\left[ {t{\text{Bu}}_{{\text{4}}} {\text{Pc}}} \right]}^{{\,\, - }}_{2} } \right)} \), respectively. Upon reduction of Lu[tBu4Pc]2, the transfers of alkali metal cations from W to OCT have been studied for the first time, enabling estimation of their Gibbs transfer energies. For kinetic measurements, a thin-film electrode configuration has been used, consisting of the same electrode covered completely with a thin layer of OCT that contained the redox probe and a suitable electrolyte. Combining the fast and sensitive square-wave voltammetry with thin-film electrodes, the kinetics of \( {\text{ClO}}^{{\,\, - }}_{4} \), \( {\text{NO}}^{{\,\,{\text{ - }}}}_{{\text{3}}} \), and Cl− transfers have been estimated.
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Reymond F (2001) In: Volkov AG (ed) Liquid interfaces in chemical, biochemical and pharmaceutical applications. Marcel Dekker, New York, pp 733
Zhao YH, Abraham MH (2005) J Org Chem 70:2633
Leo A, Hansch C, Elkins D (1971) Chem Rev 71:525
Girault HH, Schiffrin DJ (1989) In: Bard AJ (ed) Electroanalytical chemistry, vol 15. Marcel Dekker, New York, pp 1–141
Gulaboski R, Mirčeski V, Scholz F (2002) Electrochem Commun 4:277
Scholz F, Komorsky-Lovrić Š, Lovrić M (2000) Electrochem Commun 2:112
Komorsky-Lovrić Š, Riedl K, Gulaboski R, Mirčeski V, Scholz F (2002) Langmuir 18:8000
Gulaboski R, Galland A, Bouchard G, Caban K, Kretschmer A, Carrupt P, Stojek Z, Girault HH, Scholz F (2004) J Phys Chem B 108:4565
Bouchard G, Galland A, Carrupt P-A, Gulaboski R, Mirčeski V, Scholz F, Girault HH (2003) Phys Chem Chem Phys 5:3748
Scholz F (2006) Annu Rep Prog Chem C 102:43
Scholz F, Gulaboski R (2005) Faraday Discuss 129:169
Quentel F, Mirčeski V, L’Her M (2005) J Phys Chem B 109:1262
Quentel F, Mirčeski V, L’Her M, Mladenov M, Scholz F, Elleouet C (2005) J Phys Chem B 109:13228
Quentel F, Mirčeski V, L’Her M (2005) Anal Chem 77:1939
Mirčeski V, Quentel F, L’Her M, Pondaven A (2005) Electrochem Commun 7:1122
Gulaboski R, Mirčeski V, Pereira CM, Cordeiro MNDS, Silva AF, Quentel F, L’Her M, Lovric M (2006) Langmuir 22:3404
Pondaven A, Cozien Y, L’Her M (1992) New J Chem 16:711
L’Her M, Pondaven A (2003) In: Kadish KM, Smith KM, Guilard R (eds) The porphyrin handbook, vol 16, phtalocyanines: spectroscopic and electrochemical characterization. Academic Press, pp 177–170
Scholz F, Gulaboski R, Caban K (2003) Electrochem Commun 5:929
Lovrić M (2002) In: Scholz F (ed) Electroanalytical methods, guide to experiments and applications. Springer, Berlin Heidelberg New York, pp 111–133
De Ligny CL, Alfenaar M, Van Der Veen NG (1968) Rec Trav Chim Pays-Bas 87:585
Marcus Y (1997) Ion properties. Marcel Dekker, New York
Osakai T, Ogata A, Ebina K (1997) J Phys Chem B 101:8341
Mirčeski V (2004) J Phys Chem B 108:13719
Mirčeski V, Gulaboski R, Scholz F (2004) J Electroanal Chem 566:351
Acknowledgment
The authors acknowledge the framework of French–Macedonian Integrated Action (Integrafm 2006) for a financial support. V. Mirčeski also acknowledges the financial support of A. V. Humboldt-Stiftung.
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Dedicated to Professor Dr. Yakov I. Tur’yan on the occasion of his 85th birthday.
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Quentel, F., Mirčeski, V. & L’Her, M. Electrochemical study of the thermodynamics and kinetics of hydrophilic ion transfers across water | n-octanol interface. J Solid State Electrochem 12, 31–39 (2008). https://doi.org/10.1007/s10008-007-0363-8
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DOI: https://doi.org/10.1007/s10008-007-0363-8