FTIR-ATR-spectroscopic analysis of Bis-Crown ether based PVC-membranes - III. In situ spectroscopic and electrochemical methods to study surface and bulk membrane processes


To get more information on the phase boundary and bulk membrane processes, the short and long time behaviour of potassium selective solvent polymeric membranes was studied. In parallel with the measurement of the dynamic response of model membranes, in situ spectroscopic measurements applying the Attenuated Total Reflection (ATR) technique in the infrared region, were carried out in solutions containing anions of different lipophilicity (Cl- and SCN-). Thin membranes (thinner than the penetration depth of IR beam) coated on the germanium reflection element by the dipping technique show no time dependence of the SCN bands in contact with KSCN solution of different concentrations, while the diffusion process of species can be monitored in thick membranes as it was shown in a time resolved study. The extremely short response times of ionophore based solvent polymeric membranes (determined under appropriate experimental conditions in this work) imply that the fundamental potential determining step of the overall response of this type of electrodes is a phase boundary process. Thus the slow inner membrane diffusion process followed by IR spectroscopy on the molecular level may affect only the long-term membrane behaviour. © 1988 Springer-Verlag.

Publication Title

Fresenius' Zeitschrift für Analytische Chemie