Potentiometric Determination of Non-Ionic Surfactants by Liquid Membrane Electrodes

• Published in: Electroanalysis (New York, N.Y.) N.Y.), 2003-10, Vol.15 (20), p.1598-1605
• Main Authors: Giannetto, Marco, Minari, Claudia, Mori, Giovanni
• Format: Article
• Language: English
• Subjects: Ca/Mg ISEs; Liquid membrane ion selective electrodes; Non-ionic surfactants; Seawater; Tegopren 5863
• ISSN: 1040-0397; 1521-4109
• DOI: 10.1002/elan.200302727

It is well known that non‐ionic surfactants (NIS) influence remarkably the potentiometric measurements with liquid membrane ion selective electrodes (ISEs), interfering particularly on performance of ISEs for earth‐alkali metals, for which the loss of selectivity with regard to alkali metals has been documented. These studies indicate that such interferences are due to the extraction of surfactants within the membrane, where a competition takes place between the originally present ionophore and the surfactant which also acts as a ligand for alkali metals. The interpretation of such phenomena enabled one to exploit this interference for analytical purposes by membrane/solution extraction experiment monitored by UV measurements and by impedance FRA analysis on coated wire electrodes. Using Ca/Mg ISEs based on the neutral ionophore ETH 4030, it has been established that the logarithm of the Ca/Mg over Na potentiometric selectivity constant is linearly correlated with the concentration of NIS like Tegopren 5863 and Triton X‐100. The proposed method has been applied for the development of a new potentiometric analytical procedure for the determination of Tegopren 5863 in synthetic seawater (SSW), ranging from 0.25 to 5 ppm. Our procedure consists in the exposure of the electrode to stirred SSW containing the surfactant; the progressive extraction of Tegopren 5863 causes a growth in electrode's sensitivity to Na+ and K+, losing selectivity for Ca2+ and Mg2+. In turn this induces an increase of EMF, as all these ions are present in the studied matrix. The potential drift was monitored for 15 hours, showing that the process reaches thermodynamic equilibrium after about 12 hours of exposure. This method presents a value of 210 ppb of Tegopren 5863 as detection limit.