Effect of dissolved CO2 on the potential stability of all-solid-state ion-selective electrodes

The influence of dissolved CO2 on the potentiometric responses of all-solid-state ion-selective electrodes (ISEs) was systematically examined with four different types of electrodes fabricated by pairing pH-sensitive and pH-insensitive metal electrodes (Pt and Ag/AgCl, respectively) with pH-sensitive and pH-insensitive ion-selective membranes (H+-selective membrane based on tridodecylamine and Na+-selective membrane based on tetraethyl calix[4]arenetetraacetate, respectively). The experimental results clearly showed that the carbonic acid formed by the diffused CO2 and water vapor at the membrane/metal electrode interface varies the phase boundary potentials both at the inner side of the H+-selective membrane (deltaE(in)mem) and at the metal electrode surface (deltaEelec). The potential changes, deltaE(in)mem and deltaEelec, occurring at the facing boundaries, are opposite in their sign and result in a canceling effect if both the membrane and metal surface are pH-sensitive. Consequently, the H+-selective membrane coated on a pH-sensitive electrode (Pt) tends to exhibit a smaller CO2 interference than that on a pH-insensitive electrode (Ag/AgCl). When the all-solid-state Na+ and K+ ISEs were fabricated with both pH-insensitive metal electrode and ion-selective membrane, they did not suffer from CO2 interference. It was also confirmed that plasticization of the PVC leads to increased CO2 permeation. Various types of intermediate layers were examined to reduce the CO2 interference problem in the fabrication of H+-selective all-solid-state ISEs. The results indicated that the H+-selective electrode needs an intermediate layer that maintains a constant pH unless the carbonic acid formation at the interfacial area is effectively quenched.