Characterisation of an optical sensor membrane based on the metal ion indicator Pyrocatechol Violet

A non-specific photometric metal ion indicator Pyrocatechol Violet (PV) was tested for its potential use in a metal-sensitive optrode membrane. The water soluble indicator was lipophilised in the form of an ion pair with tetraoctylammonium cation (TOA), and subsequently immobilised in a plasticised PVC membrane. The spectral response of the membrane in the presence of various transition metal ions was studied. It was found that the ability of PV to form complexes with metal ions significantly reduced following immobilisation, with the exception of Cu(II). A number of factors responsible for the improved selectivity and high sensitivity of immobilised PV towards Cu(II) were identified. Amongst those, the most important is the presence of quaternary ammonium salt in the membrane which induced a significant bathochromic shift of the PV–Cu(II) chelate absorption maximum, as well as the intensification of the chelate absorption band. The membrane responds to Cu(II) irreversibly by changing colour from yellow to green (absorption maximum at 740 nm), and typically, an exposure time of 10 min enables the determination of Cu(II) in the 1–100 μM range. A comparison of selectivity and sensitivity characteristics between the water soluble form of the indicator and the immobilised form was performed, and the effects of pH and lipophilic surfactant additives on the response mechanism are discussed.