Potentiometric Chemical Sensors Based on Metal Halide Doped Chalcogenide Glasses for Sodium Detection

Abstract

Chalcogenide glasses are widely used as sensitive membranes in the chemical sensors for heavy metal ions detection. The lack of research work on sodium ion-selective electrodes (Na⁺-ISEs) based on chalcogenide glasses is due to the high hygroscopicity of alkali dopes chalcogenides. However, sodium halide doped Ga₂S₃-GeS₂ glasses are more chemically stable in water and could be used as Na⁺-sensitive membranes for the ISEs. In this work we have studied the physico-chemical properties of mixed cation (AgI)_x(NaI)_30-x(Ga₂S₃)₂₆(GeS₂)₄₄ chalcogenide glasses (where x = 0, 7.5, 15, 22.5 and 30 mol.% AgI) using density, DSC, and conductivity measurements. The mixed cation effect with shallow conductivity and glass transition temperature minimum was found for silver fraction r = Ag/(Na + Ag) ≈ 0.5. Silver addition decreases the moisture resistance of the glasses. Only (AgI)_22.5(NaI)_7.5(Ga₂S₃)₂₆(GeS₂)₄₄ composition was suitable for chemical sensors application, contrary to the single cation sodium halide doped Ga₂S₃-GeS₂ glasses, where 15 mol.% sodium-halide-containing vitreous alloys are stable in water solutions. The analytical parameters of (NaCl)₁₅(Ga₂S₃)₂₃(GeS₂)₆₂; (NaI)₁₅(Ga₂S₃)₂₃(GeS₂)₆₂ and (AgI)_22.5(NaI)_7.5(Ga₂S₃)₂₆(GeS₂)₄₄ glass compositions as active membranes in Na⁺-ISEs were investigated, including detection limit, sensitivity, linearity, ionic selectivity (in the presence of K⁺, Mg²⁺, Ca²⁺, Ba²⁺, and Zn²⁺ interfering cations), reproducibility and optimal pH-range.

Keywords: chalcogenide glasses; chemical sensors; conductivity; mixed cations; sodium detection.