RI 8318 Use of Gas Diffusion Membrane Electrodes To Investigate Coordination Species in the Sulfur Dioxide/Citrate System

The ability of potentiometric, gas-sensing electrodes to reliably monitor free gaseous molecules in solution has been recently demonstrated. A gas such as sulfur dioxide from a dilute sample solution diffuses through a hydrophobic, gas-permeable membrane to an internal filling solution. The latter solution contains a sufficiently large excess of sodium bisulfite, the concentration of which can be considered constant regardless of the quantity of sulfur dioxide entering by diffusion. The electrode response is essentially due to the liberated hydrogen ions from the bisulfite-sulfur dioxide equilibrium. This Bureau of Mines report describes a new technique used to detect the formation, and to estimate the stability constant, of gas-molecule and gas-ion complexes in solution, as part of an effort to minimize the undesirable environmental impacts associated with mining and mineral processing. Although the unknown activity coefficients of the neutral and ionic species in the external solution complicate the quantitation of results, methods to circumvent these difficulties are presented. The technique is based on the isometric shift of the Nernst diagram of ion-selective electrodes to higher concentrations relative to the standard aqueous calibration curve. The method is applied to detect and estimate the formation constant of a sulfitocitrate complex, and agrees well with an independently determined stability constant of the disulfitomercu-rate complex.