Abstract: The flow injection technique is shown to provide fast, reliable and sensitive determination of solubility product constants of silver acetate, silver sulfate, silver oxide, silver bromate and silver chloride in microliter volume samples. Potentiometric detection using electrodes of the first kind and second kind was used for measuring silver ions and chloride ions, respectively. The solubilities were determined from measurement of the silver ion concentration in the saturated solutions. In the case of silver chloride, the solubility product constant was calculated from the concentrations corresponding to the intersection of the silver ion calibration curve and the chloride ion calibration curve, i.e., where the potentials of the two electrodes are equal. Tenth-molar sodium nitrate was used for all solutions to maintain constant ionic strength. At a concentration range of 1.00 x 10-2 - 1.00 x 10-5 M silver, and 1.00 x 10-2 - 1.00 x 10-4 M chloride, a Nernstian response of 60 m V per decade was obtained. At a sampling rate of 50-70 samples per hour, with 50 µl sample injections, high reproducibility of measurements was achieved, with a pL 2% relative standard deviation in measured concentrations. The scope and applications of this system are discussed.