Semiautomatic indirect titration of alkaline-earth ions with catalytic endpoint indication

A semiautomatic spectrophotometric method of endpoint indication for indirect catalytic titrations of microamounts of alkaline-earth ions is described. The manganese(II)-catalyzed autoxidation of 1,4-dihydroxyphthalimide dithiosemicarbazone is used as indicator reaction. Calcium and magnesium (10–150 μg), strontium (20–250 μg), and barium (20–450 μg) can be determined by adding a known excess of EDTA to the sample solution and back-titrating the unconsumed inhibitor agent with standard manganese(II) solution. This catalytic method was applied to determine the total concentration in calcium and magnesium (total hardness) in natural waters and milk. The method is fast, accurate (1–3%), precise (0.2–0.8%, relative standard deviation), and specially useful for the determination of microamounts where metallochromic indicator are ineffective (for concentrations ranges below 10^?4M).