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This paper describes the theoretical basis of a new program for refinement of complex stability constants together with the other parameters of various protometric titrations. The method is based on minimization of the sum of the weighted squares of the residuals of the experimental variables reagent volume and E or pH. A new exploitation of mathematical relations allows simultaneous refinement of the various parameters and unknown free ion concentrations. After convergence, the program PROTAF also provides the adjusted values of experimental variables.