Method of determining, with the aid of an ion-selective electrode ion selective electrode the concentration of a substance to be determined, which comprises taking a known volume of a sample, a buffer is added to a sample solution in order to produce a medium in which a potential of the ion selective electrode is directly related to the concentration of a respective ion and, after a set reaction time, an initial potential of the electrode pair including an ion-selective electrode and reference electrode is measured, then a known volume of a solution having an accurately known concentration of the substance to be determined which is a standard solution is added and a change in potential produced is measured, and the concentration of the substance to be determined is calculated therefrom, including the steps of providing that the addition of the standard solution to a reaction mixture is carried out in steps, the first addition being a small one which brings about a change in potential which indicates what the concentration of a substance to be determined is approximately, then further additions are made on the basis of the change in potential produced until a final change in potential is such that it corresponds to an increase in concentration of 1.5 to 10 times the concentration of the substance to be determined which was present in the sample.