Jannik Bjerrum (son of Niels Bjerrum) developed the first general method for the determination of stability constants of metal-ammine complexes in 1941. The reasons why this occurred at such a late date, nearly 50 years after Alfred Werner had proposed the correct structures for coordination complexes, have been summarised by Beck and Nagypál. The key to Bjerrum's method was the use of the then recently developed glass electrode and pH meter to determine the concentration of hydrogen ions in solution. Bjerrum recognised that the formation of a metal complex with a ligand was a kind of acid–base equilibrium: there is competition for the ligand, L, between the metal ion, M, and the hydrogen ion, H. This means that there are two simultaneous equilibria that have to be considered. In what follows electrical charges are omitted for the sake of generality. The two equilibria are
Hence by following the hydrogen ion concentration during a titration of a mixture of M and HL with base, and knowing the acid dissociation constant of HL, the stability constant for the formation of ML could be determined. Bjerrum went on to determine the stability constants for systems in which many complexes may be formed.
The following twenty years saw a veritable explosion in the number of stability constants that were determined. Relationships, such as the Irving-Williams series were discovered. The calculations were done by hand using the so-called graphical methods. The mathematics underlying the methods used in this period are summarised by Rossotti and Rossotti. The next key development was the use of a computer program, LETAGROP to do the calculations. This permitted the examination of systems too complicated to be evaluated by means of hand-calculations. Subsequently, computer programs capable of handling complex equilibria in general, such as SCOGS and MINIQUAD were developed so that today the determination of stability constants has almost become a "routine" operation. Values of thousands of stability constants can be found in two commercial databases.