History
Jannik 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, Mn+, 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
- H + L HL
- M + L ML
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.
- M + qL MLq
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.
Read more about this topic: Stability Constants Of Complexes
Famous quotes containing the word history:
“Let us not underrate the value of a fact; it will one day flower in a truth. It is astonishing how few facts of importance are added in a century to the natural history of any animal. The natural history of man himself is still being gradually written.”
—Henry David Thoreau (1817–1862)
“We are told that men protect us; that they are generous, even chivalric in their protection. Gentlemen, if your protectors were women, and they took all your property and your children, and paid you half as much for your work, though as well or better done than your own, would you think much of the chivalry which permitted you to sit in street-cars and picked up your pocket- handkerchief?”
—Mary B. Clay, U.S. suffragist. As quoted in History of Woman Suffrage, vol. 4, ch. 3, by Susan B. Anthony and Ida Husted Harper (1902)
“The custard is setting; meanwhile
I not only have my own history to worry about
But am forced to fret over insufficient details related to large
Unfinished concepts that can never bring themselves to the point
Of being, with or without my help, if any were forthcoming.”
—John Ashbery (b. 1927)