an ion is an ion
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
⇋
H
L
{\displaystyle \mathrm {H+L} \leftrightharpoons \mathrm {HL} }
M
+
L
⇋
M
L
{\displaystyle \mathrm {M+L} \leftrightharpoons \mathrm {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
+
q
L
⇋
M
L
q
{\displaystyle \mathrm {M} +q\mathrm {L} \leftrightharpoons \mathrm {ML} _{q}}
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.
Chelation is a type of bonding of ions and their molecules to metal ions. It involves the formation or presence of two or more separate coordinate bonds between a polydentate (multiple bonded) ligand and a single central metal atom. These ligands are called chelants, chelators, chelating agents, or sequestering agents. They are usually organic compounds, but this is not a necessity.
The word chelation is derived from Greek χηλή, chēlē, meaning "claw"; the ligands lie around the central atom like the claws of a crab. The term chelate was first applied in 1920 by Sir Gilbert T. Morgan and H. D. K. Drew, who stated: "The adjective chelate, derived from the great claw or chele (Greek) of the crab or other crustaceans, is suggested for the caliperlike groups which function as two associating units and fasten to the central atom so as to produce heterocyclic rings."
Comments
Post a Comment