kinetic electrolyte effect (kinetic ionic-strength effect)

Also contains definitions of: primary kinetic electrolyte effect, secondary kinetic electrolyte effect
The general effect of an added electrolyte (i.e. an effect other than, or in addition to, that due to its possible involvement as a reactant or @C00876@) on the observed @O04322@ of a reaction in solution. At low concentrations (when only long-range coulombic forces need to be considered) the effect on a given reaction is determined only by the @I03180@ of the solution and not by the chemical identity of the ions. For practical purposes, this concentration range is roughly the same as the region of validity of the @D01533@–Hückel limiting law for activity coefficients. At higher concentrations, the effect of an added electrolyte depends also on the chemical identity of the ions. Such specific action can usually be interpreted as the incursion of a @R05174@ involving an ion of the electrolyte as reactant or @C00876@, in which case the action is not properly to be regarded just as a kinetic electrolyte effect. Kinetic electrolyte effects are usually (too restrictively and therefore incorrectly) referred to as 'kinetic @S05447@ effects'. A kinetic electrolyte effect ascribable solely to the influence of the @I03180@ on activity coefficients of ionic reactants and transition states is called a 'primary kinetic electrolyte effect'. A kinetic electrolyte effect arising from the influence of the @I03180@ of the solution upon the @P04810@ concentration of an ionic species that is involved in a subsequent @R05140@ of a reaction is called a 'secondary kinetic electrolyte effect'. A common case encountered in practice is the effect on the concentration of hydrogen ion (acting as @C00876@) produced from the @I03183@ of a weak acid in a buffer solution. Synonymous with @K03403@.
See also:
common-ion effect
order of reaction
kinetic ambiguity
PAC, 1994, 66, 1077. (Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994)) on page 1133 [Terms] [Paper]