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Kinetic Salt Effects and Structure of the Aqueous Solution
Author(s) -
Indelli A.
Publication year - 1971
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.197100048
Subject(s) - chemistry , debye–hückel equation , ion , salt (chemistry) , aqueous solution , thermodynamics , debye , kinetic energy , chemical physics , statistical physics , computational chemistry , classical mechanics , physics , electrode , organic chemistry , electrolyte
The salt effects in many reactions between anions are compared with the predictions of the Brønsted‐Debye theory, and with the assumption of formation of reactive ion pairs; both approaches appear to be inadequate. Clear evidence is available (change of activation energy, effect of organic ions, effect of complex ions) that at least part of the salt effects is non‐electrostatic in nature, so that the introduction of appropriate structural parameters in a general electrostatic treatment is required for their explanation. The Debye‐Hückel theory cannot be used as a frame for the introduction of such parameters, but a more flexible and self‐consistent theory is required. Evidence is presented that the Mayer theory can interpret thermodynamic properties even in cases where the Debye‐Hückel theory fails, and a method is suggested whereby the Mayer theory is used to interpret the salt effect and to give a structural meaning to the empirical parameters which must be introduced.