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Studies on the effect of the cation nature on the kinetics of the isotopic exchange reaction between chloride ion and O , O ‐diphenylphosphorochloridothionate in acetonitrile
Author(s) -
Reimschüssel W.,
Tilk S.,
Mikołajczyk M.,
Ślebockatilk H.
Publication year - 1981
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550130408
Subject(s) - chemistry , acetonitrile , reaction rate constant , kinetics , chloride , ion , inorganic chemistry , lithium chloride , dissociation (chemistry) , kinetic isotope effect , salt (chemistry) , lithium (medication) , medicinal chemistry , deuterium , organic chemistry , medicine , physics , quantum mechanics , endocrinology
Rate constants and activation parameters for the isotopic exchange reactions between (PhO) 2 PSCl and M 36 Cl (M = Me 4 N + , Et 4 N + , n ‐Bu 4 N + , Et 3 HN + , EtH 3 N + , Li + ) in acetonitrile were measured in order to find the effect of the cation nature onthe kinetics of the reaction. The rate constants measured for a range of concentrations of Et 3 HN 36 Cl, EtH 3 N 36 Cl, and Li 36 Cl were analyzed using the Acree equation. The equivalent conductance of LiCl in acetonitrile was determined. The nature of the cation has no effect on the mechanism of the reaction. The cation changes only the experimental rate constant proportionally to the dissociation degree of the salt. Smaller values of the rate constant and smaller activation parameters Δ H ‡ and Δ S ‡ for the reaction with Li 36 Cl indicate the existenceof the intermolecular interaction between lithium ions and O , O ‐diphenylphosphorochloridothionate.