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 |
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Authors: | W Reimschüssel S Tilk M Mikoajczyk H
lebocka-tilk |
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Institution: | W. Reimschüssel,S. Tilk,M. Mikołajczyk,H. Ślebocka-tilk |
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Abstract: | Rate constants and activation parameters for the isotopic exchange reactions between (PhO)2PSCl and M36Cl (M = Me4N+, Et4N+, n-Bu4N+, Et3HN+, EtH3N+, 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 Et3HN36Cl, EtH3N36Cl, and Li36Cl 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 ΔH? and ΔS? for the reaction with Li36Cl indicate the existenceof the intermolecular interaction between lithium ions and O,O-diphenylphosphorochloridothionate. |
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