Kinetic Evidence of a Common Mechanism in the Oxidations of Diethyl Sulfide by Dichromates and Halochromates of Heterocyclic Bases

摘要

The oxidations of diethyl sulfide by potassium dichromate, pyridinium dichromate, quinolinium dichromate, imidazolium dichromate, nicotinium dichromate, isonicotinium dichromate, pyridinium fluorochromate, quinolinium fluorochromate, imidazolium fluorochromate, pyridinium chlorochromate, quinolinium chlorochromate, and pyridinium bromochromate follow identical kinetic orders-first-order each with respect to the chromium (VI) reagents, sulfide and hydrogen ion, and moderately inhibited by manganese (II) ion. The energy of activation varies linearly with the logarithm of frequency factor and so does the enthalpy of activation with the entropy of activation. Also, the activation free energies do not differ significantly. The dichromates and ahlochromates of heterocyclic bases oxidize diethyl sulfide via a common mechanism.