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The N(α), N(β)-rearrangement of the two N-atoms which can be observed in solutions of [β-15N]-labelled p-substituted benzenediazonium ions follows dual substituent parameter treatments. The reaction yields a negative field and a positive resonance reaction constant (pF =−3.35, pR = 2.47). The magnitude of these constants is, within experimental error, the same as the respective reaction constants for solvolytic dediazoniation. The exchange of the diazonio group of 15N-labelled p-substituted benzenediazonium ion yields, however, field and resonance reaction constants which are close to zero. This result is attributed to cancellation of the reaction constants for the forward and reverse steps in the complex mechanism of the exchange reaction.

Presents a more convenient approach to studying the kinetics of the hydrolysis of benzenediazonium ion.