It has become common practice to estimate the numbers of electrons (n, eq mol−1) transferred in faradaic reactions at rotated disk electrodes (RDEs) from the slope of plots of reciprocal current (1/I) vs. reciprocal square root of rotational velocity (1/ω1/2). This practice is based on the Koutecký‐Levich equation derived for a one‐step electron‐transfer mechanism. Furthermore, the intercept of the Koutecký‐Levich plot is assumed to be a reciprocal function of the heterogeneous rate constant (kh, cm s−1) for the electron‐transfer process. In this review, we examine the validity of the practice of estimating values of n and kh for various multi‐step mechanisms at RDEs.

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