In the case of two-electron reduction of a compound, potential inversion refers to the situation where introduction of the second electron occurs with greater ease than the first. That is E-1(0) -E-2(0) < 0 where E-1(0) and E-2(0) are the standard potentials for the two steps of reduction. The extent of potential inversion in the reduction of 9, 10-dinitroanthracene, 1, and 3,6-dinitrodurene, 2, has been assessed by steady-state microelectrode voltammetry, cyclic voltammetry under conditions of near-reversible behavior, cyclic voltammetry under conditions of quasireversible behavior and electrochemical impedance spectroscopy (EIS). The studies were conducted in acetonitrile at 298 K. Cyclic voltammetry under quasireversible conditions and EIS were most sensitive to small changes in E-1(0) - E-2(0) The value of E-1(0) - E-2(0) for 1 was found to be -107 mV and that for 2 was -280 mV. (C) 2003 Elsevier B.V. All rights reserved.