The electrochemical reduction of triphenylethylene (TriPE) was studied in dimethylsulfoxide (DMSO) containing 0.1 M tetra-n-butylammonium perchlorate supporting electrolyte through the use of cyclic voltammetry. Experiments were conducted using two different mercury hemisphere electrode sizes (radii 3 and 25 mu m) and with TriPE concentrations of 0.50 and 2.00 mM so as to span fully the transition from convergent to linear diffusion and steady state to transient voltammetry. Voltammetric responses obtained display two sucessive reduction waves with formal potentials separated by ca. 290 mV. Taking the diffusion coeffient of TriPE, TriPE(.-) and TriPP(2-) to be 2.8 x 10(-10) m(2) s(-1), excellent fits between simulation and experiments were obtained across all experimental conditions, with the following DISP2 reaction scheme: Heterogeneous reactions: TriPE + e(-) = TriPE(-) k(1)(0) = 0.15 cm s(-1), alpha(1) = 0.5 TriPE(.-) + e(-) TriPE(2-) = k(2)(0) = 0.032 cm s(-1), alpha(2) = 0.5 (E-f.2(0) - E-f.1(0) = 290 mV) Homogeneous reactions: TriPE(-) + TriPE(-) = TriPE + TriPE(2-) K-DISP = 1.3 x 10(-5), k(f.DISP) = 5.0 x 10(4) mol(-1) dm(3)s(-1) TriPE(2-) -> products K-eq > 1.5 x 10(6), k(f) > 1.0 x 10(6) s(-1) where k(0) denotes the standard electrochemical rate constant, a the transfer coefficient, E-f(0) the standard formal potential. K-DISP the equilibrium constant of the disproportionation reaction, k(f,DISP) the rate of the forward reaction of disproportionation, K-eq the equilibrium constant of the decay of TriPE(2-), and k(f) the rate of the forward reaction of the decay of TriPE(2-). (C) 2012 Elsevier B.V. All rights reserved.