We report the detection of an unstable intermediate generated during Br- oxidation to Br-3 in nitrobenzene by scanning electrochemical microscopy (SECM), and we attempt to simulate the collection of the intermediate using a proposed mechanism of Br oxidation to Br-3. At a distance of similar to 3.5 mu m between the tip and the substrate electrode in the SECM experiment, we observed two waves as we measured the collection efficiency, N-ss, while holding the tip at an anodic potential and scanning the substrate toward cathodic potentials. The second wave obtained at more negative substrate potentials was associated with the collection of Br3 , and the first wave was associated with the collection of an intermediate generated in Br- oxidation to Br-3. The Nss as a function of d, estimated at the constant substrate potential of 0.27 V vs. TMPD/TMPD broken vertical bar, abruptly increased as d was brought below 2.5 mu m. We simulated this approach curve by using the following mechanism of Br- oxidation to Br-3 : (1) Br- + e reversible arrow Br center dot, (2) 2Br center dot reversible arrow Br-2, (3) Br center dot + Br center dot reversible arrow Br-2 center dot, (4) Br-2 center dot + e reversible arrow Br-2, and (5) Br-2 + Br reversible arrow Br-3. (C) 2017 Elsevier Ltd. All rights reserved.