Theoretical aspects of electrochemistry at low temperature

International audienceThis paper aims at providing theoretical basis on electrochemical processes performed at low temperature (T) according to three different aspects. First, the effect of T-decrease is treated in terms of thermodynamics, mass-transfer, and kinetics of electron transfer (ET) heterogeneous reactions. In particular, predictions of ET kinetics at low temperature are discussed in the frame of Marcus-Hush’s model. The second part is focused on the changes associated to temperature decrease for different electrochemical methods including cyclic voltammetry (CV), chronoamperometry (CA), AC Impedance (ACI) and AC voltammetry (ACV). This section gives keys to extract electrochemical data from low-T experimental curves. In the third part, theoretical aspects of low-T cyclic voltammetry for multiple or chemically-coupled electron-transfer reactions are discussed. CVs of typical molecular mechanisms (EE, EC, ECE…) are provided in order to better visualize the impact of temperature on the redox behavior