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Chapter 3 Characterisation Methods In this chapter, the characterisation methods used throughout the work are introduced. The methods are all electrochemical in nature, and therefore a short overview of the concepts of electrochemistry is given first. 3.1 Electrochemistry Electrochemistry is the study of chemical processes where electrons are exchanged between an electrode and a redox-active compound, which is typically dissolved in a liquid elec- trolyte surrounding the electrode. This is commonly represented by the reaction scheme Red Ox + ne− (3.1) where Red and Ox are the reduced and oxidised species of a redox couple, and n is the number of electrons exchanged with the electrode. In the rest of the text, the subscripts Red and Ox will be used to distinguish the parameters of reduced and oxidised species. The typical electrochemistry experiment consists of measuring the net current I as a result of a potential E imposed on the electrode, or vice versa for an imposed current. An imposed potential will cause the concentrations of Red and Ox near the electrode surface to shift until a new equilibrium point is reached. For a redox couple with fast electron transfer kinetics, this equilibrium is governed by the Nernst equation, written here for the forward half-reaction of Equation 3.1: E = E0′ + RT ln cOx(0) (3.2) nF cRed (0) whereEistheelectrodepotential,E0′ istheformalpotentialoftheredoxcouple,Risthe ideal gas constant, T is the absolute temperature, and c(0) is the surface concentration. A system that follows the Nernst equation is said to be electrochemically reversible, and the equations presented in the following are strictly only valid for reversible systems. The formal potential of a redox couple is the redox potential under a specific set of conditions, such as concentrations, pH, and ionic strength of the system. The formal 19PDF Image | Organic Redox Flow Batteries 2023
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