Chronopotentiometry involves applying a constant current to an electrochemical cell and measuring the change in potential over time. Initially, there is a sharp decrease in potential as the double layer charges, followed by a slow decrease determined by the Nernst equation as the surface concentration of the reduced species decreases due to electrolysis. Eventually, the surface concentration reaches zero and the potential changes sharply again as the current can no longer be supported by the initial reaction. The technique provides information about electron transfer kinetics and surface concentrations through analysis of the potential-time curve.
Chronopotentiometry involves applying a constant current to an electrochemical cell and measuring the change in potential over time. Initially, there is a sharp decrease in potential as the double layer charges, followed by a slow decrease determined by the Nernst equation as the surface concentration of the reduced species decreases due to electrolysis. Eventually, the surface concentration reaches zero and the potential changes sharply again as the current can no longer be supported by the initial reaction. The technique provides information about electron transfer kinetics and surface concentrations through analysis of the potential-time curve.
Chronopotentiometry involves applying a constant current to an electrochemical cell and measuring the change in potential over time. Initially, there is a sharp decrease in potential as the double layer charges, followed by a slow decrease determined by the Nernst equation as the surface concentration of the reduced species decreases due to electrolysis. Eventually, the surface concentration reaches zero and the potential changes sharply again as the current can no longer be supported by the initial reaction. The technique provides information about electron transfer kinetics and surface concentrations through analysis of the potential-time curve.
Chronopotentiometry involves applying a constant current to an electrochemical cell and measuring the change in potential over time. Initially, there is a sharp decrease in potential as the double layer charges, followed by a slow decrease determined by the Nernst equation as the surface concentration of the reduced species decreases due to electrolysis. Eventually, the surface concentration reaches zero and the potential changes sharply again as the current can no longer be supported by the initial reaction. The technique provides information about electron transfer kinetics and surface concentrations through analysis of the potential-time curve.
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CHRONOPOTENTIOME
TRY Presented by : Drakhshaan Presented by: Tahira azam • In this technique the current flowing in the cell is instantaneously stepped fromzero to some finite value. The solution is not stirred and a large excess of supportingelectrolyte is present in the solution diffusion is the only mass transfer process to beconsidered. • Electrolysis at constant current is conducted with the apparatus schematically presented in Figure where P is a power supply whose output current remains constantregardless of the processes occurring in the cell. The potential of the working electrode E1 against the reference electrode E2 is recorded by means of instrument V. • or a simple reaction as described by Equation (1), a chronopotentiogram willtypically look like the plot in Figure (2). • O+ne- = R
• As the electrolysis proceeds, there is a progressive depletion of the
electrolyzed species atthe surface of the working electrode. As the current pulse is applied there is an initialsharp decrease in the potential as the double layer capacitance is charged, until a potentialat which O is reduced to R is reached. There is then a slow decrease in the potentialdetermined by the Nernst Equation, until the surface concentration of O reachesessentially zero. The flux of O to the surface is then no longer sufficient to maintained the • Chronopotentiometry (CP) is the most basic constant current experiment and is a standard technique for the epsilon. In CP, a current step is applied (Fig1) across an electrochemical cell (without stirring). In double step chronopotentiometry (DSCP), a second current step is applied (Fig2). It should be noted that the time scale of a DSCP experiment is typically shorter (seconds or milliseconds) than that of CP experiment (minutes or seconds). The protocol for defining the sampling rate is therefore different for the two techniques. CP is a standard technique, whereas DSCP is only available as an optional addition. Analysis of the Potential vs. Time Curve Analysis of the Potential vs. Time Curve
• Let us consider the electron transfer reaction O + e- = R. Before the current step, the concentration of O at the electrode surface is the same as in the bulk solution (i.e., 5 mM). The initial potential is the rest potential or the open circuit potential (Eo.c.). Once the (reducing) current step has been applied, O is reduced to R at the electrode surface in order to support the applied current, and the concentration of O at the electrode surface therefore decreases. This sets up a concentration gradient for O between the bulk solution and the electrode surface, and molecules of O diffuse down this concentration gradient to the electrode surface. The potential is close to the redox potential for O + e- = R, and its precise value depends upon the Nernst equation:
• Nernst equation • here CsO and CsR are the surface concentrations of O and R, respectively. These concentrations vary with time, so the potential also varies with time, which is reflected in the finite slope of the potential vs. time plot at this stage. Once the concentration of O at the electrode surface is zero, the applied current can no longer be supported by this electron transfer reaction, so the potential changes to the redox potential of another electron transfer reaction. If no other analyte has been added to the solution, the second electron transfer reaction will involve reduction of the electrolyte; that is, there is a large change in the potential (Fig6).
