Current step techniques chronopotentiometry

In chronopotentiometry, a current is applied to the electrode and the potential changes to a value at which the flux of the electroaclive species is sufficient to supply the applied current. After a certain time, the flux of redox species to the surface cannot sustain this current and the potential changes rapidly to a new value at which another species (often solvent or electrolyte) is reduced (or oxidized). This time, termed the transition time t, follows the Sand equation  

The two primary advantages of chronopotentiometry are that the measured quantity (t) is directly proportional to D, and that r is the same regardless of heterogeneous electrode kinetics (although the break in the E-t curve is less sharp when the reaction is not reversible). The primary disadvantages of chronopotentiometry include some of those 

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Other Techniques - Other electrochemical techniques that could be employed in sensor technology would include potential-step methods (or chrono-amperometry, as current is recorded with time), current-step methods (or chronopotentiometry, as potential is recorded with time) and AC impedance. None of these techniques appear to have yet been applied to catalyst sensing in a systematic way. 

Chronopotentiometry is the electrochemical technique in which a current step is impressed across an electrochemical cell containing unstirred solution [1-5]. The resulting potential response of the working electrode versus a reference electrode is measured as a function of time (thus, chronopotentiometry), giving a chronopotentiogram as shown in Figure 4.3. 

Chronopotentiometry — is a controlled-current technique (- dynamic technique) in which the - potential variation with time is measured following a current step (also cyclic, or current reversals, or linearly increasing currents are used). For a - nernstian electrode process,... 

Current step— The excitation signal used in controlled current techniques in which the potential is measured at a designated time [i]. See also - chronopotentiometry, -> cyclic chronopotentiometry, - staircase voltammetry. Ref. [i] Heineman WR, Kissinger PT (1984) In Kissinger PT, Heine-man WR (eds) Laboratory techniques in electroanalytical chemistry. Marcel Dekker, New York, pp 129-142... 

Nowadays, most chemists know the name "Sand" only because it appears attached to a partic ilar equation in texts that describe chronopotentiometry. This technique can be useful in the diagnosis of electrode reactions (l). A current step i is Impressed across an electrochemical cell containing iinstirred solution, the potential of the working electrode is measured with respect to time and the transition time x is noted. According to the Sand equation, the product ix /2 should be constant for an uncomplicated linear diffusion-controlled electrode reaction at a planar electrode. 

Chronoamperometry, chronocoulometry, and chronopotentiometry belong to the family of step techniques [1-4]. In chronoamperometry the current, while in chronocoulometry the charge is measured as a function of time after application of a potential step perturbation. In the case of chronopotentiometry, a current step is applied, and the change of the potential with time is detected. 

Chronopotentiometry is a controlled-current technique in which the potential variation with time (0 is measiued following a current step. Other ciurent perturbations such as linear, cyclic, or current reversals are also used [1,3,4,12]. For a reversible electrode reaction following a ciurent step, chronopotentiograms shown in Fig. 7 can be obtained. 

The possibility that adsorption reactions play an important role in the reduction of telluryl ions has been discussed in several works (Chap. 3 CdTe). By using various electrochemical techniques in stationary and non-stationary diffusion regimes, such as voltammetry, chronopotentiometry, and pulsed current electrolysis, Montiel-Santillan et al. [52] have shown that the electrochemical reduction of HTeOj in acid sulfate medium (pH 2) on solid tellurium electrodes, generated in situ at 25 °C, must be considered as a four-electron process preceded by a slow adsorption step of the telluryl ions the reduction mechanism was observed to depend on the applied potential, so that at high overpotentials the adsorption step was not significant for the overall process. 

For controlled-current DC polarography, especially its current density mode, see under Chronopotentiometry at a dme (p. 172). For charge-step polarography, i.e., a controlled charge of coulostatic technique, see ref. 9, pp. 424-429, and ref. 3, pp. 270-276. 

Chronopotentiometry is a transient constant-current technique in which the potential of the electrode is followed, as a function of time, in a quiet solution (Figure 6). Double-step applications [30], as well as programmed current experiments [31] have been described. 

In this section, we will show that the stationary responses obtained at microelectrodes are independent of whether the electrochemical technique employed was under controlled potential conditions or under controlled current conditions, and therefore, they show a universal behavior. In other words, the time independence of the I/E curves yields unique responses independently of whether they were obtained from a voltammetric experiment (by applying any variable on time potential), or from chronopotentiometry (by applying any variable on time current). Hence, the equations presented in this section are applicable to any multipotential step or sweep technique such as Staircase Voltammetry or Cyclic Voltammetry. 

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