Single-sweep techniques

A new polarographic analytical procedure that should prove useful in the direct analysis of RDX and HMX in admixts is described in Ref 88. This single-sweep technique is rapid and sensitive to about 50 parts-per-billion of either RDX or HMX alone or in admixt in natural w effluent. The method can also be used to analyze for... 

Distinction should be made between the so-called single-sweep technique and the multisweep method.In the former method, a single current-potential curve is recorded and the system is brought back to its original condition before a second sweep is made. On the other hand, in the multisweep method, several consecutive i-E curves are recorded and the concentration gradient of the electroactive species changes from one sweep to another, particularly from the first to the subsequent ones. 

In linear sweep voltammetric techniques the applied electrode potential is varied from an initial value E to a final value f at a constant scan rate v (single sweep voltammetry). Once the value is reached the direction of the scan can be reversed, maintaining the same scan rate v, and the potential brought back to the initial value (cyclic voltammetry). In the two cases the form of the potential-time impulse can be represented as shown in Figure 1. 

Potential Sweep Method, In the transient techniques described above, a set of measurements of the potential for a given current or the current for a given potential is measured in order to construct the current-potential function, i = f(E). For example, the Tafel lines shown in Figure 6.20 were constructed from a set of galvanostatic transients of the type shown in Figure 6.18. In the potential sweep technique, i = f(E), curves are recorded directly in a single experiment. This is achieved by sweeping the potential with time. In linear sweep voltammetry, the potential of the test electrode is varied linearly with time (Fig. 6.23a). If the sweep rate is... 

In measuring detonation velocities of explosives, a variety of techniques for time base presentations on the cathode-ray screen have been developed. These include single sweep (and its multichannel modification), raster sweep, zigzag sweep and spiral sweep... 

A complete comprehension of Single Pulse electrochemical techniques is fundamental for the study of more complex techniques that will be analyzed in the following chapters. Hence, the concept of half-wave potential, for example, will be defined here and then characterized in all electrochemical techniques [1, 3, 8]. Moreover, when very small electrodes are used, a stationary current-potential response is reached. This is independent of the conditions of the system prior to each potential step and even of the way the current-potential was obtained (i.e., by means of a controlled potential technique or a controlled current one) [9, 10]. So, the stationary solutions deduced in this chapter for the current-potential curves for single potential step techniques are applicable to any multipotential step or sweep technique such as Staircase Voltammetry or Cyclic Voltammetry. Moreover, many of the functional dependences shown in this chapter for different diffusion fields are maintained in the following chapters when multipulse techniques are described if the superposition principle can be applied. 

This chapter offers a study of the application of the multipulse and sweep techniques Cyclic Staircase Voltammetry (CSCV) and Cyclic Voltammetry (CV) to the study of more complex electrode processes than single charge transfer reactions (electronic or ionic), which were addressed in Chap. 5. 

The kind of voltammetry described in Sect. 4.2. is of the single-sweep type, ie., only one current-potential sweep is recorded, normally at a fairly low scan rate (0.1-0.5 V/min), or by taking points manually. Cyclic voltammetry is a very useful extension of the voltammetric technique. In this method, the potential is varied in a cyclic fashion, in most cases by a linear increase in electrode potential with time in either direction, followed by a reversal of the scan direction and a linear decrease of potential with time at the same scan rate (triangular wave voltammetry). The resulting current-voltage curve is recorded on an XY-recorder,... 

The use of a potential-step technique such as cyclic staircase voltammetry represents a simple alternative to Ichise s method (j0 of obtaining information on both adsorption and electron transfer kinetics. The current decay immediately after a step is primarily capacitive while current at later times is almost totally due to electron transfer reactions. Thus, by measuring the current at several times during each step and by changing the scan rate, information on both the kinetics of the electrode process and the differential capacity can be obtained with a single sweep. 

Apart from this d.c. mode of operation, a number of electrochemical techniques exists in which there is no attainment of a stationary diffusion pattern. Instead, the transient current response to v oltage changes are observed, either once (single sweep) or repetitively (square v ave, pulse, alternating current). The main advantages are as follows ... 

The widespread use of large-amplitude relaxation techniques in the investigations of anodic organic oxidations, requires further comment on the value of these methods. Reinmuth divided these techniques into three classes based on the types of applications quantitative kinetic studies, qualitative kinetic studies, and analytical studies. We are not concerned here with the analytical applications. For studies in kinetics, controlled-potential techniques, particularly linear-potential scan, in either single sweep or in cycles, and to some extent chronopotentiometry, have been primarily employed. Chronopotentiometry has been successfully utilized in the study of transient reactions, e.g., the reaction of CO with platinum oxide or the reaction of oxalic acid with platinum oxide, and the study of simple charge-transfer reactions with linear diffusion (cf. Refs. 159-161). However, since the general application of chronopotentiometry is severely limited for the study of anodic organic oxidations, as commented previously, this technique will not be further discussed. The quantitative analysis of data obtained by linear potential scan techniques is complicated because the form of theoretical results even for the simplest cases, requires the use of computers and consequently very little quantitative kinetic information has been obtained. This... 

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