Ramp scanning

FIGURE 6.6 A calibration of optimum lens voltages is used to ramp-scan the ion lens in concert with the mass scan of the analyzer. (From E.R. Denoyer, D. Jacques, E. Debrah, S. D. Tanner, Atomic Spectroscopy, 16[1], 1,1995.)... 

When it comes to quantifying an isotopic signal in ICP-MS, there are basically two approaches to consider. One is the multichannel ramp scanning approach, which uses a continuous smooth ramp of l-n channels (where n is typically 20) per mass across the peak profile. This is shown in Figure 12.4. 

FIGURE 12.4 Multichannel ramp scanning approach using 20 channels per amu. 

Fig. 20.13 Current flow in response to a potential ramp (scan rate v V/s) for (a) a capacitive circuit and (b) a resistive circuit.

In situ XRD stndies of thermally and chemically induced transformations were monitored with a totally automated diffractometer-micrometer system (9). Samples were thermally ramped in 5°C increments from 30 to 160°C, maintained at 160°C for 0.5 hr, and then cooled in 5°C increments to 30°C under 500 torr hydrogen. 20 scans were obtained after each temperatnre increment. The individnal scans conld be stacked to show the temperature evolution of the stracture. 

Shown in Figure 15.5 are the temperature dependent XRD data for the 5% Pd-1% Sn catalyst. As noted above, the scans were offset in the order that they were obtained (the Time axis, as shown, is the scan sequence number and not the actual temperature). The inset of Figure 15.5 illustrates the temperature profile for the scan sequence. The first scan was obtained at room temperature, at which time hydrogen was introduced into the chamber at 500 Torr. The temperature was then ramped in 10°C increments to 160°C and XRD scans were taken after each increment. The sample was held at 160°C for I/2 hour, and then cooled to room temperature. After I/2 hour at room temperature, the sample was purged with dry nitrogen. 

Experimental results obtained at a rotating-disk electrode by Selman and Tobias (S10) indicate that this order-of-magnitude difference in the time of approach to the limiting current, between linear current increases, on the one hand, and the concentration-step method, on the other, is a general feature of forced-convection mass transfer. In these experiments the limiting current of ferricyanide reduction was generated by current ramps, as well as by potential scans. The apparent limiting current was taken to be the current value at the inflection point in the current-potential curve. 

We use differential scanning calorimetry - which we invariably shorten to DSC - to analyze the thermal properties of polymer samples as a function of temperature. We encapsulate a small sample of polymer, typically weighing a few milligrams, in an aluminum pan that we place on top of a small heater within an insulated cell. We place an empty sample pan atop the heater of an identical reference cell. The temperature of the two cells is ramped at a precise rate and the difference in heat required to maintain the two cells at the same temperature is recorded. A computer provides the results as a thermogram, in which heat flow is plotted as a function of temperature, a schematic example of which is shown in Fig. 7.13. 

Waves I and II in Figure 2.81(b) are due to the formation of Cu(I) and Cu(II) surface oxides. Subsequent reduction of these films occurs during the cathodic sweep to give waves III and IV. The points A to D represent the potentials at which reflectivity data were collected during the voltammetric scan. The potential was ramped at lOmV/s until one of these potentials was reached, at which the scan was stopped for the duration of the data acquisition. The spectrum collected at A represents the condition of the electrode surface... 

After tq is passed, the second step starts by scanning the potential from Ed to a potential when all the deposited metals are re-oxidized (the reverse of reaction 25). The oxidation current recorded as a function of potential is the anodic stripping voltammogram (ASV). A typical ASY of three metals (Cd, Pb, and Cu) deposited on a mercury film electrode is shown in Fig. 18b.12b. The sensitivity of ASY can be improved by increasing the deposition time and by using the pulse technique to record the oxidation current. ASV in Fig. 18b. 12b was obtained by using the square wave voltammetry. In most cases a simple linear or step ramp is sufficient to measure sub-ppm level of metals in aqueous solution. The peak current of a linear scan ASV performed on a thin mercury film electrode is given by... 

Voltammetry was described briefly in the previous chapter, when we first looked at stripping techniques. To recap during the experiment, the potential is ramped from an initial value, E, to a final value, Ef (see Figure 6.5). The potential of the working electrode is ramped, with the rate of dE/dr being known as the sweep rate, i. The sweep rate is also called the scan rate. Note that the value of v is always cited as a positive number. 

The potential of the working electrode is ramped at a scan rate of v. The resultant trace of current against potential is termed a voltamnu ram. In linear-sweep voltammetry (LSV), the potential of the working electrode is ramped from an initial potential Ei to a final potential Ef (cf. Figure 6.2). Figure 6.12 shows a linear-sweep voltammogram for the reduction of a solution-phase analyte, depicted as a function of scan rate. Note that the jc-axis is drawn as a function of overpotential (equation (6.1)), and that the peak occurs just after = 0. 

During cyclic voltammetry, the potential is similarly ramped from an initial potential E but, at the end of its linear sweep, the direction of the potential scan is reversed, usually stopping at the initial potential E (or it may commence an additional cycle). The potential at which the reverse occurs is known as the switch potential ( >.) Almost universally, the scan rate between E and Ex is the same as that between Ex and E. Values of the scan rates Vforwani and Ubackward are always written as positive numbers. 

Figure 6.12 Linear-sweep voltammogram for the reduction reaction, O - - ne" —> R, at a solid electrode, shown as a function of the scan rate u. The solution was under diffusion control, which was achieved by adding inert electrolyte and maintaining a still solution during potential ramping. Note that the x-axis has been normalized to , that is, thex-axis represents an overpotential. Reproduced from Greef, R., Peat, R., Peter, L.M., Pletcher, D. and Robinson, J., Instrumental Methods in Electrochemistry, Ellis Horwood, Chichester, 1990, with permission of Profes.sor D. Pletcher, Department of Chemistry, University of Southampton, Southampton, UK.

A thermochemical method that simultaneously measures differences in heat flow into a test substance and a reference substance (whose thermochemical properties are already well characterized) as both are subjected to programmed temperature ramping of the otherwise thermally isolated sample holder. The advantage of differential scanning calorimetry is a kinetic technique that allows one to record differences in heat absorption directly rather than measuring the total heat evolved/... 

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