Current pulse relaxation method

Electron spin relaxation in aqueous solutions of Gd3+ chelates is too rapid to be observed at room temperature by the usual pulsed EPR methods, and must be studied by continuous wave (cw) techniques. Two EPR approaches have been used to study relaxation studies of the line shape of the cw EPR resonance of Gd3+ compounds in aqueous solution, and more direct measurement of Tle making use of Longitudinally Detected EPR (LODEPR) [70]. Currently, LODESR is available only at X-band, and the frequency dependence of relaxation is studied by following the frequency dependence of the cw EPR line shape, and especially of the peak-to-peak line width of the first derivative spectrum (ABpp). 

The most satisfactory experimental methods are (a) analysis of potential relaxation after current interruption from a prior steady-state potentials and (b) ac impedance spectroscopy at steady-state potentials. These methods have been referred to in Section VI. They both have the advantages that no H2 reoxidation occurs and no surface oxidation of the electrode takes place, as can arise in the current pulse method (121). The principal applications of the potential-relaxation method to determination of OPD H have been in the work of Bai and Conway (75) on H adsorption in the HER at Ni, Ni-Mo composites, and Pt (136), and by Conway and Brousseau (162) at bulk, single-phase Ni-Mo alloys (Mo 0 to 19 at%). 

To conduct proton conductivity measurements, Buchi et al. [3] designed a current interruption device that used an auxiliary current pulse method and an instrument for generating fast current pulses (i.e. currents > 10 A), and determined the time resolution for the appropriate required voltage acquisition by considering the relaxation processes in the membrane of a PEM fuel cell [3]. They estimated that the dielectric relaxation time, or the time constant for the spontaneous discharge of the double-layer capacitor, t, is about 1.4 x 10 ° s. They found that the potential of a dielectric relaxation process decreased to <1% of the initial value after 4.6r (6.4 x 10 s) and that the ohmic losses almost vanished about half a nanosecond after the current changes. Because there is presently no theory about the fastest electrochemical relaxation processes in PEM fuel cells, the authors assumed a conservative limit of 10 s, based on observations of water electrolysis membranes. They concluded that the time window for accurate current interruption measurements on a membrane is between 0.5 and 10 ns. Another typical application of the current interruption method was demonstrated by Mennola et al. [1], who used a PEM fuel cell stack and identified a poorly performing individual cell in the stack. 

The temperature-jump relaxation method and other relaxation methods avoid mixing and therefore the limitation due to rate of mixing. Instead, the relaxation technique starts with a system at equilibrium and disturbs it by a sudden alteration of temperature or pressure. The discharge of a capacitor provides a short-duration pulse of electric current which gives a sudden increase in temperature. Detections of changes at some distance removed from the electrodes will not be complicated by the chemical... 

The physical basis of current MRI methods has its origin in the fact that, in a strong magnetic field, the nuclear spins of water protons in different tissues relax back to equilibrium at different rates, when subject to perturbation from the resting Boltzmann distribution by the application of a short radio frequency (rf) pulse. For the most common type of spin-echo imaging, return to equilibrium takes place in accord with equation 1 and is governed by two time constants T and T2, the longitudinal and transverse relaxation times, respectively. 

The FT technique has been applied in a multitude of different areas. Starting at low frequencies, FT methods have been used for dielectric response spectroscopy of solids (sometimes called time domain reflectometry). A short picosecond voltage pulse is applied to a dielectric and the current response is measured. Fourier transformation of the current gives the dielectric response function, s v), which is typically interpreted as the Debye relaxation of dipoles. 

There are in fact two slightly different types of non-steady state technique. In the first an instantaneous perturbation of the electrode potential, or current, is applied, and the system is monitored as it relaxes towards its new steady state chronoamperometry and chronopotentiometry are typical examples of such techniques. In the second class of experiment a periodically varying perturbation of current or potential is applied to the system, and its response is measured as a function of the frequency of the perturbation cyclic and a.c. voltammetry are examples of this type of approach. In both cases the rate of mass transport varies with the time (or frequency), and by obtaining data over a wide range of these variables and by using curve fitting procedures, kinetic parameters are obtainable. Pulse techniques will be discussed later in this chapter, whilst sweep methods are described in Chapter 6 and a.c. methods in Chapter 8. 

---