Reflectance, potential-modulated

Electrochemical impedance spectroscopy leads to information on surface states and representative circuits of electrode/electrolyte interfaces. Here, the measurement technique involves potential modulation and the detection of phase shifts with respect to the generated current. The driving force in a microwave measurement is the microwave power, which is proportional to E2 (E = electrical microwave field). Therefore, for a microwave impedance measurement, the microwave power P has to be modulated to observe a phase shift with respect to the flux, the transmitted or reflected microwave power APIP. Phase-sensitive microwave conductivity (impedance) measurements, again provided that a reliable theory is available for combining them with an electrochemical impedance measurement, should lead to information on the kinetics of surface states and defects and the polarizability of surface states, and may lead to more reliable information on real representative circuits of electrodes. We suspect that representative electrical circuits for electrode/electrolyte interfaces may become directly determinable by combining phase-sensitive electrical and microwave conductivity measurements. However, up to now, in this early stage of development of microwave electrochemistry, only comparatively simple measurements can be evaluated. 

An interesting special application has been proposed by Schlichthorl and Peter.31,41 It aims at deconvolution of electrochemical impedance data to separate space charge and surface capacitance contributions. The method relies on detection of the conductivity change in the semiconductor associated with the depletion of majority carriers in the space charge region via potential-modulated microwave reflectivity measurements. The electrode samples were n-Si(lll) in contact with fluoride solution. 

A linear expansion of this equation for a small-amplitude potential modulation, SU, leads to the microwave reflectivity change... 

Gutierrez, C. Potential-Modulated Reflectance Spectroscopy Studies of the Electronic Transitions of Chemisorbed Carbon Monoxide 28... 

The reflectance, R, is defined as the ratio of the reflected light intensity to the intensity of the incident beam. Usually, one determines the change in reflectance, A/ , induced by some parameter, such as the electrode potential. Experimentally, one measures only the intensity of the reflected beam, 4. So if the incident intensity remains constant, the reflected beam gives hJl/R = A4/4. Experimental results are presented as plots of A/J/R vs. the parameter of interest, such as the frequency of the incident light or electrode potential. Modulation schemes, wherein the beam is chopped or the potential is modulated, are used to enhance the signal-to-noise ratio. 

FIG. 9 Real component of the AC current (a) and imaginary part of the normalized potential-modulated reflectance (b) for the TCNQ reduction by ferrocyanide at the water-DCE interface. Experimental conditions as in Fig. 5. The potential modulation was 30 mV rms at 3.2 EIz. (c) Optical Randles plot obtained from the frequency-dependent analysis of the PMR responses. (Reprinted from Ref 43 with permission from Elsevier Science.)... 

The three most commonly applied external reflectance techniques can be considered in terms of the means employed to overcome the sensitivity problem. Both electrically modulated infrared spectroscopy (EMIRS) and in situ FTIR use potential modulation while polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) takes advantage of the surface selection rule to enhance surface sensitivity. 

Polarisation modulation infrared rejiection-absorption spectroscopy (PM-IRRAS or JRRAS). Potential modulation IR studies rely on switching the potential at a reflective electrode between rest and active states, generating difference spectra. However, the EMIRS technique has several drawbacks the relatively fast potential modulation requires that only fast and reversible electrochemical process are investigated the absorption due to irreversibly chemisorbed species would be gradually eliminated by the rapid perturbation. Secondly, there is some concern that rapid modulation between two potentials may, to some extent, in itself induce reactions to occur. 

Figure 3.23 Reflection difference X-ray diffraclograms from platinised Pt in 1 M H2SO in oxygen adsorption region. Potential modulated between 0.2 V vs. SCF. and (a) 0.8 V, (b) 1 OV (c) 1.2 V Data collection time 3 x I04 seconds. From Fleischmann and Mao (1987).

In order to study the identity and nature of the intermediate, Aylmer-K.elly et al. (1973) employed modulated specular reflectance spectroscopy. They studied the reduction reaction at a lead cathode in both aqueous and non-aqueous electrolytes. A phase-sensitive detection system was employed by the authors, locked-in to the frequency of the potential modulation. The potential was modulated at 30 Hz between the reference potential of — 1.0 V vs. Ag/AgCl and a more cathodic limit. 

Larramona, G. Gutierrez, C. (1989) The passive film on iron at pH 1-14. A potential-modulated reflectance study. J. Electrochem. 

Electronic spectra (Table 1.1, Fig. 1.2) have been measnred for the orange soln-tions of (RuO ] in aqueous base from 250-600 nm. [212-215, 222], and reproduced [215, 222]. There are two at 460 and 385 nm. [212, 213, 222] or three bands in the visible-UV region, at 460, 385 and 317 nm [214, 215]. These appear to be at the same positions as those for [RuO ] but the intensities and hence the general outline of the two spectra are very different. Woodhead and Fletcher reviewed the published molar extinction coefficients and their optimum values / dm (mol" cm" ) are 1710 for the 460 nm. band, 831 for the 385 nm. band and 301 for the 317 nm. band - the latter band was not observed by some workers [214]. The distinctive electronic spectrum of ruthenate in solution is useful for distinguishing between it, [RuO ]" and RuO [212, 222]. Measurements of the electronic spectra of potassium ruthenate doped in K CrO and K SeO and of barium ruthenate doped into BaSO, BaCrO, and BaSeO (in all cases the anions of these host materials are tetrahedral) indicate that in that these environments at least the Ru is tetrahedrally coordinated. Based on this evidence it has been suggested that [RuO ] in aqueous solution is tetrahedral [RuO ] rather than franx-[Ru(0H)3(0)3] [533, 535]. Potential modulated reflectance spectroscopy (PMRS) was used to identify [RuO ] and [RuO ] " in alkaline aqueous solutions during anodic oxidation of Ru electrodeposited on platinum from [Ru3(N)Clg(H30)3] [228]. 

Figure 13.5 Potential modulated reflectance spectrum of p-aminonitrobenzene (PANB) on platinum (solution phase 0.5 mM Na2S04 + 0.05 mM PANB). Applied dc 0.44 V vs. SHE. Modulation amplitude 50 mV. Modulation frequency 33 Hz. Incidence angle 65°. 11 signifies incident polarization parallel to incident plane and perpendicular to electrode surface. J signifies incident polarization perpendicular to incident plane (hence parallel to electrode surface). [From Ref. 50.]...

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