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Electrochemical impedance spectroscopy (EIS) is a widely-used diagnostic technique to characterize electrochemical processes. It is based on the dynamic analysis of two electrical observables, that is, current and voltage. Electrochemical cells with gaseous reactants or products (e.g., fuel cells, metal/air cells, electrolyzers) offer an additional observable, that is, the gas pressure. The dynamic coupling of current and/or voltage with gas pressure gives rise to a number of additional impedance definitions, for which we use the term electrochemical pressure impedance. It also gives rise to different experimental probing approaches. In this article we present a model-based study of electrochemical pressure impedance spectroscopy (EPIS). Possible quantifications and realizations of EPIS are discussed. The study of generic cell geometries consisting of gas reservoir, diffusion layer(s) and electrochemically active layer(s) reveals distinct spiral-shaped features in the Nyquist plot. Using the example of a sodium/oxygen (Na/O2) cell, the dynamic spatiotemporal behavior of the state variables is quantified and interpreted. Results are compared to first experimental EPIS measurements by Hartmann et al. [J. Phys. Chem. C118, 1461, 2014]. A sensitivity analysis highlights the properties of EPIS with respect to geometric, transport, and kinetic parameters. We demonstrate that EPIS is sensitive to transport parameters that are not well-accessible with standard EIS.
Raman spectra from three different binary gasoline-ethanol blends (with ratios 95:5, 90:10, and 85:15) have been obtained by using a low-cost, frequency precise Fourier-transform Raman spectrometer (FT-Raman) prototype. The spectral information is presented in the range of 0 to 3500 cm-1 with a resolution of 1.66 cm-1, which is greater than the required for most liquid and solid chemical samples. This set-up delivers spectral information about the sample with a reduced spectral deviation compared to theoretical values (less than 0.4 cm-1 without compensation for instrumental response). The robust and highly fexible FT-Raman prototype presented for the spectral analysis, consisting mainly of a Michelson interferometer and a self-designed photon counter, is able to deliver high resolution and frequency precise Raman spectra from the gasoline-ethanol blends comparable to the obtained by using commercial devices. This FT-Raman set-up does not need additional complex hardware or software control and relies on re-sampling and interpolation algorithms. The qualitative spectral information obtained has been used to calculate the proportion of gasoline and ethanol present in the used chemical samples without using extra calibrations methods or chemical markers.