TY - JOUR
T1 - High Sensitivity Internal Reflection Spectroelectrochemistry for Direct Monitoring of Diffusing Species Using Signal Averaging
AU - Winograd, Nicholas
AU - Kuwana, Theodore
AU - Winograd, Nicholas
PY - 1971/2/1
Y1 - 1971/2/1
N2 - Internal reflection spectrometry (IRS) at optically transparent electrodes (OTE) appears to be an excellent technique for quantitative studies of species produced or perturbed electrochemically within a distance δ of the electrode surface. Quantitative applications employing IRS at OTE, however, require an understanding of the sensitivity variation of absorbance. This variation was formulated as a sensitivity factor, Neff, in the quantitative relationships describing absorbance and could be correlated with the optical constants of the system and the Fresnel equations describing the reflectivity. Further, the absorbance as a function of time during an electrochemical potential perturbation could be quantitatively analyzed, and good agreement was found with experimental results. Signal to noise ratios were greatly improved by signal averaging techniques, and small changes (<10–5unit) could be resolved at very short times (ca. 10 μsec).
AB - Internal reflection spectrometry (IRS) at optically transparent electrodes (OTE) appears to be an excellent technique for quantitative studies of species produced or perturbed electrochemically within a distance δ of the electrode surface. Quantitative applications employing IRS at OTE, however, require an understanding of the sensitivity variation of absorbance. This variation was formulated as a sensitivity factor, Neff, in the quantitative relationships describing absorbance and could be correlated with the optical constants of the system and the Fresnel equations describing the reflectivity. Further, the absorbance as a function of time during an electrochemical potential perturbation could be quantitatively analyzed, and good agreement was found with experimental results. Signal to noise ratios were greatly improved by signal averaging techniques, and small changes (<10–5unit) could be resolved at very short times (ca. 10 μsec).
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U2 - 10.1021/ac60297a022
DO - 10.1021/ac60297a022
M3 - Article
AN - SCOPUS:0001197330
SN - 0003-2700
VL - 43
SP - 252
EP - 259
JO - Analytical Chemistry
JF - Analytical Chemistry
IS - 2
ER -