TY - JOUR
T1 - Fundamental and second harmonic alternating current cyclic voltamemmeric theory and experimental results for systems in which a first-order chemical reaction follows the charge-transfer step; the EC mechanism
AU - Band, A. M.
AU - O'Halloran, R. J.
AU - Ružić, I.
AU - Smith, D. E.
PY - 1982/1/25
Y1 - 1982/1/25
N2 - A theory-experiment comparison is made for ac cyclic voltammetry with the first-order EC mechanism. Theoretical rate laws are presented and their predictions examined. Experiments used the model electroactive species, cis-Cr(CO)2(dpm)2, [dpmbis(diphenylphosphino)mathane]. One-electron oxidation of this molecule at platinum is followed by isomerization of the cis cation to the trans cation. The rate constant for the cis-trans isomerization was measured using the fundamental harmonic reverse/forward peak height ratio, assuming a Nernstian heterogeneous charge-transfer step. Temperatures employed were 261 K (- 12°C), 273 K (0°C), and 293 K(20°C). The isomerization rate constants obtained and the assumption of Nernstian behavior produced good to excellent theory -experiment agreement for the dc, fundamental harmonic ac, and second harmonic ac cyclic voltammograms.
AB - A theory-experiment comparison is made for ac cyclic voltammetry with the first-order EC mechanism. Theoretical rate laws are presented and their predictions examined. Experiments used the model electroactive species, cis-Cr(CO)2(dpm)2, [dpmbis(diphenylphosphino)mathane]. One-electron oxidation of this molecule at platinum is followed by isomerization of the cis cation to the trans cation. The rate constant for the cis-trans isomerization was measured using the fundamental harmonic reverse/forward peak height ratio, assuming a Nernstian heterogeneous charge-transfer step. Temperatures employed were 261 K (- 12°C), 273 K (0°C), and 293 K(20°C). The isomerization rate constants obtained and the assumption of Nernstian behavior produced good to excellent theory -experiment agreement for the dc, fundamental harmonic ac, and second harmonic ac cyclic voltammograms.
UR - https://www.scopus.com/pages/publications/49049134136
U2 - 10.1016/0022-0728(82)85004-3
DO - 10.1016/0022-0728(82)85004-3
M3 - Article
AN - SCOPUS:49049134136
SN - 0022-0728
VL - 132
SP - 39
EP - 57
JO - Journal of Electroanalytical Chemistry and Interfacial Electrochemistry
JF - Journal of Electroanalytical Chemistry and Interfacial Electrochemistry
IS - C
ER -