Second harmonic alternating current voltammetry

As already stated, other electrochemical techniques have been used to derive thermodynamic data, some of them considered to yield more reliable (reversible) redox potentials than cyclic voltammetry. This is the case, for instance, of second harmonic alternating current voltammetry (SHACV) [219,333], Saveant and co-workers [339], however, concluded that systems that appear irreversible in slow-scan CV are also irreversible in SHACV experiments. We do not dwell on these matters, important as they are. Instead, we concentrate on a different methodology to obtain redox potentials, which was developed by Wayner and colleagues [350-352]. 

M. R. Wasielewski, R. Breslow. Thermodynamic Measurements on Unsubstituted Cyclopropenyl Radical and Anion, and Derivatives, by Second Harmonic Alternating Current Voltammetry of Cyclopropenyl Cations. J. Am. Chem. Soc. 1976, 98, 4222—4229. 

C. P. Andrieux, P. Hapiot, J. Pinson, J.-M. Saveant. Determination of Formal Potentials of Chemically Unstable Redox Couples by Second-Harmonic Alternating Current Voltammetry and Cyclic Voltammetry. Application to the Oxidation of Thiophenoxide Ions. J.Am. Chem. Soc. 1993,115, 7783-7788. 

Faradaic rectification — When the electrode potential of the working - electrode is modulated with a sinusoidal -> alternating current the mean potential is shifted from the DC value by a small increment in many cases when the AC modulation is sufficiently large. This effect has been named faradaic rectification, it is caused by the nonlinearity of the electrode response, in particular the variation of current with electrode potential [i]. A theoretical treatment for an electrode in contact with a solution containing a redox system has been provided [ii]. It was extended to reactions where one reactant is present in its element form dissolved in the liquid metallic phase (e.g., Cd2+ + 2e -> Cd(Hg)) [iii]. An improved evaluation technique has been proposed [iv], and some inherent problems have been reviewed [v]. A variant of this method applied to -> polarography has been described [vi]. Second and higher harmonics in - AC voltammetry (polarography) [vii] also arise from this nonlinearity, and hence these techniques also have some characteristics that resemble those found in - faradaic rectification voltammetry. 

Second harmonic — Any nonlinear oscillating system produces higher harmonic oscillations. The second harmonic is the response having twice the frequency of the basic oscillation. The - current response of a faradaic electrode reaction (- faradaic reaction) to perturbations of the - electrode - potential is generally nonlinear, and thus higher harmonic oscillations of the - alternating current (AC) are produced in - AC voltammetry. Since the -> capacitive current is a much more linear function of the electrode potential, the capacitive contribution to higher harmonic currents are rather small which allows a desirable discrimination of theses currents in electro-analytical applications. 

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