Electroanalytical chemistry — IUPAC-V analytical chemistry at the electrode/electrolyte interface, distinct from electrochemistry-at-the-methods-grain. Foundations: potentiometry uses equilibrium electrode potentials (no net current) to…
electroanalytical-chemistry
Nernst equation: E = E° − (RT/nF) ln Q (equilibrium-potentiometry backbone)
Foundational framework of potentiometric electroanalysis: the Nernst equation relates the cell voltage E of an electrochemical…
Butler-Volmer: i = i₀ [exp(αFη/RT) − exp(−(1−α)Fη/RT)] (symmetric α=1/2 ⇒ 2 i₀ sinh)
Framework for voltammetric electrode-kinetics analysis: the Butler-Volmer equation captures the overpotential (η = E − E_eq) dependence of…
Faraday's law: n = Q/(zF); m = n·M (coulometry / electroplating stoichiometry)
Framework for coulometric electroanalysis: Faraday's laws (1834) establish the strict linearity between charge passed through an electrode…
Nernst: Q=1 ⇒ E = E°; log(1) = 0; E − E° = 0 at standard state
Sympy-exact symbolic witness of the Nernst equation's Q=1 limit recovering E = E°. Setup: symbolically declare (E°, R, T, n, F, Q) and…
α=1/2 BV: i = 2 i₀ sinh(Fη/(2RT)); rewrite(exp) residual 0; i(η=0)=0
Sympy-exact symbolic witness of the symmetric Butler-Volmer equation's identity with the exponential-expansion form and its…
Cu²⁺+2e⁻→Cu, M=127/2 g/mol, Q=2F ⇒ n=1 mol, mass = 127/2 g
Sympy-exact symbolic witness of Faraday's law applied to copper electrodeposition from Cu²⁺ solution. Setup: M_Cu = 63.5 g/mol = 127/2…
Cyclic voltammetry (Randles-Ševčík)
Randles 1948 / Ševčík 1948: peak current i_p = 0.4463 nFA C √(nFvD/RT) for reversible diffusion-controlled electrode-reaction at scan-rate…
Electrochemical impedance spectroscopy (EIS)
Sluyters 1960 / Macdonald 1987: small-amplitude AC perturbation across frequency range yields complex impedance Z(ω); Nyquist + Bode plots…
Tafel equation (charge transfer kinetics)
Tafel 1905: at high overpotential η, current density j ≈ j_0 exp(αFη/RT) — log-linear rectification. Tafel-slope b = 2.303RT/(αF) probes…
Marcus theory of electron transfer
Marcus 1956 (Nobel 1992): outer-sphere ET rate k_ET = ν_n κ exp(-ΔG*/k_BT) with ΔG* = (λ + ΔG°)²/(4λ); inverted-region prediction λ <…
Ion-selective electrode (ISE)
Cremer 1906 / Sørensen 1909: glass-membrane pH electrode; modern ISEs use ionophore-doped membranes for K+/Na+/Ca²+/F- selectivity. …
Coulometric titration (Faradaic)
Lingane 1948 / Bard-Faulkner: titration via electrochemically-generated reagent; total charge Q = nFN integrated to determine analyte…
Cyclic voltammetry (Randles-Sevcik)
Nicholson-Shain 1964 + Randles-Sevcik 1948: i_p = (2.69e5) n^(3/2) A D^(1/2) C v^(1/2); peak-current scales sqrt(scan-rate); diagnostic for…
Polarography (Heyrovsky 1922)
Heyrovsky 1922 (Nobel 1959): dropping-mercury-electrode wave i_d = 607 n D^(1/2) m^(2/3) t^(1/6) C; trace-metal analysis at micromolar…
Clark electrode (1956)
L Clark 1956 dissolved-O2 electrode: Pt cathode + Ag/AgCl anode + permeable membrane; O2 + 4H+ + 4e- -> 2H2O; basis of clinical blood-gas…
ISE (glass pH electrode, Cremer 1906)
Cremer 1906 + Haber-Klemensiewicz 1909: glass-membrane H+ activity yields E = const + (RT/F) ln a_H+; modern combination electrode +…
Differential pulse voltammetry (Barker)
Barker 1958 differential-pulse: superimpose small pulse + sample current before/after; eliminates capacitive background; ng/L sensitivity…
SECM (Bard 1989)
A J Bard 1989 SECM: ultramicroelectrode tip raster-scans in solution; substrate Faraday-current modulates tip-current via feedback-mode;…
Nernst electrode (1889)
W Nernst 1889 (Nobel 1920) electrochemical-cell EMF; modern reference-electrode SHE + Ag/AgCl + ion-selective membrane.
Clark electrode (1956)
L Clark 1956 O2-electrode; modern blood-gas analyzer + dissolved-oxygen + Clark-derived enzyme-electrode glucose-monitoring.
ISE (Pungor 1962)
E Pungor 1962 ion-selective-electrode; modern silicone-membrane + Severinghaus pCO2 + LaF3 fluoride + glass-pH SH electrode.
SECM (Bard 1989)
A Bard 1989 scanning-electrochemical-microscopy; modern resolution 50 nm + redox-cycling + cellular metabolism + neurotransmitter.
CV (Nicholson-Shain 1965)
R Nicholson-I Shain 1965 CV reversibility-criteria; modern fast-scan + ultramicroelectrode + neurochem + 2024 ML-CV-deconvolution.
Biofuel cell (Davis 1962)
A Davis 1962 + Heller 1995 enzyme-biofuel-cell; modern wearable + implantable + cofactor-tethered DET-direct-electron-transfer.