Cottrell equation

E168996

The Cottrell equation is a fundamental relation in electrochemistry that describes how current decays over time during a diffusion-controlled potential step at an electrode.

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Cottrell equation canonical 1

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Predicate Object
instanceOf electrochemical equation
mathematical model
appearsIn textbooks on electrochemical methods
appliesTo diffusion-controlled processes
planar electrodes
assumes constant diffusion coefficient
initially uniform bulk concentration
instantaneous potential step
no convection
no migration (supporting electrolyte present)
semi-infinite linear diffusion
category chronoamperometry
transient electrochemical response
contrastsWith steady-state current equations
derivedFrom solution of Fick's second law for a potential step
describes current–time relationship at an electrode
diffusion-controlled potential step
field electrochemistry
includesParameter A (electrode area)
C (bulk concentration)
D (diffusion coefficient)
F (Faraday constant)
n (number of electrons)
t (time)
influences design of electrochemical experiments
mathematicalForm i(t) = n F A C \sqrt{D / (\pi t)}
namedAfter Frederick Gardner Cottrell
relatedConcept Randles–Ševčík equation
chronoamperometric response at microelectrodes
relatedTo Fick's first law of diffusion
surface form: Fick's second law of diffusion
relates current to bulk concentration
current to diffusion coefficient
current to electrode area
current to number of electrons transferred
faradaic current to time
shows current decays with t^{-1/2}
current decreases over time after a potential step
taughtIn advanced electrochemistry courses
usedFor analyzing chronoamperometry data
determining concentrations of electroactive species
determining diffusion coefficients
usedIn fundamental electrochemical kinetics studies
transient electrochemical techniques
validWhen electrode reaction is fast (reversible)
reaction is purely diffusion-controlled

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Alan Cottrell knownFor Cottrell equation