Theory for chronoamperometry with a first-order disproportionation reaction following electron transfer

Evans, Dennis H.; Rosanske, Thomas W.; Jiménez, Pedro J.

doi:10.1016/s0022-0728(74)80260-3

Cited by 14 publications

(2 citation statements)

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“…Here we outline the algorithm to find k f and k b : 3 We can in fact show the stronger result that lim 1. If for all t, the function J (t) is constant, then k f = 0 and k b cannot be determined mathematically, since P = 0 and so k b P = 0.…”

Section: Procedures To Determine K F and K Bmentioning

confidence: 99%

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The analytical determination of kinetic parameters for a bimolecular EC mechanism from chronoamperometric data

2011

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We study the dependence of chronoamperometric data on the kinetic parameters for a bimolecular reaction, characterizing the behavior of an electrochemical mechanism that pertains to lithium/sulfur dioxide batteries. The reaction entails first the reduction of a reactant O to a product R by an instantaneous charge transfer, followed by a homogeneous chemical reaction between O and R to produce an electrochemically inert product P. We model this by a semilinear reaction-diffusion system with discontinuous initial conditions and mixed Dirichlet and Neumann boundary conditions, and develop a procedure to extract from a single potential step experiment the forward and reverse rate constants for the reaction. To do so we define a functionwhere j (t) is the current density from the chronoamperometric output, and use maximum principle and scaling arguments to exploit the location of the minimum of J (t) versus t.

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Section: Procedures To Determine K F and K Bmentioning

confidence: 99%

“…There is the first order decay of the reduction product, R, to produce an electrochemically inactive product, P (Eq. 2) [1][2][3],…”

Section: Introductionmentioning

confidence: 99%