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The analytical determination of kinetic parameters for a bimolecular EC mechanism from chronoamperometric data
| Content Provider | Semantic Scholar |
|---|---|
| Author | Gimre, K. T. Whiteley, R. V. Günther, C. |
| Copyright Year | 2011 |
| Abstract | 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 function $${\mathcal{J}(t):=j(t)\sqrt{t}}$$ , where 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 $${\mathcal{J}(t)}$$ versus t. |
| Starting Page | 805 |
| Ending Page | 818 |
| Page Count | 14 |
| File Format | PDF HTM / HTML |
| DOI | 10.1007/s10910-011-9925-1 |
| Volume Number | 50 |
| Alternate Webpage(s) | http://www.math.columbia.edu/~gimre/Electrochem |
| Alternate Webpage(s) | https://doi.org/10.1007/s10910-011-9925-1 |
| Journal | Journal of Mathematical Chemistry |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
