Determination of electrochemical kinetic parameters in high resistance solutions using semiintegration

VandenBorn, H. W.; Evans, Dennis H.

doi:10.1021/ac60342a005

Cited by 44 publications

(21 citation statements)

References 9 publications

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“…However, this hardware approach requires a specific resistor‐capacitor ladder network suited to a particular time domain and numerical generation is preferred if a wide range of scan rates is investigated . Evans and co‐workers developed a computerized digital data acquisition system for collecting experimental data and then transferred the data to a larger computer to transform and analyze . A generalized differintegration algorithm based on the Grünwald definition for any value of the differintegration order v was developed .…”

Section: Determining M(t)mentioning

confidence: 99%

Semioperations and Convolutions in Voltammetry

Mahon

Oldham

2018

ChemElectroChem

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It is often useful to transform a measured signal into a form that is more easily interpreted. Thus, in voltammetry, where the measurement is of a current responding to a perturbation of the electrode potential, the complications arising from diffusional transport may be readily alleviated through the use of semioperators or convolutions. The use of semiintegration enables the voltammetric current to be transformed into an alternative signal that, in the case of a planar electrode, is linearly related to the concentrations of reactant and product at the electrode surface. Numerous advantages of semiintegration have been widely demonstrated. However, semiintegration is but a special case of the more general procedure of convolution. Convolving the voltammetric current with specifically designed functions of time allows the benefits of semiintegration to be applied to other electrode geometries and other experimental circumstances. The prime motive for semiintegration or convolution is to gain access to information about concentrations at the electrode surface. This information opens the door to the measurement of such quantities as bulk concentrations, rate constants, standard potentials, and diffusivities, as well as suggesting mechanisms and enabling the calibration of electrodes.

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Section: Determining M(t)mentioning

confidence: 99%

Semioperations and Convolutions in Voltammetry

Mahon

Oldham

2018

ChemElectroChem

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“…or by equivalent methods [12,20,42,43], where Δ is a small increment of the total time. A Microsoft Excel macro containing a semiintegration algorithm is available free online [44].…”

Section: Theorymentioning

confidence: 99%

Electroanalytical Applications of Semiintegral and Convolution Voltammetry in Room-Temperature Ionic Liquids

Bentley

Bond

Hollenkamp

et al. 2015

Electrochemistry in Ionic Liquids

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“…More importantly, the method described here is theoretically strict. A similar relationship also exists in the semi-integrated voltammogram for bulk species, which has been successfully utilized for the determination of the electron-transfer kinetics of bulk species [24,33,34]. The above equation was applied to several sets of simulated data.…”

Section: Simple Electron-transfer Process (E)mentioning

confidence: 99%

“…Another attractive advantage of the semi-integration approach over other existing non-global methods is its applicability to ohmic-drop contaminated linear sweep voltammograms [31,32]. Practical aspects of these methods when applied to the determination of electrontransfer reaction kinetics have also been discussed [33,34]. Unfortunately, it is theoretically invalid to use the semi-integrated/convoluted voltammogram of a diffusionless system in a similar way as in the diffusion case to perform global analysis of the current response.…”

Section: Introductionmentioning

confidence: 99%