Voltammetric measurement of ultraslow diffusion rates in polymeric media with microdisk electrodes

Longmire, M. L.; Watanabe, Masayoshi; Zhang, H.; Wooster, T. T.; Murray, Royce W.

doi:10.1021/ac00206a020

Cited by 61 publications

(37 citation statements)

References 36 publications

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“…These Dapp values were obtained by using a steady-state current and the Cottrell equation from the literature [6]. Considering the dimensionless time parameter T = 4D,,,t/r2 in the method, the Dapp was generally determined by seeking two limiting experimental Diffusion of Electroactive Species in PEG.…”

Section: Principles Of Electrochemical Measurement At Microdisk Electmentioning

confidence: 99%

“…Although the error is larger than 5% [6], Equation 1 can be used within the permanent window, and the method avoids considering the dimensionless time parameter 7 = 4Dt/r2, where D needs to be estimated by CV. (iii) It is a convenient method, the Dapp does not require two separate measurements, e.g., by different techniques ( chronoamperometry, steady-state voltammetry), and can be obtained from a single potential step experiment.…”

Section: Principles Of Electrochemical Measurement At Microdisk Electmentioning

confidence: 99%

“…Murray and co-workers [5-71 have used microelectrodes to study electrochemical and transport phenomena in solid-state polyelectrolytes. They have determined diffusion coefficients of electroactive species in polyelectrolyte using steady-state current and the Cottrell equation [6]. Our interest is in estimating Dapp without knowledge of the C,, or in estimating Dapp and C , ' , from a single experiment.…”

Section: Introductionmentioning

confidence: 99%

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Study on diffusion of electroactive species in polyelectrolyte polyethylene glycol lithium perchlorate by chronoamperometry at a microdisk electrode

1997

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The mass transport dynamics of ferrocene in polyelectrolyte polyethylene glycol lithium perchlorate (PEG. LiC104) was studied by using chronoamperometry at a microdisk electrode. Chronoamperometry is a powerful method for the study of mass transport in polyelectrolyte, it has many advantages over the conventional methods at a microelectrode and the steady-state method at an ultramicroelectrode. By using this method the apparent diffusion coefficient D,,, and concentration C, of the electroactive species, can be estimated from a single experiment without previous knowledge of either one. We have estimated D,,, and C, of ferrocene in PEG. LiC104 polyelectrolyte from 25 "C to 75 "C. The dependence on the concentration of electroactive species was observed. The diffusion coefficients decrease with increasing ferrocene concentration and decreasing temperature. The mass transport mechanism is explained by using a free volume model.

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Section: Principles Of Electrochemical Measurement At Microdisk Electmentioning

confidence: 99%

Section: Principles Of Electrochemical Measurement At Microdisk Electmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Study on diffusion of electroactive species in polyelectrolyte polyethylene glycol lithium perchlorate by chronoamperometry at a microdisk electrode

1997

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“…If the diffusion coefficients of substance O and R have a common value D, and the diffusion condition is in the region of mixed linear-radial, the maximum current i is obtained by following equation which is the model incorporating mixed diffusion and migration by the pervious works of Murray and Osteryoung et al [16,21,22]:…”

Section: Electrochemical Properties Of Pw 12 In Pegmentioning

confidence: 99%

“…For p 0.6, 0.33, 0.21 and 0.076, the voltammograms deviate from the steady state wave by 10%, 5%, 3% and 1%, respectively. So the steady state current is obtained under radial diffusion conditions when p is smaller, i.e., for p < 0.33, the total current only includes 5% of the linear diffusion current, and the error < 5% if the total current is replaced by the radial diffusion current of solute [16,21]. Therefore the diffusion of electroactive solute can be calculated from a steady state equation.…”

Section: Electrochemical Properties Of Pw 12 In Pegmentioning

confidence: 99%

Electrochemical Study of PW₁₂O$\rm{_{40}^{3-}}$ in Poly(ethylene glycol) Electrolyte

Zhao

Liu

et al. 2003

Electroanalysis

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The electrochemical properties of PW 12 O 3À 40 (abbreviated as PW 12 ) anion in poly(ethylene glycol) (PEG) have been studied by cyclic voltammetry, complex impedance and FT-IR spectroscopy. The PW 12 anion in PEG-LiClO 4 electrolyte shows reasonable facile electrochemistry, and the diffusion coefficients of PW 12 were measured with microelectrode. It is shown that ionic conductivity of polymer electrolytes based on low molecular weight PEG can be improved by the addition of PW 12 . The increase of conductivity is coupled with decrease of transient cross-links density of polymer chains which is evidenced by the downshift of CÀOÀC stretching mode. The phenomena are explained in view of ion-ion and ion-polymer interactions.

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Electrochemical, Pulsed‐Field‐Gradient Spin‐Echo NMR Spectroscopic, and ESR Spectroscopic Study of the Diffusivity of Molecular Probes inside Gel‐Type Cross‐Linked Polymers

Corain

D’Archivio

Galantini

et al. 2007

Chemistry A European J

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The permeability of five gel-type synthetic resins, obtained by polymerization of 1-vinylpyrrolidin-2-one cross-linked with N,N'-methylenebisacrylamide (1, 2, 3, 4, and 5 wt %) and swollen by N,N-dimethylformamide (DMF), has been analyzed. The diffusion of 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxyl (TEMPONE) was studied by ultramicroelectrode voltammetry. Similar measurements were performed for solutions of non-cross-linked poly(vinylpyrrolidone) in DMF. To provide information on the rotational mobility of TEMPONE and the translational mobility of DMF, electron spin resonance (ESR) spectroscopic and pulsed-field-gradient spin-echo nuclear magnetic resonance (PGSE-NMR) spectroscopic experiments, respectively, were carried out. Comparative analysis of the results obtained by electrochemical, ESR spectroscopic, and PGSE-NMR spectroscopic measurements showed that diffusivity inside the polymer framework is significantly affected by the extent of cross-linking, the size of the diffusing probe, and the presence of electrolytes.

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Voltammetric measurement of ultraslow diffusion rates in polymeric media with microdisk electrodes

Cited by 61 publications

References 36 publications

Study on diffusion of electroactive species in polyelectrolyte polyethylene glycol lithium perchlorate by chronoamperometry at a microdisk electrode

Study on diffusion of electroactive species in polyelectrolyte polyethylene glycol lithium perchlorate by chronoamperometry at a microdisk electrode

Electrochemical Study of PW₁₂O$\rm{_{40}^{3-}}$ in Poly(ethylene glycol) Electrolyte

Electrochemical, Pulsed‐Field‐Gradient Spin‐Echo NMR Spectroscopic, and ESR Spectroscopic Study of the Diffusivity of Molecular Probes inside Gel‐Type Cross‐Linked Polymers

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Voltammetric measurement of ultraslow diffusion rates in polymeric media with microdisk electrodes

Cited by 61 publications

References 36 publications

Study on diffusion of electroactive species in polyelectrolyte polyethylene glycol lithium perchlorate by chronoamperometry at a microdisk electrode

Study on diffusion of electroactive species in polyelectrolyte polyethylene glycol lithium perchlorate by chronoamperometry at a microdisk electrode

Electrochemical Study of PW12O$\rm{_{40}^{3-}}$ in Poly(ethylene glycol) Electrolyte

Electrochemical, Pulsed‐Field‐Gradient Spin‐Echo NMR Spectroscopic, and ESR Spectroscopic Study of the Diffusivity of Molecular Probes inside Gel‐Type Cross‐Linked Polymers

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Electrochemical Study of PW₁₂O$\rm{_{40}^{3-}}$ in Poly(ethylene glycol) Electrolyte