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Hydrodynamics and mass transport in wall-tube and microjet electrodes: An experimental evaluation of current theory

Rees, NV, Klymenko, OV, Coles, BA and Compton, RG (2003) Hydrodynamics and mass transport in wall-tube and microjet electrodes: An experimental evaluation of current theory Journal of Physical Chemistry B, 107 (49). pp. 13649-13660.

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The application of steady-state and fast-scan linear sweep voltammetry to a high-speed wall-tube electrode (HWTE) is reported in different solvents to investigate the response of the HWTE over a wide range of Reynolds’ numbers (Re). Experiments are reported for the oxidation of N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD) in propylene carbonate (PC), water, butyronitrile (BN), acetonitrile (AN), and acetonitrile-water mixture solutions containing 0.10 M supporting electrolyte for a 24 μm radius platinum microdisk electrode housed within the HWTE using a range of average flow jet velocities from 0.03 to 19.8 m s-1 (corresponding to volume flow rates of 0.003-0.25 cm3 s-1 and center-line jet velocities from 0.05 to 39.5 m s-1). Fast scan linear sweep voltammetry is presented for the oxidation of TMPD in PC and of 9,10-diphenylanthracene (DPA) in AN. Theoretical results are derived using finite element methods for both one- and two-dimensional mass transport models. It is found that, for solvents with a kinematic viscosity above ca. 7.5 × 10-3 cm2 s-1, the hydrodynamic behavior for Re < 2000 is as expected with current responses in accordance with those predicted for a laminar, parabolic inlet flow profile. In low viscosity solvents, where Re < 2000, currents are lower than expected, indicating a departure from laminar flow in practical cells even at low Re. The HWTE is compared to the channel electrode in the light of the experimental results, theoretical limits of electron-transfer rate detectable, and conclusions drawn that the channel electrode is more reliable for kinetic measurements.

Item Type: Article
Divisions : Surrey research (other units)
Authors :
Rees, NV
Coles, BA
Compton, RG
Date : 11 December 2003
Depositing User : Symplectic Elements
Date Deposited : 17 May 2017 13:57
Last Modified : 25 Jan 2020 00:33

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