화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.107, No.49, 13649-13660, 2003
Hydrodynamics and mass transport in wall-tube and microjet electrodes: An experimental evaluation of current theory
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 mum 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 cm(3) 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 x 10(-3) cm(2) 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.