Computational Electrochemistry:  The Simulation of Voltammetry under Hydrodynamic Modulation Control

• Published in: The journal of physical chemistry. B 2002-10, Vol.106 (41), p.10668-10673
• Main Authors: Gooch, Kerry A, Fisher, Adrian C
• Format: Article
• Language: English
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp020603s

A conceptually simple and numerically efficient approach to the simulation of current/time transients under hydrodynamically modulated conditions is presented. The generality of the method is illustrated by reference to the case of hydrodynamic modulated voltammetry (HMV) within a channel cell device under pressure driven flow control. For the preliminary studies reported here, modulation refers to a stepped change in the pressure between two limits. This change occurs either instantaneously or linearly over a normalized time. The voltammetric response of a simple redox reaction is used to illustrate the predicted influence of the modulation rate on the current flowing within the flow cell. A normalization procedure is proposed to simplify data presentation and shown to be valid for a wide range of experimentally viable conditions. The simulations are also employed to assess how the current response is influenced by the form of the pressure change between two limits. Simulations are presented for cases where an instantaneous pressure change is employed and compared to results where a linear variation in the pressure is used.