Abstract

An analytical expression is presented for the magnetic force generated during steady-state voltammetry at a hemispherical microelectrode immersed in a uniform magnetic field. Diffusion of electrogenerated ions through the magnetic field results in a magnetic force that induces convective solution flow near the electrode surface. The magnetic force per unit volume,[Formula: see text] (i.e., force density), is shown to decrease as r(-)(2), where r is the distance away from the center of the hemispherical electrode. A consequence of the inverse square dependence of[Formula: see text] on r is that the magnetic force is confined to a microscopic solution volume near the electrode surface (e.g., ∼2 × 10(-)(9) L for a 12.5-μm-radius hemispherical electrode). The net magnetic force acting on the diffusion layer volume,[Formula: see text] , is computed as a function of magnetic field strength and orientation and used in an approximate analysis of experimental data obtained at an inlaid 12.5-μm-radius Pt microdisk electrode. Enhancements in voltammetric currents are shown to result from magnetic forces as small as 2 × 10(-)(11) N.

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