Simulations, based on the backward implicit method, for the square wave vol
tammetry (SWV) experiment are reported for the general case of quasi-revers
ible Butler-Volmer kinetics and a finite diffusion layer thickness. In the
limiting cases of fast electrode kinetics, or semi-infinite diffusion, the
results are in excellent agreement with independent calculations confirming
the validity of the approach and its implementation. Under the previously
unexplored conditions of finite diffusion, the effect of the diffusion laye
r thickness on the peak characteristics-width, height, and voltage-are iden
tified and quantified, so providing a quantitative basis for the use of SWV
at hydrodynamic electrodes for the determination of electrochemical kineti
c parameters.