화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.111, No.24, 6761-6765, 2007
Dimensional analysis of chronoamperometry: Proof and verification of Cottrellian behavior of systems with composition-dependent diffusion coefficients
Chronoamperometry with a Dirichlet boundary condition and semi-infinite linear diffusion exhibits Cottrellian behavior, that is, the product it(1/2) is constant as a function of time as long as the system is initially homogeneous, a conclusion that can be reached using only dimensional analysis; no detailed mathematical analysis is required. The generality of this result is known to include purely diffusional systems and systems in which transport also involves migration. In the present work, it is shown that Cottrellian behavior obtains, even when the system diffusion coefficients are a function of system composition, regardless of the exact form of that function. These conclusions are confirmed by simulations of examples for purely diffusional systems as well as for systems with migration. Some experimental examples from the literature are cited.