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Abstract Dual‐porosity models are often used to describe solute transport in heterogeneous media, but the parameters within these models (e.g., immobile porosity and mobile/immobile exchange rate coefficients) are difficult to identify experimentally or relate to measurable quantities. Here, we performed synthetic, pore‐scale millifluidics simulations that coupled fluid flow, solute transport, and electrical resistivity (ER). A conductive‐tracer test and the associated geoelectrical signatures were simulated for four flow rates in two distinct pore‐scale model scenarios: one with intergranular porosity, and a second with an intragranular porosity also defined. With these models, we explore how the effective characteristic‐length scale estimated from a best‐fit dual‐domain mass transfer (DDMT) model compares to geometric aspects of the flow field. In both model scenarios we find that: (1) mobile domains and immobile domains develop even in a system that is explicitly defined with one domain; (2) the ratio of immobile to mobile porosity is larger at faster flow rates as is the mass‐transfer rate; and (3) a comparison of length scales associated with the mass‐transfer rate (L_α) and those associated with calculation of the Peclet number (L_Pe) showL_Peis commonly larger thanL_α. These results suggest that estimated immobile porosities from a DDMT model are not only a function of physically mobile or immobile pore space, but also are a function of the average linear pore‐water velocity and physical obstructions to flow, which can drive the development of immobile porosity even in single‐porosity domains.