For a well-engineered compacted clay landfill liner, diffusive transport through the liner is the main mass transport mechanism from the landfill. Therefore, accurate estimates of diffusion coefficients for clay liners are essential for the engineering design of liner systems. A long-standing problem has been the effect of ion pairing on the estimation of diffusion coefficients for multicomponent ionic solutions migrating through clay liners. This paper considers the solution of a fully coupled set of transport equations describing the simultaneous diffusion of several ion species through a clayey soil. The analysis takes into account the diffusion coefficient for each ion species, ion pairing (as required by electroneutrality of the solution), and time-dependent first-order ion and (or) ligand exchange reactions with the clay particles. The behaviour of a double-reservoir diffusion cell, often employed for the estimation of diffusion coefficients in the laboratory, is analyzed using the coupled transport model. A detailed theoretical analysis is made of sodium fluoride transport through saturated kaolinitic clay.