G Puerta-Falla, M Balonis, G Falzone, M Bauchy, N Neithalath, G Sant
Industrial & Engineering Chemistry Research
Publication year: 2016

This study reveals ion exchange kinetics in hydrated calcium-alumino layered double hydroxides of the AFm (alumino-ferrite monosubstituent) sub-group. By careful analysis of solution phase (ion) concentrations and solid phases, the rate of exchange of NO3 for Cl ions from the interlayer positions is studied across a range of temperature, solution compositions, and solution conditions (i.e., static and convectively mixed). Ion exchange kinetics conform to an exponential first order reaction that follows an Arrhenius formalism. The activation energy of ion exchange is 38.2 ± 4.6 kJ/mol for exchange occurring in the thermodynamically preferred (i.e., NO3 for Cl ion exchange) direction and it is 1.8x higher, for the inverse less-preferred pathway. For ion exchange occurring in the favored direction NO3-AFm converts to Cl-AFm; whereas in the disfavored direction the compositional change occurs in two-steps with the formation of a Cl-NO3-AFm solid-solution as an intermediate step; before Cl species are exhausted and NO3-AFm forms as the product. By comparison of ion exchange rates in static and mixed solutions, transport through the Nernst diffusion layer (NDL) is identified as the rate-limiting step in ion exchange kinetics.