Ternary diffusivities by model-based analysis of Raman spectroscopy measurements

Even though multicomponent mixtures are ubiquitous in mass transfer processes, mutual diffusion data in these systems are scarce. This is due to the fact that established diffusion measurements are laborious. In particular, several experiments are required to determine multicomponent diffusion coefficients at a single composition. In order to overcome these deficiencies, a diffusion experiment employing one‐dimensional Raman spectroscopy is presented. Concentrations of the individual species are resolved with high spatial and temporal resolution during the diffusion process. In this work, it is shown that these data allow determining the ternary Fick diffusion matrix from a single isothermal diffusion experiment. The experimental procedure is further optimized using model‐based experimental design techniques, where general design guidelines for diffusion experiments are derived. Thereby, precision of the diffusion measurements can be improved by an order of magnitude. The theoretical calculations are validated by experimental results for the system n‐propanol + 1‐chlorobutane + n‐heptane. © 2006 American Institute of Chemical Engineers AIChE J, 2006