The intrabead diffusion coefficients of acetophenone and phenethyl alcohol were measured at 30 degrees C in the triphasic immobilized yeast-water-hexane system. Saccharomyces cerevisiae cells were deactivated with hydrochloric acid and entrapped in calcium-alginate beads. Measurements of dry cell loss during deactivation, shrinkage of the beads during deactivation and the final porosity of the beads were made for various cell loadings. Final concentrations of wet cells in the beads ranged from approximately 0.25 to 0.30 g/mL. Mass transfer in the hexane phase, external to the beads, was eliminated experimentally. The estimated error of 5% to 10% in the diffusion coefficients is within the experimental error associated with the bead method. The effect of significant sampling volumes on the diffusivities was estimated theoretically and accounted for experimentally. The intrabead concentration of acetophenone and phenethyl alcohol was 150 to 800 ppm. The deactivated cells were shown to be impervious to acetophenone so that the measured diffusivities are extracellular parameters. The cell volume fraction in the beads ranged from 0.70 to 0.90, significantly higher than previously reported data. The effective diffusion coefficients conform to the random pore model. No diffusional interaction between acetophenone and phenethyl alcohol was observed. The addition of 2 vol% ethanol or methanol slightly increased the diffusivities. The thermodynamic partition coefficients were measured in the bead-free water-organic system and found to be an order of magnitude lower than the values calculated from the analysis of the diffusion data for the organic-bead system, suggesting that bead-free equilibrium data cannot be used in triphasic systems.