AbstractIt is well known that chlorhexidine digluconate provides an effective microbicidal activity during oral rinsing, and therefore, it was considered worthwhile to investigate its interaction with hydroxyapatite on a fundamental level. The kinetics of uptake (or reaction) of the compound from aqueous solutions by synthetic hydroxyapatite was studied at 23°C for four time periods by monitoring its concentration. There was no uptake at low concentrations for any time period. The uptake curves for higher concentrations shifted towards the lower concentrations as the period increased and became more and more vertically oriented to the concentration axis. The concentrations of calcium ions increased, phosphate ions decreased and hydrogen ions decreased a little for a given period as the concentration of the compound was increased. All of these experimental facts can be qualitatively explained on the basis of the solubility considerations of hydroxyapatite and of chlorhexidine phosphate, the reaction product that slowly precipitates out of the solution. The needle‐shaped birefringent crystals of the phosphate salt are clearly visible in the apatite matrix under a microscope, and its refractive index and differential Fourier transform infrared spectra match almost exactly with those of a well‐characterized, synthesized phosphate salt. To explore the nature of interaction, the uptake of chlorhexidine base was studied from p‐dioxane and it is irreversible. The uptake is total below a threshold equilibrium concentration and constant above it. © 1994 John Wiley & Sons, Inc.