The presence of Ca(OH)2 (or free lime) in lime mud can cause many problems in the recovery process of kraft pulp mills. Conventional free lime analyses require extensive laboratory work and give inconsistent results. A systematic study was performed to determine if zeta potential, a quickly measurable dispersion characteristic, can be used to indicate the presence of free lime in the recovery process. Measurements were made on synthetic wet lime mud to simulate samples collected after the white liquor clarifier in pulp mills. The results show that zeta potential increases from negative to positive when the free lime content in the lime mud exceeds a critical threshold. This change from negative to positive zeta potential of the lime mud slurry can be used as a basis for developing an on-line monitoring system that effectively detects free lime in the lime mud in order to avoid problems associated with overliming in the recovery process.