The mechanisms of adsorption and association for sodium carboxymethylcellulose (NaCMC) in calcium carbonate suspensions have been determined from isothermal calorimetry and adsorption measurements. The equilibrium adsorption isotherms were determined by two different methods of separation; a depletion method and a serum exchange method. The enthalpy of dilution for NaCMC was determined on supernatants obtained from the calcium carbonate suspensions in order to investigate the interaction between NaCMC and dissolved species from the mineral. For comparison, NaCMC was injected into CaCl(2) solutions in order to determine the role of calcium ions in the adsorption process. The initial part of the adsorption isotherm showed a quasi-infinite slope indicating a high affinity for the NaCMC to the calcium carbonate surface, which was significantly reduced when anionic sodium polyacrylate was preadsorbed onto the calcium carbonate implying competitive adsorption. An endothermic enthalpy change was observed between the NaCMC and the calcium carbonate surface, suggesting attachment of the carboxylic acid groups onto the hydrated calcium sites. A similar endothermic enthalpy was observed when NaCMC was injected into CaCl(2) solutions or supernatants obtained from the calcium carbonate suspensions, indicating a complexation of carboxylic acid groups and hydrated calcium ions. It was concluded that the mechanisms of interaction of NaCMC in calcium carbonate suspensions are primarily an association between NaCMC and Lewis acid sites on the calcium carbonate surface and the formation of NaCMC-Ca(2+) complexes in the bulk solution, both of which will be affected by the amount of anionic sodium polyacrylate present.