Ionic association between Cu2+(aq) and SO42- (aq) has been studied in the temperature range (298 to 473) K using a spectrophotometric technique. Experiments were designed to minimize the contribution of other protolytic equilibria in solution. The values of the ionic association equilibrium constant at different temperatures and pressures were fitted to an appropiate equation that allows the calculation of the thermodynamic quantities for states close to the saturation line. Using Bjerrum's model for ionic association evidence for two ion pair populations was obtained. The process of ion pairing is discussed and a possibility to reconcile the continuum model (Bjerrum) with molecular simulation results is suggested. (c) 2004 Elsevier Ltd. All rights reserved.