This paper presents an approach to the identification of time-varying, nonlinear pH processes based on the Wiener model structure. The algorithm produces an on-line estimate of the titration curve, where the shape of this static nonlinearity changes as a result of changes in the weak-species concentration and/or composition of the process feed stream. The identification method is based on the recursive least-squares algorithm, a frequency sampling filter model of the linear dynamics and a polynomial representation of the inverse static nonlinearity. A sinusoidal signal for the control reagent flow rate is used to generate the input-output data along with a method for automatically adjusting the input mean level to ensure that the titration curve is identified in the pH operating region of interest. Experimental results obtained from a pH process are presented to illustrate the performance of the proposed approach. An application of these results to a pH control problem is outlined. (c) 2004 Elsevier Ltd. All rights reserved.