High purity cellulose pulp was obtained from Eucalyptus globulus wood by using an environmentally friendly delignification technique (Milox pulping) and subsequent bleaching by totally chlorine free technology. The pulp obtained under optimised experimental conditions was used for the manufacture of carboxymethylcellulose in a heterogeneous medium. By means of an experimental design. the effects of selected operational variables on the composition and chemical properties of reaction products from the carboxymethylation reaction were assessed for optimisation purposes. The distribution of the different carboxymethylglucose mole fractions (un-, mono-, di- and tri-substituted) was determined and compared with theoretical predictions. The maximum average degree of substitution (1.26) was determined at a NaOH/cellulose mole ratio of 4.8 and at a MCA/cellulose mole ratio of 2.0. (C) 2003 Elsevier Science Ltd. All rights reserved.