Brown coals have a considerable number of acidic functional groups of which the main component is carboxyl groups, and the acidity has a wide distribution. In this paper, changes of the acidity distribution were examined by aqueous titration when brown coal was heat-treated to control its acidity distribution. For Loy Yang brown coal from Australia dried at 50 degreesC under vacuum (LY50), the acid dissociation constant, Ka, was distributed over a wide pKa range between 2 and 9. Then, using Gaussian functions, the acidity distribution was divided into four groups, which were characterized by average pKa values: average pKa value of 3.8 (hereafter referred to as Group A), 5.2 (Group B), 6.8 (Group Q, and 8.3 (Group D). Among them, Groups A, B, and C were assigned to carboxyl groups. From the changes of the number of carboxyl groups when brown coal was heat-treated up to 400 degreesC, it was found that the way of decrease was different among these acidic groups. The decrease of the amount of carboxyl groups in Group C was significant, and at 325 degreesC most of them disappeared. On the other hand, the carboxyl groups in Group A remained even at a high temperature of 400 degreesC. We estimated approximately the structures around carboxyl groups for LY50 and their structural changes by heat treatment using the known pKa values for simple carboxylic acids and the pKa values calculated by the MOPAC program for complicated carboxylic acids. (C) 2003 Elsevier Science (USA). All rights reserved.